WO2010087392A1 - バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を有する基板 - Google Patents
バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を有する基板 Download PDFInfo
- Publication number
- WO2010087392A1 WO2010087392A1 PCT/JP2010/051103 JP2010051103W WO2010087392A1 WO 2010087392 A1 WO2010087392 A1 WO 2010087392A1 JP 2010051103 W JP2010051103 W JP 2010051103W WO 2010087392 A1 WO2010087392 A1 WO 2010087392A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal element
- film
- alloy film
- copper
- plating
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 85
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 68
- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 230000004888 barrier function Effects 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000007772 electroless plating Methods 0.000 claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 33
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- 239000010937 tungsten Substances 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 17
- 239000010955 niobium Substances 0.000 claims abstract description 17
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 238000007747 plating Methods 0.000 claims description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 74
- 229910052802 copper Inorganic materials 0.000 claims description 74
- 239000010949 copper Substances 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 abstract description 109
- 239000010409 thin film Substances 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 29
- 238000006467 substitution reaction Methods 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 229910000929 Ru alloy Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- -1 copper Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- VZCCTDLWCKUBGD-UHFFFAOYSA-N 8-[[4-(dimethylamino)phenyl]diazenyl]-10-phenylphenazin-10-ium-2-amine;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(N=C2C(C=C(N)C=C2)=[N+]2C=3C=CC=CC=3)C2=C1 VZCCTDLWCKUBGD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- FNYLUKDQSKKYHG-UHFFFAOYSA-N [Ru].[W] Chemical compound [Ru].[W] FNYLUKDQSKKYHG-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- OUFGXIPMNQFUES-UHFFFAOYSA-N molybdenum ruthenium Chemical compound [Mo].[Ru] OUFGXIPMNQFUES-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ATLAQRSQSGOMOU-UHFFFAOYSA-N niobium platinum Chemical compound [Nb].[Pt] ATLAQRSQSGOMOU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ZONODCCBXBRQEZ-UHFFFAOYSA-N platinum tungsten Chemical compound [W].[Pt] ZONODCCBXBRQEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
-
- 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
- C23C16/06—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 metallic material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a substrate in which an alloy film of a metal element having a barrier function and a metal element having a catalytic function is formed on a base material.
- an alloy film of a metal element having a barrier function and a metal element having a catalytic ability is used as a catalyst layer for forming a seed layer by electroless plating when forming ULSI ultrafine copper wiring (damascene copper wiring). It relates to the formed substrate.
- ULSI ultrafine copper wiring As a method for forming ULSI ultrafine copper wiring (damascene copper wiring), a method is known in which a copper seed layer is provided by electroless plating and copper is formed by electrolytic copper plating.
- electroless copper plating is performed on a mirror surface such as a semiconductor wafer, the reactivity of plating is low, and it is difficult to perform uniform plating over the entire surface of the substrate. Therefore, for example, a catalytic metal layer is provided on a barrier metal layer such as tantalum nitride, and then a copper seed layer is formed by an electroless plating method.
- Patent Document 1 describes using a molybdenum-tungsten alloy film as a barrier layer of a metal electrode.
- a molybdenum-tungsten alloy film as the barrier layer, it is possible to prevent a rise in resistance during a high-temperature process and to form a necessary circuit by dry etching.
- Both molybdenum and tungsten are metals having a barrier function, and are different from the catalyst layer for forming the seed layer by electroless plating.
- Patent Document 2 describes that ruthenium on a substrate (Si and SiO 2 ) exhibits excellent barrier properties. It has also been pointed out that this ruthenium layer is considered promising in that copper can be disposed by direct plating without providing a PVD copper seed layer thereon. However, at the same time, it has been pointed out that this ruthenium layer has an unacceptably poor bond strength with the substrate. This document describes the development of a ruthenium alloy that can be used for vapor deposition and atomic layer volume (ALD) in order to solve this problem. What has been studied in detail and specifically disclosed relates to a laminate material comprising a ruthenium layer.
- ALD atomic layer volume
- a ruthenium-based material or a ruthenium-based alloy is specifically proposed as a barrier structure that solves this problem and has a good barrier strength and can be electrochemically plated with copper.
- at least one layer containing at least one element from Group IV, Group V, Group VI of the periodic table, or a combination thereof, specifically TiZr / Ru. , TiZrN / Ru, and TaN / Ru, and a ruthenium layer is used as the layer containing the ruthenium-based material or ruthenium-based alloy.
- the specific description of the ruthenium alloy is merely a description (paragraph 0017) as a component constituting the sputtering target.
- the present invention eliminates the complexity of forming these two layers prior to the formation of the copper seed layer, and provides a layer having a catalytic function and a barrier function that are excellent in coverage with a very thin film and film formation uniformity.
