WO2010016358A1 - 無電解めっきにより銅薄膜を形成しためっき物 - Google Patents
無電解めっきにより銅薄膜を形成しためっき物 Download PDFInfo
- Publication number
- WO2010016358A1 WO2010016358A1 PCT/JP2009/062662 JP2009062662W WO2010016358A1 WO 2010016358 A1 WO2010016358 A1 WO 2010016358A1 JP 2009062662 W JP2009062662 W JP 2009062662W WO 2010016358 A1 WO2010016358 A1 WO 2010016358A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- thin film
- metal
- plating
- electroless
- Prior art date
Links
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 147
- 239000010949 copper Substances 0.000 title claims abstract description 147
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000010409 thin film Substances 0.000 title claims abstract description 72
- 238000007772 electroless plating Methods 0.000 title claims abstract description 25
- 238000007747 plating Methods 0.000 claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000010408 film Substances 0.000 claims abstract description 34
- 230000004888 barrier function Effects 0.000 claims abstract description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009792 diffusion process Methods 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- 238000006073 displacement reaction Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 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
- 230000008021 deposition Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- 239000011800 void material 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
- 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
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- -1 tetramethyl hydroxide Chemical compound 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
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-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
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- 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
-
- 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
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
- C23C18/31—Coating with metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—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
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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
- H01L21/70—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
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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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
- H01L21/70—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
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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
- H01L21/70—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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/1284—W-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12847—Cr-base component
- Y10T428/12854—Next to Co-, Fe-, or Ni-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
Definitions
- the present invention relates to a plated product in which a copper thin film is formed by electroless plating.
- the present invention relates to a plated product in which a copper thin film is formed by electroless plating as a seed layer in forming ULSI ultrafine copper wiring (damascene copper wiring).
- the electroless copper plating method is expected to replace the current sputtering method and electrolytic copper plating method.
- electroless copper plating is performed on a mirror surface such as a semiconductor wafer, it has been difficult to obtain sufficient adhesion to the deposited plating film. Moreover, the reactivity of plating was low, and it was difficult to perform uniform plating over the entire surface of the substrate.
- a copper seed layer is formed on a barrier metal layer such as tantalum nitride by an electroless plating method, there is a problem that it is difficult to form a uniform plating and adhesion is not sufficient.
- the present inventors have already added a water-soluble nitrogen-containing polymer having a small weight average molecular weight (Mw) as an additive to the electroless copper plating solution, while attaching a catalytic metal to the substrate of the object to be plated before dipping the plating solution.
- Mw weight average molecular weight
- the inventors previously deposited the catalyst metal on the outermost surface, and then immersed in a plating solution to adsorb the polymer via the nitrogen atom on the catalyst metal, It has been shown that the deposition rate of plating is suppressed, and the crystal is very fine so that a uniform thin film having a thickness of 6 nm or less can be formed on a mirror surface such as a wafer.
- a barrier layer for preventing copper diffusion is previously formed separately from the catalyst metal layer. Therefore, before the copper seed layer is formed, two layers of the barrier layer and the catalytic metal layer are formed. The problem was found to be difficult to apply.
- film formation uniformity and adhesion when a seed layer is formed by electroless copper plating are compared with the case where electroless copper plating is performed on a single metal such as tungsten or molybdenum. Further improved, and further eliminating the complexity of the two layers prior to the formation of the copper seed layer, the formation of a thin and uniform film thickness of the seed layer capable of forming ultrafine wiring The purpose is to provide.
- the present inventors have found that in the electroless copper plating solution, copper ions contained in the electroless copper plating solution can be replaced with metal B having a barrier property against copper, and the pH is 10 or more.
- metal B having a barrier property against copper
- the pH is 10 or more.
- the present invention is as follows. (1) On the substrate, copper ions contained in the electroless copper plating solution can be replaced with metal B having a barrier property against copper, and an ionization tendency in an electroless copper plating solution having a pH of 10 or more.
