JP5268160B2 - 基板、及びその製造方法 - Google Patents
基板、及びその製造方法 Download PDFInfo
- Publication number
- JP5268160B2 JP5268160B2 JP2009546201A JP2009546201A JP5268160B2 JP 5268160 B2 JP5268160 B2 JP 5268160B2 JP 2009546201 A JP2009546201 A JP 2009546201A JP 2009546201 A JP2009546201 A JP 2009546201A JP 5268160 B2 JP5268160 B2 JP 5268160B2
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- JP
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- Prior art keywords
- copper
- plating
- film
- electroless
- barrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000758 substrate Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 122
- 229910052802 copper Inorganic materials 0.000 claims description 122
- 239000010949 copper Substances 0.000 claims description 122
- 230000004888 barrier function Effects 0.000 claims description 87
- 238000007747 plating Methods 0.000 claims description 87
- 229910052751 metal Inorganic materials 0.000 claims description 64
- 239000002184 metal Substances 0.000 claims description 50
- 239000010410 layer Substances 0.000 claims description 41
- 238000009792 diffusion process Methods 0.000 claims description 40
- 230000003197 catalytic effect Effects 0.000 claims description 38
- 229910052721 tungsten Inorganic materials 0.000 claims description 34
- 239000010937 tungsten Substances 0.000 claims description 34
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- 238000007772 electroless plating Methods 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- 239000011733 molybdenum Substances 0.000 claims description 25
- 229910052758 niobium Inorganic materials 0.000 claims description 25
- 239000010955 niobium Substances 0.000 claims description 25
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000004544 sputter deposition Methods 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 230000002265 prevention Effects 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 26
- 239000010409 thin film Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- -1 tungsten nitride Chemical class 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000010438 heat treatment 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
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 4
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base 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
- 238000005259 measurement Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005477 sputtering target Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000929 Ru alloy Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 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
- 239000008139 complexing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 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
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 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 1
- 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 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
- 238000010306 acid treatment Methods 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
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 238000000137 annealing 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
- 239000000306 component Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation 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
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002755 poly(epichlorohydrin) Chemical group 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 230000009257 reactivity Effects 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
- 230000003595 spectral effect Effects 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
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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 System
- H01L21/2855—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 System by physical means, e.g. sputtering, evaporation
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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
-
- 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
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