- a pretreatment technology that can form a seed layer with a thin and uniform film thickness that enables ultra-fine wiring to be formed. Using this, a thin and uniform film thickness is formed by electroless plating. It is an object to provide a substrate including a seed layer and a method for manufacturing the substrate.
- the present inventors have found that a chemical vapor deposition (CVD) method is used to form an alloy film made of a metal element having a barrier function such as tungsten and a metal element having a catalytic ability for electroless plating such as ruthenium.
- CVD chemical vapor deposition
- the present inventors have found that a layer having a catalytic function and a barrier function excellent in coverage and film formation uniformity can be obtained even at a film thickness of 0.5 to 5 nm. That is, the present invention is as follows.
- the alloy film is formed to a thickness of 0.5 to 5 nm using a chemical vapor deposition (CVD) method so that the metal element having the barrier function is 5 atomic% to 90 atomic%.
- a substrate characterized by that.
- An alloy film with a metal element is formed by using a chemical vapor deposition (CVD) method so that the metal element having the barrier function is 5 atomic% or more and 90 atomic% or less with a film thickness of 0.5 to 5 nm.
- CVD chemical vapor deposition
- the alloy film is formed to a thickness of 0.5 to 5 nm using a chemical vapor deposition (CVD) method with a composition in which the metal element having the barrier function is 5 atomic% to 90 atomic%.
- CVD chemical vapor deposition
- the alloy film has a single function having both a barrier function and a catalytic function.
- the coverage and uniformity of the ultrathin film with a film thickness of 0.5 to 5 nm can be determined by physical vapor deposition such as vacuum evaporation or sputtering. This can be improved as compared with the case where the film is formed by the (PVD) method, and a finer and lower electric resistance value can be formed.
- the substrate of the present invention has a metal element having one or more barrier functions selected from tungsten, molybdenum, and niobium in advance on the base material, ruthenium, and An alloy film with a metal element having catalytic ability for electroless plating made of platinum is formed by using a chemical vapor deposition (CVD) method so that the metal element having the barrier function is 5 atomic% or more and 90 atomic% or less. And having a film thickness of 0.5 to 5 nm.
- CVD chemical vapor deposition
- Ruthenium and platinum have a catalytic ability for a reaction to reduce a metal ion such as copper in the electroless plating solution to form a plating film.
- Tungsten, molybdenum, and niobium are metals having a barrier function with respect to metals such as copper, and one or more metal elements having a barrier function selected from tungsten, molybdenum, and niobium, ruthenium, and
- tungsten, molybdenum, and niobium can be replaced with metal ions contained in the electroless plating solution.
- Electroless plating when forming a seed layer by electroless plating on the alloy film is electroless replacement. And it becomes reduction plating, and the film thickness can be uniformly reduced.
- the composition in the alloy film of one or more metal elements having a barrier function selected from tungsten, molybdenum, and niobium and a metal element having catalytic ability for electroless plating composed of ruthenium and / or platinum is as follows:
- the composition ratio of the metal element having a barrier function is 5 atom% or more and 90 atom% or less, and preferably 5 atom% or more and 80 atom% or less. More preferably, it is 20 atom% or more and 80 atom% or less, and particularly preferably 50 atom% or more and 80 atom% or less.
- the substitution reaction becomes more dominant than the reduction reaction of the plating solution, the material to be plated cannot be eroded and a uniform thin film cannot be formed, and the adhesion is deteriorated. Further, since the film is non-uniform, holes are formed on the surface of the electroless plating film, or an extremely thin part is formed, resulting in a decrease in barrier function. In addition, a certain amount of time is required for the catalytic reaction to start deposition.
- the substitution reaction starts relatively quickly, the substitution at the initial stage of plating can be performed by setting the metal element having a barrier function to 50 atomic% or more. The rate of reaction increases, and the film thickness reproducibility and uniformity of the resulting plating film can be increased. Moreover, when the ratio of the metal element having a barrier function is increased, the cost is significantly reduced.
- Ruthenium has poor adhesion to the base material layer (Si, SiO 2 ), and if the ruthenium layer is provided directly on the base material, the ruthenium layer is easily peeled off, which causes a problem, but the ruthenium alloy film having the above composition ratio. By doing so, the adhesion between the base material and the alloy thin film is improved, and there is no problem.
- a tungsten-ruthenium alloy film As a preferable alloy film of an alloy film of a metal element having a barrier function and a metal element having a catalytic function, a tungsten-ruthenium alloy film, a molybdenum-ruthenium alloy film, a tungsten-platinum alloy film, a niobium-platinum alloy film, and the like can be given. It is done.