- a barrier alloy thin film for preventing copper diffusion composed of metal A smaller than metal B, and the barrier alloy thin film for preventing copper diffusion is composed of the metal A in an amount of 15 atomic% to 35 atomic%,
- a plated product comprising a copper thin film formed thereon by electroless plating using an electroless copper plating solution having a pH of 10 or more.
- the metal B capable of displacement plating with copper ions contained in the electroless copper plating solution and having a barrier property against copper.
- the barrier metal thin film for preventing copper diffusion having a specific composition is formed from the metal A whose ionization tendency is smaller than that of the metal B, and the copper thin film is formed thereon by electroless plating using an electroless copper plating solution having a pH of 10 or more.
- the interface between the copper diffusion preventing barrier alloy thin film and the electroless copper plating layer thereon can be substantially free of oxygen, and the resistance of the copper thin film can be lowered.
- the alloy thin film can form a copper seed layer having excellent film forming uniformity and adhesion by electroless copper plating without providing a catalytic metal layer thereon, in damascene copper wiring formation, The complexity of forming the two layers of the barrier layer and the catalytic metal layer can be eliminated, and the film can be made thinner.
- a metal B capable of displacement plating with a copper ion contained in an electroless copper plating solution and having a barrier property against copper, and an ionization in an electroless copper plating solution having a pH of 10 or more.
- a barrier alloy thin film for preventing copper diffusion having a specific composition is formed of metal A having a tendency smaller than that of metal B, and a copper thin film is formed thereon by electroless plating using an electroless copper plating solution having a pH of 10 or more.
- Examples of the metal B that can be substituted with copper ions contained in the electroless copper plating solution and have a barrier property against copper include tungsten and molybdenum, and any one of these metals is used. Is preferred.
- the metal A having a smaller ionization tendency in an electroless copper plating solution having a pH of 10 or higher than that of tungsten or molybdenum includes nickel, cobalt, tin, magnesium, aluminum, zinc, and the like. Nickel, cobalt, and tin are preferable, and nickel and cobalt are more preferable. Nickel and cobalt have a relatively high melting point, can be alloyed with tungsten and molybdenum and powder materials, and are useful as gate electrode materials.
- substitution plating of tungsten or molybdenum and copper is started first, but the substitution reaction occurs on the entire surface because the initiation of substitution is uneven.
- the reduction reaction proceeds on the copper previously deposited by substitution, and the reduced plating film also covers portions where substitution plating has not occurred.
- the reduced plating film is formed on the substitutional unreacted portion, it is considered that the adhesion is deteriorated because a gap is left between them.
- electroless copper plating is performed using an electroless copper plating solution having a pH of 10 or more thereon, so that substitution plating of the metal B and copper is likely to occur.
- metal B has a higher ionization tendency than metal A, and local battery corrosion occurs. Dissolution of metal B progresses, and as a result, substitution reaction proceeds and substitution unreacted parts decrease, adhesion and uniform film formation. It is thought that the property improves.
- the composition ratio of metal A is preferably 15 atomic% or more and 35 atomic% or less, and more preferably 25 atomic% or less.
- the metal A is less than 15 atomic%, the substitutional unreacted portion increases as described above, the copper deposition becomes nonuniform, and the adhesion of the copper film decreases. On the other hand, if it exceeds 35 atomic%, the metal A diffuses into the copper film and the resistance increases.
- the said alloy thin film can be formed by the well-known method of forming a thin film, using the sputtering alloy target containing the said metal A and the metal B, it is preferable to form by sputtering on a base material.
- the alloy thin film having the above composition can be formed by a sputtering target containing a metal A and a metal B having substantially the same composition as that of the desired alloy thin film.
- the thickness of the alloy thin film is preferably 3 to 20 nm, more preferably 5 to 15 nm.
- the substrate for forming the alloy thin film in the present invention is preferably a semiconductor wafer, and the substrate is cleaned, wetted by performing acid treatment, alkali treatment, surfactant treatment, ultrasonic cleaning or a combination thereof. It is possible to improve the performance.
- the copper thin film formed by electroless copper plating is initially deposited as a metal by the substitution reaction of copper ions and metal B contained in the electroless copper plating solution at the beginning of the reaction. Formed.