- H01L2221/1068—Formation and after-treatment of conductors
- H01L2221/1073—Barrier, adhesion or liner layers
- H01L2221/1084—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L2221/1089—Stacks of seed 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
Description
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。
さらに、高温加熱時におけるバリア性に優れ、長時間使用した場合においても信頼性が高い半導体ウェハーを提供することを目的とする。
(1) 基材上に、バリア機能と触媒能とを兼ね備えた単一の層からなるバリア膜を有する基板であって、該バリア膜がタングステン、モリブデン及びニオブから選択した1種以上の金属元素を60〜75原子%含有し、無電解めっきに対する触媒能を有するルテニウム、ロジウム、及びイリジウムから選択した1種以上の金属元素を10〜30原子%含有し、残余が、前記タングステン、モリブデン及びニオブから選択した1種以上の金属元素との窒化物の形態で少なくとも3原子%以上含有される窒素からなる銅拡散防止用バリア膜であることを特徴とする基板。
(2)前記銅拡散防止用バリア膜上に、前記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)に記載の基板。
(3)前記銅拡散防止用バリア膜上に、前記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備え、さらに該銅シード層上に形成されたダマシン銅配線を有することを特徴とする前記(1)または(2)に記載の基板。
(4)前記(3)に記載の基板を用いた半導体ウェハー。
(5)基材上に、タングステン、モリブデン及びニオブから選択した1種以上の金属元素と、無電解めっきに対する触媒能を有するルテニウム、ロジウム、及びイリジウムから選択した1種以上の金属元素とを含有するターゲットを用いて、窒素雰囲気中でスパッタリングし、銅拡散防止用バリア膜を形成することを特徴とする前記(1)に記載の基板の製造方法。
(6)前記銅拡散防止用バリア膜上に、前記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銅シード層を形成することを特徴とする前記(5)記載の基板の製造方法。
(7)前記銅拡散防止用バリア膜上に、前記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銅シード層を形成し、さらに該銅シード層上にダマシン銅配線を形成することを特徴とする前記(5)または(6)に記載の基板の製造方法。
窒素雰囲気中でスパッタリングを行う際に、タングステン、モリブデン、またはニオブの成膜速度のみが遅くなっていき、ルテニウム等の触媒能を有する金属の基板への成膜速度は遅くならず、相対的に触媒能を有する金属の膜中比率が上がっていくことから、窒素がタングステン、モリブデン、またはニオブの窒化物の形態として含有されていると判断できる。
バリア機能を有するタングステン、モリブデン、ニオブが窒化される事により、バリア機能が高くなる。窒化物とすることにより高温加熱時のバリア性が400℃から500℃まで向上する。
本発明の銅拡散防止バリア膜を用いて無電解置換および還元めっきを行う際に用いる無電解銅めっき方法としては、一般的な方法を用いることができる。同様に使用する銅めっき液も一般的なめっき液を用いることができる。
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、無電解銅めっき液は、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ことが好ましい。
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銅薄膜の厚さは、1〜10nm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、ダマシン銅配線がより好ましい。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、第三アルキルアミンおよびポリエピクロルヒドリンからなる第四アンモニウム塩付加物(第四エピクロルヒドリン)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WO2005−038086号公報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。
様々な組成比のタングステンとルテニウムのスパッタリング合金ターゲットを用いて、スパッタ時のチャンバー内のアルゴン・窒素ガス圧比を変化させて、最表面にSiO2膜のついたシリコン基板上に、膜厚10nmの窒化タングステン・ルテニウム合金膜を作製し、その上に無電解銅めっき膜を膜厚5〜8nmで成膜した。
スパッタ成膜には3インチRFスパッタ装置(ANELVA製SPF−332HS)を使用した。窒化タングステン・ルテニウム合金膜の作製は、チャンバー内をクライオポンプで5×10-5Paとした後、ある一定比率の窒素・アルゴン混合ガスを全圧0.8Paとなるまで導入し、50Wの出力でプラズマを発生させ、15分間のプレスパッタ後、本成膜を実施した。
(無電解めっき液とめっき条件)
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
pH12.5(水酸化テトラメチルアンモニウム)
500℃×30分間の真空アニール処理後のバリア性を、AESデプスプロファイル測定により確認した。銅の窒化タングステン・ルテニウム合金膜中への拡散、あるいはその逆の現象がいずれも見られないものを「○」とし、いずれか一方の現象でも見られるものは「×」とした。
なお、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。
様々な組成比のモリブデンとロジウムのスパッタリング合金ターゲットを用いて、スパッタ時のチャンバー内のアルゴン・窒素ガス圧比を変化させて、最表面にSiO2膜のついたシリコン基板上に、膜厚10nmの窒化モリブデン・ロジウム合金膜を作製し、その上に無電解銅めっき膜を膜厚5〜8nmで成膜した。スパッタ成膜、無電解めっきの条件は実施例1と同様である。
また、バリア性、めっき膜均一性、耐酸化性、めっき膜密着性、埋め込み性、及び総合評価を実施例1と同様の方法で評価した。
この結果を表2にまとめた。
様々な組成比のニオブとイリジウムのスパッタリング合金ターゲットを用いて、スパッタ時のチャンバー内のアルゴン・窒素ガス圧比を変化させて、最表面にSiO2膜のついたシリコン基板上に、膜厚10nmの窒化ニオブ・イリジウム合金膜を作製し、その上に無電解銅めっき膜を膜厚5〜8nmで成膜した。銅スパッタ成膜、無電解めっきの条件は実施例1と同様である。
また、バリア性、めっき膜均一性、耐酸化性、めっき膜密着性、埋め込み性、及び総合評価を実施例1と同様の方法で評価した。
この結果を表3にまとめた。
Claims (7)
- 基材上に、バリア機能と触媒能とを兼ね備えた単一の層からなるバリア膜を有する基板であって、該バリア膜がタングステン、モリブデン及びニオブから選択した1種以上の金属元素を60〜75原子%含有し、無電解めっきに対する触媒能を有するルテニウム、ロジウム、及びイリジウムから選択した1種以上の金属元素を10〜30原子%含有し、残余が、前記タングステン、モリブデン及びニオブから選択した1種以上の金属元素との窒化物の形態で少なくとも3原子%以上含有される窒素からなる銅拡散防止用バリア膜であることを特徴とする基板。
- 前記銅拡散防止用バリア膜上に、前記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に記載の基板。
- 前記銅拡散防止用バリア膜上に、前記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備え、さらに該銅シード層上に形成されたダマシン銅配線を有することを特徴とする請求項1または2に記載の基板。
- 請求項3に記載の基板を用いた半導体ウェハー。
- 基材上に、タングステン、モリブデン及びニオブから選択した1種以上の金属元素と、無電解めっきに対する触媒能を有するルテニウム、ロジウム、及びイリジウムから選択した1種以上の金属元素とを含有するターゲットを用いて、窒素雰囲気中でスパッタリングし、銅拡散防止用バリア膜を形成することを特徴とする請求項1記載の基板の製造方法。
- 前記銅拡散防止用バリア膜上に、前記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銅シード層を形成することを特徴とする請求項5に記載の基板の製造方法。
- 前記銅拡散防止用バリア膜上に、前記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銅シード層を形成し、さらに該銅シード層上にダマシン銅配線を形成することを特徴とする請求項5または6に記載の基板の製造方法。
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