- the alloy film is formed on a substrate using a CVD method.
- the CVD method By using the CVD method, the coverage and uniformity of film formation with an ultra-thin film with a thickness of 0.5 to 5 nm can be improved compared to the case where the film is formed by a physical vapor deposition (PVD) method such as vacuum deposition or sputtering. It is possible to improve, and it is possible to form a finer semiconductor wiring having a low electric resistance value.
- PVD physical vapor deposition
- a known method for forming the alloy film by the CVD method can be used as a known method for forming the alloy film by the CVD method can be used.
- ruthenium (II) or the like tris (acetylacetonato) ruthenium (II) or the like is used as the ruthenium source, tungsten fluoride or the like is used as the tungsten source, and vaporization is performed in an inert gas such as argon to form a tungsten-ruthenium alloy film.
- Niobium pentachloride (NbCl 5 ) or the like can be used as the niobium source
- molybdenum pentachloride (MoCl 5 ) or the like can be used as the molybdenum source
- (PtCl 2 ) 2 (CO) 3 or the like can be used as the platinum source.
- an alloy film can be formed.
- an alloy film having a desired composition can be obtained by adjusting the amount of the metal element source having catalytic ability to be introduced and the amount of the metal element source having a barrier function.
- the film thickness of the alloy film is preferably 0.5 to 5 nm, more preferably 1 to 3 nm.
- the thickness of the alloy film exceeds 5 nm, in a fine damascene wiring having a line width of 50 nm or less, the remaining space becomes small, the wiring becomes thin, and the resistance of the wiring increases.
- a metal thin film (seed layer) formed by electroless substitution and reduction plating is a substitution reaction between metal ions contained in the electroless plating solution and a metal element having a barrier function such as tungsten,
- a metal element having catalytic ability such as ruthenium acts as a catalyst for reducing metal ions in the electroless plating solution, so that metal ions contained in the electroless plating solution are deposited and formed as a metal.
- the metal thin film include a thin film made of at least one metal selected from gold, silver, copper, nickel, cobalt, iron, and tin. Copper or a thin film of an alloy containing copper as a main component is preferable. Is particularly preferred.
- substitution plating removes oxides on the surface of the alloy film in the course of substitution plating, and at the same time, reduction plating occurs to form a film necessary for forming a seed layer having desired conductivity.
- the thickness can be reduced uniformly.
- the seed layer can have a thickness of 10 nm or less and a resistivity of 10 ⁇ ⁇ cm or less. By reducing the film thickness of the seed layer, it can be applied to damascene copper wiring having a line width of 50 nm or less.
- the oxygen concentration at the interface between the alloy film and a metal thin film formed by electroless substitution and reduction plating such as copper was analyzed by Auger electron spectroscopy (AES). Below the limit).
- AES Auger electron spectroscopy
- the base material for forming the alloy film in the present invention a semiconductor substrate such as a silicon wafer is preferable, and the base material is obtained by performing an acid treatment, an alkali treatment, a surfactant treatment, an ultrasonic cleaning, or a combination thereof. Cleaning and wettability can be improved.
- a general method can be used as the electroless plating method used when performing electroless substitution and reduction plating using the alloy film of the present invention.
- a general plating solution can be used as the plating solution.
- Electroless plating is preferably electroless copper plating.
- Metal elements having catalytic ability such as ruthenium have catalytic activity for electroless copper plating, and metal elements having a barrier function such as tungsten can be replaced with copper ions contained in the electroless copper plating solution.
- the electroless copper plating solution usually contains copper ions, a complexing agent of copper ions, a reducing agent, a pH adjusting agent, and the like.
- the reducing agent for the electroless copper plating solution it is preferable to use glyoxylic acid in view of the adverse effects of formalin on the human body and the environment.
- phosphinic acid does not show a reducing action on copper, it shows a high reducing action on a catalytic metal such as ruthenium, so that it has an effect of increasing the initial plating reactivity via the catalytic metal. They do not contain sodium, which is an impurity that should be avoided in semiconductor applications.
- glyoxylic acid and phosphinic acid at the same time as the reducing agent.
- This combination makes plating more reactive than when glyoxylic acid is used alone, and as a result, electroless plating is possible at lower temperatures on a mirror surface such as a semiconductor wafer where plating reaction is unlikely to occur.
- a copper plating solution is obtained. High plating reactivity enables plating at a lower temperature, and further lower temperature increases the liquid stability, and the precipitated copper particles tend to be fine and uniform.
- the concentration of glyoxylic acid is preferably 0.005 to 0.5 mol / L, more preferably 0.01 to 0.2 mol / L in the plating solution.
- concentration of phosphinic acid is preferably 0.001 to 0.5 mol / L, more preferably 0.005 to 0.2 mol / L in the plating solution.