- the copper thin film is formed by displacement plating at the initial stage of the reaction, whereby the oxide on the surface of the alloy thin film is removed in the process of displacement plating.
- AES Auger electron spectroscopy
- the copper thin film can have a thickness of 10 nm or less and a resistivity of 10 ⁇ ⁇ cm or less.
- the thickness of the seed layer By reducing the thickness of the seed layer, application to damascene copper wiring having a line width of several tens of nanometers becomes possible.
- a general method can be used as the electroless copper plating method used when performing electroless copper plating using the barrier alloy thin film for preventing copper diffusion in the present invention.
- a general electroless copper plating solution having a pH of 10 or more can be used as the 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.
- glyoxylic acid As 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.
- 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. When the concentration is less than 0.005 mol / L, the plating reaction does not occur, and when it exceeds 0.5 mol / L, the plating solution becomes unstable and decomposes.
- 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.
- the concentration of the copper ion source in the electroless copper plating solution is preferably 0.005 to 0.1 mol / L.
- a complexing agent of copper ions all commonly used complexing agents can be used, and examples thereof include ethylenediaminetetraacetic acid and tartaric acid.
- the concentration of the complexing agent in the electroless copper plating solution is preferably 0.02 to 0.5 mol / L.
- 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 thin film as described above.
- the thickness of the copper thin film produced by electroless plating of the present invention is more preferably 3 to 10 nm.
- the copper thin film produced by electroless plating of 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 100 nm or less, resulting in the generation of defects such as voids and seams. A semiconductor wafer is obtained.
- a wiring portion can be further provided by plating on a copper thin film formed by electroless plating.
- electroplating or electroless plating can be used.
- 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.
- 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 plated product of the present invention has the specific alloy thin film formed on a substrate, and has a copper thin film acting as a seed layer formed by electroless plating thereon.
- a copper seed layer having good film forming uniformity and adhesion can be provided thereon by electroless copper plating.
- a single layer having a function can be formed, and it is not necessary to form two layers of a catalytic metal layer and a barrier layer having a thickness of several tens of nanometers.
- a specific alloy thin film can be used for electroless plating and a single layer having a barrier function, and the film thickness of the copper thin film acting as the seed layer Can be made to be 10 nm or less, so that a metal element to be a wiring part is formed on this copper thin film by a conventional method, so that a semiconductor element that can be applied to a damascene copper wiring with a line width of several tens of nm is obtained. be able to.
- the resistivity of the copper thin film acting as the seed layer can be set to 10 ⁇ ⁇ cm or less, and subsequent uniform film formation at the initial stage of electroplating is facilitated.
- Example 1 As a metal B capable of displacement plating with copper ions contained in the electroless copper plating solution on the semiconductor substrate and having a barrier property against copper, the ionization tendency in the electroless copper plating solution having a pH of 10 or more is metal.
- An alloy thin film having a thickness of 10 nm was prepared using a sputtering alloy target made of nickel as metal A smaller than B, and a copper plating thin film was formed on the alloy film by an electroless plating method.
- Table 1 shows the composition of the alloy thin film formed using the sputtering alloy target and the film thickness of the copper plating thin film formed by electroless plating.
- the formation of the copper film by electroless plating was carried out using a plating solution having the following composition under the conditions of pH 12.5 (adjusting agent: potassium hydroxide) and 50 ° C. ⁇ 30 to 40 seconds.
- Plating solution composition Copper sulfate 0.02 mol / L Ethylenediaminetetraacetate 0.21 mol / L Glyoxylic acid 0.03 mol / L 2,2'-bipyridyl 20mg / L
- the adhesion of the plated thin film was 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 adhesion of the copper-plated thin film was confirmed by performing a tape peeling test using a cellophane tape (CT24, manufactured by Nichiban). .
- CT24 cellophane tape
- the evaluation was as follows: ⁇ : no plating film peeling, x: plating film peeling.
- Table 1 The results are summarized in Table 1.
- the sputtered alloy thin film and electroless copper plating thin film were formed on a semiconductor substrate with a trench pattern having a line width of 90 nm and an aspect ratio of 4, and then wiring was embedded by electrolytic copper plating using the sputtered alloy thin film and electroless copper plating thin film as a seed layer. .