- the copper ion source of the electroless copper plating solution all commonly used copper ion sources can be used, and examples thereof include copper sulfate, copper chloride, and copper nitrate.
- a complexing agent of copper ions all commonly used complexing agents can be used, and examples thereof include ethylenediaminetetraacetic acid and tartaric acid.
- additives generally used in plating solutions such as 2,2′-bipyridyl, polyethylene glycol, potassium ferrocyanide and the like can be used.
- the electroless copper plating solution in the present invention is preferably used at a pH of 10 to 14, more preferably at a pH of 12 to 13.
- the pH adjuster commonly used ones such as sodium hydroxide and potassium hydroxide can be used. However, when it is desired to avoid alkali metals such as sodium and potassium in semiconductor applications, tetramethyl hydroxide is used. Ammonium may be used.
- the electroless copper plating solution in the present invention is preferably used at a bath temperature of 40 to 90 ° C. from the viewpoint of bath stability and copper deposition rate.
- the material to be plated when plating is performed using an electroless copper plating solution, the material to be plated is immersed in a plating bath.
- the material to be plated is obtained by forming the alloy film.
- the thickness of the metal thin film prepared by electroless substitution and reduction plating according to the present invention is more preferably 3 to 10 nm.
- the metal thin film produced by electroless substitution and reduction plating according to the present invention has a thin plating film and a uniform film thickness. Therefore, when used as a seed layer for damascene copper wiring, it is possible to form a thin film seed layer with a uniform film thickness even in fine vias and trenches with a wiring width of 50 nm or less, resulting in defects such as voids and seams. A semiconductor wafer in which no occurrence occurs is obtained.
- substrate of this invention can provide a wiring part by plating further on the metal thin film formed by electroless plating.
- electroplating or electroless plating can be used. If a wiring part is provided directly on the alloy film without providing a metal thin film by electroless plating, defects such as voids are likely to occur due to the effect of electricity being difficult to flow, so it is necessary to provide a wiring part on the metal thin film.
- the wiring portion is preferably copper or an alloy containing copper as a main component, and more preferably copper.
- the electrolytic copper plating solution is not particularly limited as long as it is a composition generally used for embedding damascene copper wiring.
- copper sulfate and sulfuric acid as main components chlorine, polyethylene glycol, bis (2 disulfide) (3 -Sulfopropyl) Liquid containing disodium, Janus green, etc. can be used.
- an electroless copper plating solution used for embedding for example, a plating solution for embedding copper wiring described in International Publication No. 2005/038086 pamphlet can be used.
- the substrate of the present invention has a specific alloy film formed on a base material, and a metal thin film acting as a seed layer formed by electroless substitution and reduction plating thereon.
- the specific alloy film is a single layer having both catalytic ability and barrier function, it is not necessary to form a barrier layer having a thickness of several tens of nanometers.
- the alloy film can be formed into a single layer having both a barrier function and a catalytic function, and can be thinned. Further, the alloy film can be formed by a CVD method so as to have a film thickness of 0.5 to 5 nm excellent in coverage and film formation uniformity, and can be further reduced in thickness.
- the thickness of the metal thin film acting as the seed layer can be reduced to 10 nm or less, and metal plating to be a wiring portion is formed on this metal thin film by a conventional method.
- a semiconductor element that can be applied to a damascene copper wiring having a line width of 50 nm or less can be obtained.
- the resistivity of the metal thin film acting as the seed layer can be 10 ⁇ ⁇ cm or less, uniform film formation at the initial stage of electroplating thereafter becomes easy.
- Examples 1-6 On the Si wafer, an alloy film having a thickness of 2 nm having a composition shown in Table 1 was produced by a CVD method, and a copper plating thin film was formed on the alloy film by an electroless plating method. Table 1 shows the composition of the formed alloy film and the film thickness of the copper plating thin film formed by electroless plating.
- the W—Ru alloy films of Examples 1 to 3 use tris (acetylacetonato) ruthenium (II) (hereinafter Ru (acac) 3 ) as the ruthenium source and tungsten fluoride (hereinafter Ru (acac) 3 ). Thereafter, WF 6 ) was used.
- Ru (acac) 3 was vaporized by heating to 150 to 180 ° C. under an argon atmosphere, and then introduced into the reaction chamber via a mass flow controller. WF 6 was also introduced into the reaction chamber via a mass flow controller.
- a Si wafer serving as a base material for forming an alloy film was fixed in the reaction chamber, and kept at 600 ° C. by a high-frequency heater.
- the reaction chamber was maintained at 10 ⁇ 5 Pa using a turbo molecular pump until just before the introduction of the raw material gas, and the exhaust was terminated simultaneously with the introduction of the raw material gas.
- a W-Ru alloy film having a desired composition was obtained by changing the amount of each introduced Ru (acac) 3 and WF 6 by a mass flow controller.
- Example 4 to 6 the above compound was used as the ruthenium source and the tungsten source, niobium pentachloride (NbCl 5 ) as the niobium source, molybdenum pentachloride (MoCl 5 ) as the molybdenum source, and platinum source.
- (PtCl 2 ) 2 (CO) 3 was used to form an alloy film by the CVD method in the same manner as in Example 1 so as to obtain an alloy film having the composition shown in Table 1.
- the film thickness and composition of the obtained alloy film were determined. The film thickness was confirmed by cross-sectional TEM observation.
- the composition was determined by AES depth profile measurement.
- Electroless copper plating solution composition Copper sulfate 0.02 mol / L Ethylenediaminetetraacetate 0.21 mol / L Glyoxylic acid 0.03 mol / L Phosphinic acid 0.09 mol / L 2,2'-bipyridyl 20mg / L pH 12.5 (adjusted with potassium hydroxide)
- the thickness of the obtained copper plating thin film, the presence or absence of holes having a hole diameter of 10 nm or more, the resistivity, the presence or absence of copper diffusion into the alloy film, and the state of the interface between the copper film and the alloy film during plating were evaluated.
- the film thickness was confirmed by cross-sectional TEM observation.
- the presence or absence of holes was confirmed by surface SEM observation.
- the resistivity was calculated from the sheet resistance measurement by the four-end needle method and the film thickness measurement result by cross-sectional TEM observation.
- the presence or absence of copper diffusion and the oxidation state of the interface were determined by AES depth profile measurement. The results are summarized in Table 1.
- the CVD alloy film and the electroless copper plating thin film were formed on a semiconductor substrate with a trench pattern having a line width of 45 nm and an aspect ratio of 4, and then wiring was embedded by electrolytic copper plating using the film as a seed layer. .
- the wiring was embedded by electrolytic copper plating at 25 ° C. for 60 seconds and a current density of 1 A / dm 2 using a plating solution having the following composition. Copper sulfate 0.25 mol / L Sulfuric acid 1.8 mol / L Hydrochloric acid 10mmol / L Trace additive (polyethylene glycol, disodium bis (3-sulfopropyl) disulfide, Janus green)
- the adhesiveness of the plating film was evaluated by a tape peeling test after electrolytic copper plating.
- a cellophane tape (CT-24, manufactured by Nichiban) was brought into close contact with the plating surface by the belly of the finger, and then the tape was peeled off to confirm the peeling of the plating film, and the following determination was made.
- CT-24 cellophane tape
- ⁇ No peeling of plating film
- ⁇ With peeling of plating film The results are summarized in Table 1.
- Comparative Examples 1 to 4 The manufacturing method of the alloy film in Example 1 was changed to the PVD method, and the electroless film was electrolessly formed in the same manner as in Example 1 except that the alloy film described in Table 1 was formed to have a surface portion film thickness of 2 nm using an alloy target. Copper plating and electrolytic copper plating were performed and evaluated. The results are shown in Table 1.