- the wiring was embedded by electroplating using a plating solution having the following composition at 25 ° C. for 60 seconds and a current density of 1 A / dm 2 .
- Example 2 to 3 Comparative Examples 1 to 3 An alloy thin film was prepared in the same manner as in Example 1 except that the composition of the alloy thin film in Example 1 was changed as shown in Table 1, and electroless plating was performed for evaluation. The results are shown in Table 1.
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Abstract
Description
特にULSI超微細銅配線(ダマシン銅配線)を形成する際のシード層として、無電解めっきにより銅薄膜を形成しためっき物に関する。
従来、半導体ウェハーのような鏡面上に無電解銅めっきを行った場合、析出しためっき膜に十分な密着性を得るのは困難であった。また、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も困難であった。従来は、例えば、窒化タンタルなどのバリアメタル層上に無電解めっき法で銅シード層を形成する場合、めっきを均一に形成することが難しく密着力が十分でないという問題があった。また、バリアメタル層として、タングステンやモリブデンなどの金属単体上に無電解めっき法で銅シード層を形成する場合も、めっきを均一に形成することが難しく密着力が十分でないという問題があった。従って、窒化タンタルなどのバリアメタル層上に無電解めっき法で銅シード層を均一に形成するためには、めっき前に触媒付与工程が必要であった。
(1)基材上に、無電解銅めっき液に含まれる銅イオンと置換めっきが可能でかつ銅に対してバリア性を持つ金属Bと、pH10以上の無電解銅めっき液中でのイオン化傾向が金属Bより小さな金属Aからなる銅拡散防止用バリア合金薄膜が形成され、該銅拡散防止用バリア合金薄膜が、前記金属Aを15原子%以上、35原子%以下とする組成であり、その上にpH10以上の無電解銅めっき液を用いた無電解めっきにより銅薄膜が形成されたことを特徴とするめっき物。
(2)前記金属Bが、タングステンまたはモリブデンであり、前記金属Aが、ニッケル、コバルト、スズから選ばれる少なくとも1種の金属であることを特徴とする前記(1)記載のめっき物。
(3)前記無電解めっきにより形成された銅薄膜が膜厚10nm以下で、抵抗率10μΩ・cm以下であることを特徴とする前記(1)又は(2)記載のめっき物。
さらに、前記合金薄膜は、その上に触媒金属層を設けなくても、無電解銅めっきにより成膜均一性、密着性に優れる銅シード層の形成が可能であるので、ダマシン銅配線形成における、バリア層と触媒金属層との二層を形成する煩雑さを解消でき、さらに薄膜化が可能となる。
合金薄膜の膜厚は3~20nmであることが好ましく、より好ましくは5~15nmである。
本発明において、反応初期に置換めっきにより、銅薄膜が形成されることにより、前記合金薄膜の表面の酸化物が置換めっきの過程で除かれる。また上記の作用により、前記合金薄膜と銅薄膜との界面の酸素濃度をオージェ電子分光法(AES)にて分析したところ1原子%以下(検出限界以下)とすることができる。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。
また、その結果、銅薄膜の厚みを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、線幅が数十nmレベルのダマシン銅配線への適用が可能となる。
無電解銅めっき液は、通常、銅イオン、銅イオンの錯化剤、還元剤、およびpH調整剤等を含んでいる。
グリオキシル酸の濃度は、めっき液中0.005~0.5mol/Lが好ましく、0.01~0.2mol/Lがより好ましい。濃度が0.005mol/L未満であるとめっき反応が起こらず、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。
本発明の無電解めっきにより作製した銅薄膜の厚さは、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。
実施例1
半導体基板上に、無電解銅めっき液に含まれる銅イオンと置換めっきが可能でかつ銅に対してバリア性を持つ金属Bとしてタングステン、pH10以上の無電解銅めっき液中でのイオン化傾向が金属Bより小さな金属Aとしてニッケルからなるスパッタリング合金ターゲットを用いて膜厚10nmの合金薄膜を作製し、その合金膜上に無電解めっき法により銅めっき薄膜を形成した。前記スパッタリング合金ターゲットを用いて形成されたこの合金薄膜の組成、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。
尚、無電解めっきによる銅膜の形成は、以下の組成のめっき液を用いて、pH12.5(調整剤:水酸化カリウム)、50℃×30~40秒の条件で実施した。
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
2、2’-ビピリジル 20mg/L
なお、電気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)