- Comparative Example 5 An alloy film having a thickness of 2 nm was prepared by the CVD method in the same manner as in Example 1 except that the composition of the alloy film in Example 1 was changed to the composition described in Table 1, and electroless copper plating was performed in the same manner as in Example 1. Electro copper plating was performed and evaluated. The results are shown in Table 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Electrodes Of Semiconductors (AREA)
- Chemically Coating (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
特にULSI超微細銅配線(ダマシン銅配線)を形成する際の、無電解めっきによりシード層を形成するための触媒層として、バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を形成した基板に関する。
半導体ウェハのような鏡面上に無電解銅めっきを行う場合、めっきの反応性が低く、基板全面に均一なめっきを行うことは困難である。従って、例えば、窒化タンタルなどのバリアメタル層上に触媒金属層を設け、次に無電解めっき法で銅シード層を形成することが行われている。
即ち、本発明は以下のとおりである。
(2)基材上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、ルテニウムからなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜したことを特徴とする前記(1)記載の基板。
(3)基材上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、プラチナまたはプラチナとルテニウムの両方からなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜したことを特徴とする前記(1)記載の基板。
(4)上記合金膜を膜厚1~3nmに成膜したことを特徴とする前記(1)~(3)のいずれか一項に記載の基板。
(5)上記合金膜がバリア機能を有する金属元素を5原子%以上80原子%以下とする組成であることを特徴とする前記(1)~(4)のいずれか一項に記載の基板。
(6)上記合金膜上に、触媒能を有する金属元素を触媒として無電解銅めっきにより形成された銅シード層を有することを特徴とする前記(1)~(5)のいずれか一項に記載の基板。
(7)上記銅シード層上にさらにダマシン銅配線を形成したことを特徴とする前記(6)記載の基板。
(8)基板上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、ルテニウム及び/又はプラチナからなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜することを特徴とする前記(1)~(7)のいずれか一項に記載の基板の製造方法。
(9)前記(7)に記載の基板を用いたことを特徴とする半導体ウェハ。
CVD法で前記合金膜を形成する方法としては、合金膜をCVD法で形成する公知の方法を用いることができる。例えば、ルテニウム源としてトリス(アセチルアセトナト)ルテニウム(II)等を用い、タングステン源としてフッ化タングステン等を用い、アルゴン等の不活性ガス中で気化させ、タングステン-ルテニウム合金膜を形成することができる。また、ニオブ源としては五塩化ニオブ(NbCl5)等を、モリブデン源としては五塩化モリブデン(MoCl5)等を、プラチナ源としては (PtCl2)2(CO)3 等を用いることができ、同様に合金膜を形成することができる。
合金膜の組成は、導入する触媒能を有する金属元素源、及びバリア機能を有する金属元素源の量を調整することにより所望の組成の合金膜を得ることができる。
その結果、シード層の厚みを10nm以下でかつ抵抗率10μΩ・cm以下とすることができる。シード層の膜厚を薄くすることにより、線幅50nm以下のダマシン銅配線への適用が可能となる。
界面に酸素が存在する場合には、配線の抵抗が上がったり、バリア機能が落ちる等の悪影響がある。
無電解銅めっき液の還元剤としては、ホルマリンの人体や環境への悪影響を考え、グリオキシル酸を用いることが好ましい。また、ホスフィン酸は銅上では還元作用を示さないものの、ルテニウムなどの触媒金属上では高い還元作用を示すため、触媒金属を介する初期のめっき反応性を高くする効果がある。また、これらは半導体用途では避けたい不純物であるナトリウムを含まない。
ホスフィン酸の濃度は、めっき液中0.001~0.5mol/Lが好ましく、0.005~0.2mol/Lがより好ましい。濃度が0.001mol/L未満であると前記の効果が見られなくなり、0.5mol/Lを超えるとめっき液が不安定になり分解する。
その他の添加剤として、めっき液に一般的に用いられている添加剤、例えば2,2’-ビピリジル、ポリエチレングリコール、フェロシアン化カリウム等を用いることができる。
また、本発明における無電解銅めっき液は、浴温40~90℃で使用するのが、浴安定性および銅の析出速度の点から好ましい。
本発明の無電解置換および還元めっきにより作製した金属薄膜の厚さは、3~10nmがより好ましい。
配線部は銅又は銅を主成分とする合金であることが好ましく、銅がより好ましい。電気銅めっき液は、一般にダマシン銅配線埋め込み用に使用されている組成であればよく、特に限定されないが、例えば主成分として硫酸銅及び硫酸、微量成分として塩素、ポリエチレングリコール、二硫化ビス(3-スルホプロピル)二ナトリウム、ヤヌスグリーンなどを含んだ液を用いることができる。また、埋め込みに使用する無電解銅めっき液としては、例えば国際公開第2005/038086号パンフレットに記載の銅配線埋め込み用めっき液を用いることができる。
また、無電解置換および還元めっきによりシード層を形成するので、シード層として作用する金属薄膜の膜厚を10nm以下とすることができ、この金属薄膜上に常法により配線部となる金属めっきすることにより、線幅が50nm以下のダマシン銅配線への適用が可能な半導体素子とすることができる。加えて、前記シード層として作用する金属薄膜の抵抗率を10μΩ・cm以下とすることができるので、その後の電気めっき初期の均一成膜が容易となる。
Siウェハ上に、表1記載の組成からなる厚さ2nmの合金膜をCVD法によって作製し、その合金膜上に無電解めっき法による銅めっき薄膜を形成した。形成されたこの合金膜の組成、および無電解めっきにより形成された銅めっき薄膜の膜厚を表1に示す。