得られた銅めっき膜の断面TEM観察により、線幅90nmトレンチ部の埋め込み性を評価した。ボイド・シームの有無を判定し、○:ボイド・シーム無、×:ボイド・シーム有とした。
結果を表1に示す。
実施例1における合金薄膜の組成を表1記載のように変えた以外は実施例1と同様にして合金薄膜を作製し、無電解めっきを行い、評価した。
結果を表1に示す。
Claims (3)
- 基材上に、無電解銅めっき液に含まれる銅イオンと置換めっきが可能でかつ銅に対してバリア性を持つ金属Bと、pH10以上の無電解銅めっき液中でのイオン化傾向が金属Bより小さな金属Aからなる銅拡散防止用バリア合金薄膜が形成され、該銅拡散防止用バリア合金薄膜が、前記金属Aを15原子%以上、35原子%以下とする組成であり、その上にpH10以上の無電解銅めっき液を用いた無電解めっきにより銅薄膜が形成されたことを特徴とするめっき物。
- 前記金属Bが、タングステンまたはモリブデンであり、前記金属Aが、ニッケル、コバルト、スズから選ばれる少なくとも1種の金属であることを特徴とする請求項1記載のめっき物。
- 前記無電解めっきにより形成された銅薄膜が膜厚10nm以下で、抵抗率10μΩ・cm以下であることを特徴とする請求項1又は2記載のめっき物。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US12/737,399 US8283051B2 (en) | 2008-08-07 | 2009-07-13 | Plated product having copper thin film formed thereon by electroless plating |
EP09804845A EP2309025B1 (en) | 2008-08-07 | 2009-07-13 | Plated object with copper thin film formed by electroless plating |
JP2010523812A JP5300156B2 (ja) | 2008-08-07 | 2009-07-13 | 無電解めっきにより銅薄膜を形成しためっき物 |
CN2009801303460A CN102112660B (zh) | 2008-08-07 | 2009-07-13 | 通过非电解镀形成铜薄膜的镀件 |
KR1020117005170A KR101254407B1 (ko) | 2008-08-07 | 2009-07-13 | 무전해도금에 의해 구리 박막을 형성한 도금물 |
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JP2008-203930 | 2008-08-07 | ||
JP2008203930 | 2008-08-07 |
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WO2010016358A1 true WO2010016358A1 (ja) | 2010-02-11 |
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PCT/JP2009/062662 WO2010016358A1 (ja) | 2008-08-07 | 2009-07-13 | 無電解めっきにより銅薄膜を形成しためっき物 |
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US (1) | US8283051B2 (ja) |
EP (1) | EP2309025B1 (ja) |
JP (1) | JP5300156B2 (ja) |
KR (1) | KR101254407B1 (ja) |
CN (1) | CN102112660B (ja) |
TW (1) | TWI390080B (ja) |
WO (1) | WO2010016358A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010275572A (ja) * | 2009-05-26 | 2010-12-09 | Jx Nippon Mining & Metals Corp | 貫通シリコンビアを有するめっき物及びその形成方法 |
JP2013038393A (ja) * | 2011-07-13 | 2013-02-21 | Hitachi Metals Ltd | 電子部品用積層配線膜 |
JP2015193909A (ja) * | 2014-03-25 | 2015-11-05 | Jx日鉱日石金属株式会社 | スパッタリングターゲット及びその製造方法並びにスパッタリング法で形成した膜 |
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---|---|---|---|---|
JP6497391B2 (ja) * | 2014-07-31 | 2019-04-10 | 住友金属鉱山株式会社 | タッチパネル用導電性基板、タッチパネル用導電性基板の製造方法 |
US10508351B2 (en) * | 2017-03-16 | 2019-12-17 | Lam Research Corporation | Layer-by-layer deposition using hydrogen |
JP2019169579A (ja) | 2018-03-23 | 2019-10-03 | 株式会社東芝 | 半導体装置及びその製造方法 |
JP6754151B1 (ja) * | 2020-02-18 | 2020-09-09 | 日本高純度化学株式会社 | めっき積層体 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002275639A (ja) * | 2000-10-25 | 2002-09-25 | Shipley Co Llc | シード層堆積 |
JP2002302773A (ja) * | 2001-04-06 | 2002-10-18 | Sony Corp | 無電解メッキ装置およびその方法 |
WO2005038086A1 (ja) | 2003-10-17 | 2005-04-28 | Nikko Materials Co., Ltd. | 無電解銅めっき液 |
JP2008223100A (ja) | 2007-03-14 | 2008-09-25 | Nikko Kinzoku Kk | ダマシン銅配線用シード層形成方法、及びこの方法を用いてダマシン銅配線を形成した半導体ウェハー |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4080513A (en) * | 1975-11-03 | 1978-03-21 | Metropolitan Circuits Incorporated Of California | Molded circuit board substrate |
US5882498A (en) * | 1997-10-16 | 1999-03-16 | Advanced Micro Devices, Inc. | Method for reducing oxidation of electroplating chamber contacts and improving uniform electroplating of a substrate |
JP3979791B2 (ja) * | 2000-03-08 | 2007-09-19 | 株式会社ルネサステクノロジ | 半導体装置およびその製造方法 |
US6416812B1 (en) * | 2000-06-29 | 2002-07-09 | International Business Machines Corporation | Method for depositing copper onto a barrier layer |
US6824665B2 (en) * | 2000-10-25 | 2004-11-30 | Shipley Company, L.L.C. | Seed layer deposition |
-
2009
- 2009-07-13 KR KR1020117005170A patent/KR101254407B1/ko active IP Right Grant
- 2009-07-13 JP JP2010523812A patent/JP5300156B2/ja active Active
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002275639A (ja) * | 2000-10-25 | 2002-09-25 | Shipley Co Llc | シード層堆積 |
JP2002302773A (ja) * | 2001-04-06 | 2002-10-18 | Sony Corp | 無電解メッキ装置およびその方法 |
WO2005038086A1 (ja) | 2003-10-17 | 2005-04-28 | Nikko Materials Co., Ltd. | 無電解銅めっき液 |
JP2008223100A (ja) | 2007-03-14 | 2008-09-25 | Nikko Kinzoku Kk | ダマシン銅配線用シード層形成方法、及びこの方法を用いてダマシン銅配線を形成した半導体ウェハー |
Non-Patent Citations (1)
Title |
---|
See also references of EP2309025A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010275572A (ja) * | 2009-05-26 | 2010-12-09 | Jx Nippon Mining & Metals Corp | 貫通シリコンビアを有するめっき物及びその形成方法 |
JP2013038393A (ja) * | 2011-07-13 | 2013-02-21 | Hitachi Metals Ltd | 電子部品用積層配線膜 |
JP2015193909A (ja) * | 2014-03-25 | 2015-11-05 | Jx日鉱日石金属株式会社 | スパッタリングターゲット及びその製造方法並びにスパッタリング法で形成した膜 |
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TWI390080B (zh) | 2013-03-21 |
US20110129688A1 (en) | 2011-06-02 |
TW201012967A (en) | 2010-04-01 |
KR101254407B1 (ko) | 2013-04-15 |
EP2309025A4 (en) | 2011-09-21 |
EP2309025B1 (en) | 2012-09-26 |
EP2309025A1 (en) | 2011-04-13 |
KR20110038731A (ko) | 2011-04-14 |
CN102112660B (zh) | 2013-07-10 |
US8283051B2 (en) | 2012-10-09 |
JP5300156B2 (ja) | 2013-09-25 |
CN102112660A (zh) | 2011-06-29 |
JPWO2010016358A1 (ja) | 2012-01-19 |
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