CVD法の実施にあたって、実施例1~3のW-Ru合金膜は、ルテニウム源としてトリス(アセチルアセトナト)ルテニウム(II)(以後Ru(acac)3)を用い、タングステン源としてフッ化タングステン(以後WF6)を用いた。
Ru(acac)3をアルゴン雰囲気下において150~180℃まで加熱し気化させた後、マスフローコントローラを介し、反応室内に導入した。WF6においてもマスフローコントローラを介し、反応室内に導入した。反応室内に合金膜形成の基材となるSiウェハを固定し、高周波加熱器により600℃に保持した。反応室内は原料ガス導入の直前まで、ターボ分子ポンプを用いて10-5Paに保持し、原料ガス導入と同時に排気を終了した。マスフローコントローラによりRu(acac)3、WF6それぞれの導入量を変化させることで所望の組成のW-Ru合金膜を得た。
得られた合金膜の膜厚および組成を求めた。膜厚は断面TEM観察により確認した。組成はAESデプスプロファイル測定により求めた。
無電解銅めっき液組成
硫酸銅 0.02mol/L
エチレンジアミン四酢酸塩 0.21mol/L
グリオキシル酸 0.03mol/L
ホスフィン酸 0.09mol/L
2、2’-ビピリジル 20mg/L
pH12.5(水酸化カリウムで調整)
得られた銅めっき薄膜の膜厚、穴径10nm以上の孔の有無、抵抗率、合金膜中への銅の拡散の有無、めっき時の銅膜と合金膜の界面の状態について評価した。膜厚は断面TEM観察により確認した。孔の有無は、表面SEM観察により確認した。抵抗率は、四端針法によるシート抵抗測定、および断面TEM観察による膜厚測定結果より算出した。銅の拡散の有無および界面の酸化状態は、AESデプスプロファイル測定により判定した。結果を表1にまとめた。
なお、電気銅めっきによる配線の埋め込みは、以下の組成のめっき液を用いて25℃×60秒、電流密度1A/dm2で実施した。
硫酸銅 0.25mol/L
硫酸 1.8mol/L
塩酸 10mmol/L
微量添加剤(ポリエチレングリコール、二硫化ビス(3-スルホプロピル)二ナトリウム、ヤヌスグリーン)
○:ボイド・シーム無
×:ボイド・シーム有
とした。
○:めっき膜の剥離なし
×:めっき膜の剥離あり
結果を表1にまとめた。
実施例1における合金膜の製造方法を、PVD法に変え、合金ターゲットを用い表1記載の合金膜を表面部膜厚が2nmになるように成膜した以外は実施例1同様にして無電解銅めっき、電気銅めっきを行い、評価した。
結果を表1に示す。
実施例1における合金膜の組成を表1記載の組成に変えた以外は実施例1と同様にして厚さ2nmの合金膜をCVD法によって作製し、実施例1同様にして無電解銅めっき、電気銅めっきを行い、評価した。
結果を表1に示す。
Claims (9)
- 基材上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、ルテニウム及び/又はプラチナからなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜したことを特徴とする基板。
- 基材上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、ルテニウムからなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜したことを特徴とする請求項1記載の基板。
- 基材上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、プラチナまたはプラチナとルテニウムの両方からなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜したことを特徴とする請求項1記載の基板。
- 上記合金膜を膜厚1~3nmに成膜したことを特徴とする請求項1~3のいずれか一項に記載の基板。
- 上記合金膜がバリア機能を有する金属元素を5原子%以上80原子%以下とする組成であることを特徴とする請求項1~4のいずれか一項に記載の基板。
- 上記合金膜上に、触媒能を有する金属元素を触媒として無電解銅めっきにより形成された銅シード層を有することを特徴とする請求項1~5のいずれか一項に記載の基板。
- 上記銅シード層上にさらにダマシン銅配線を形成したことを特徴とする請求項6記載の基板。
- 基板上に、タングステン、モリブデン、及びニオブから選択される1種又は2種以上のバリア機能を有する金属元素と、ルテニウム及び/又はプラチナからなる無電解めっきに対する触媒能を有する金属元素との合金膜を、化学的気相成長(CVD)法を用いて、前記バリア機能を有する金属元素を5原子%以上90原子%以下とする組成で、膜厚0.5~5nmに成膜することを特徴とする請求項1~5のいずれかに記載の基板の製造方法。
- 請求項7に記載の基板を用いたことを特徴とする半導体ウェハ。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010548545A JP5399421B2 (ja) | 2009-01-30 | 2010-01-28 | バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を有する基板 |
KR1020117017461A KR101277357B1 (ko) | 2009-01-30 | 2010-01-28 | 배리어 기능을 가진 금속 원소와 촉매능을 가진 금속 원소의 합금막을 가진 기판 |
US12/998,802 US8395264B2 (en) | 2009-01-30 | 2010-01-28 | Substrate comprising alloy film of metal element having barrier function and metal element having catalytic power |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009019471 | 2009-01-30 | ||
JP2009-019471 | 2009-01-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010087392A1 true WO2010087392A1 (ja) | 2010-08-05 |
Family
ID=42395650
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/051103 WO2010087392A1 (ja) | 2009-01-30 | 2010-01-28 | バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を有する基板 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8395264B2 (ja) |
JP (1) | JP5399421B2 (ja) |
KR (1) | KR101277357B1 (ja) |
TW (1) | TWI415962B (ja) |
WO (1) | WO2010087392A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000012544A (ja) * | 1998-06-23 | 2000-01-14 | Toshiba Corp | 半導体装置の製造方法 |
JP2000183003A (ja) * | 1998-10-07 | 2000-06-30 | Toshiba Corp | 銅系金属用研磨組成物および半導体装置の製造方法 |
JP2004115885A (ja) * | 2002-09-27 | 2004-04-15 | Tokyo Electron Ltd | 無電解メッキ方法 |
JP2006513325A (ja) * | 2003-01-23 | 2006-04-20 | アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド | 触媒を用いた無電解めっきによりパターン化された絶縁体上に金属層を形成する方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6387800B1 (en) * | 1999-12-20 | 2002-05-14 | Taiwan Semiconductor Manufacturing Company | Method of forming barrier and seed layers for electrochemical deposition of copper |
US6432811B1 (en) * | 2000-12-20 | 2002-08-13 | Intel Corporation | Method of forming structural reinforcement of highly porous low k dielectric films by Cu diffusion barrier structures |
US6472310B1 (en) * | 2002-04-08 | 2002-10-29 | Advanced Micro Devices, Inc. | Tin palladium activation with maximized nuclei density and uniformity on barrier material in interconnect structure |
JP2003309181A (ja) | 2002-04-16 | 2003-10-31 | Mitsubishi Electric Corp | 半導体装置の製造方法及び、キャパシタの製造方法 |
US8404035B2 (en) | 2003-10-17 | 2013-03-26 | Nippon Mining & Metals Co., Ltd. | Electroless copper plating solution |
CN101208444A (zh) | 2005-04-21 | 2008-06-25 | 霍尼韦尔国际公司 | 钌基材料和钌合金 |
US20080124484A1 (en) * | 2006-11-08 | 2008-05-29 | Asm Japan K.K. | Method of forming ru film and metal wiring structure |
JP5142550B2 (ja) * | 2007-02-22 | 2013-02-13 | 株式会社半導体エネルギー研究所 | 半導体装置の作製方法 |
-
2010
- 2010-01-28 KR KR1020117017461A patent/KR101277357B1/ko active IP Right Grant
- 2010-01-28 US US12/998,802 patent/US8395264B2/en active Active
- 2010-01-28 JP JP2010548545A patent/JP5399421B2/ja active Active
- 2010-01-28 WO PCT/JP2010/051103 patent/WO2010087392A1/ja active Application Filing
- 2010-01-29 TW TW099102534A patent/TWI415962B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000012544A (ja) * | 1998-06-23 | 2000-01-14 | Toshiba Corp | 半導体装置の製造方法 |
JP2000183003A (ja) * | 1998-10-07 | 2000-06-30 | Toshiba Corp | 銅系金属用研磨組成物および半導体装置の製造方法 |
JP2004115885A (ja) * | 2002-09-27 | 2004-04-15 | Tokyo Electron Ltd | 無電解メッキ方法 |
JP2006513325A (ja) * | 2003-01-23 | 2006-04-20 | アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド | 触媒を用いた無電解めっきによりパターン化された絶縁体上に金属層を形成する方法 |
Also Published As
Publication number | Publication date |
---|---|
US8395264B2 (en) | 2013-03-12 |
JPWO2010087392A1 (ja) | 2012-08-02 |
KR101277357B1 (ko) | 2013-06-20 |
TWI415962B (zh) | 2013-11-21 |
JP5399421B2 (ja) | 2014-01-29 |
KR20110106905A (ko) | 2011-09-29 |
TW201035357A (en) | 2010-10-01 |
US20110241209A1 (en) | 2011-10-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4376959B2 (ja) | 無電解めっきにより金属薄膜を形成しためっき物およびその製造方法 | |
JP4376958B2 (ja) | 無電解めっきにより金属薄膜を形成しためっき物及びその製造方法 | |
JP2010037622A (ja) | 無電解置換めっきにより銅薄膜を形成しためっき物 | |
JP5300156B2 (ja) | 無電解めっきにより銅薄膜を形成しためっき物 | |
JP5268159B2 (ja) | 基板、及びその製造方法 | |
TWI408749B (zh) | 基板及其製造方法 | |
TWI384605B (zh) | 於基材上形成阻障兼種晶層的電子構件 | |
JP5399421B2 (ja) | バリア機能を有する金属元素と触媒能を有する金属元素との合金膜を有する基板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10735857 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12998802 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2010548545 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20117017461 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10735857 Country of ref document: EP Kind code of ref document: A1 |