CN102471918B - 无电沉积溶液和工艺控制 - Google Patents
无电沉积溶液和工艺控制 Download PDFInfo
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- CN102471918B CN102471918B CN200980160458.0A CN200980160458A CN102471918B CN 102471918 B CN102471918 B CN 102471918B CN 200980160458 A CN200980160458 A CN 200980160458A CN 102471918 B CN102471918 B CN 102471918B
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- liter
- mole
- electroless deposition
- body lotion
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- 230000008021 deposition Effects 0.000 title claims abstract description 156
- 238000004886 process control Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000006210 lotion Substances 0.000 claims description 98
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 70
- 229910017052 cobalt Inorganic materials 0.000 claims description 60
- 239000010941 cobalt Substances 0.000 claims description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 59
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 45
- 239000006227 byproduct Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 31
- 239000000376 reactant Substances 0.000 claims description 28
- 229910052721 tungsten Inorganic materials 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 27
- 239000010937 tungsten Substances 0.000 claims description 27
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 21
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 8
- 238000007772 electroless plating Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- VYVFRCHFRAPULL-UHFFFAOYSA-N [B].[P].[W].[Co] Chemical compound [B].[P].[W].[Co] VYVFRCHFRAPULL-UHFFFAOYSA-N 0.000 claims description 5
- 238000013178 mathematical model Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 17
- 238000000151 deposition Methods 0.000 description 106
- 239000003795 chemical substances by application Substances 0.000 description 22
- 229910021645 metal ion Inorganic materials 0.000 description 18
- 230000002829 reductive effect Effects 0.000 description 17
- 238000012545 processing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- -1 hydrogen cobalt oxide Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGUKXCVHOUQPPA-UHFFFAOYSA-N phosphoric acid tungsten Chemical compound [W].OP(O)(O)=O DGUKXCVHOUQPPA-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02697—Forming conducting materials on a substrate
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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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
- C23C18/1601—Process or apparatus
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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
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
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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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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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
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
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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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—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
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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
- H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
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Abstract
本发明的一个实施方式是制造集成电路的覆盖层无电沉积的方法。该方法包括控制无电沉积浴液组分以便实质上保持浴液的无电沉积属性。本发明的其他实施方式包括无电沉积溶液。本发明的另一实施方式是用于翻新无电沉积浴液的组分。
Description
背景技术
本发明涉及电子设备如集成电路的制造,更具体地,本发明涉及无电电镀液装置的方法和无电电镀液的方法。
工艺控制是制造诸如电子设备之类复杂设备的关键环节。对于如集成电路等设备,其工艺规范和工艺结果必需符合严格的规范,以便确保集成电路所需性能。不仅在获得所需工艺规范和工艺结果存在挑战,保持这些规范和过程以便在优选的经济条件下加工大量基板也是一个挑战。
为了符合电子设备的要求,诸如无电沉积之类工艺已经应用于如沉积铜电介质金属结构的覆盖层。无电沉积过程提供了覆盖层的选择性沉积,如基于钴的覆盖层以及如基于镍的覆盖层。一些更优选的覆盖层是多元素合金如钴合金,钴钨合金,钴钨磷硼合金,钴镍合金,以及镍合金。一些覆盖层所需成分的复杂性需要复杂的化学反应以生产这些层,并且在工艺设备,如无电沉积设备和相关的无电沉积浴液的工艺控制中存在相应的复杂问题。
无电沉积设备成功的工艺控制包括在所需规范内保持无电沉积浴液,以获得所需工艺结果。一般而言,操作无电沉积浴液有一个可接受的规范范围。在无电沉积实行期间保持的重要参数是沉积速率,浴液稳定性,薄膜成分,薄膜覆盖范围,以及薄膜粗糙度。这些参数通常通过控制无电沉积溶液的成分来保持,尤其是通过控制诸如金属离子源,还原剂,以及PH调节剂等反应物的量来保持。当相比于消耗的浴液成分的浓度,沉积溶液中装载的料浓度高时,并且电镀液用于再循环模式或批处理模式中时,副产物的浓度在电镀浴液中快速地增大。无电浴液成分中这种的变化能改变沉积工艺,以及,因此改变沉积速率和薄膜的一些特征属性。
已经有公知的监测和保持无电沉积浴液操作的方法。大多数情况下,除了浴液温度,还监测还原剂浓度,金属离子浓度,以及电镀浴液的PH。为了保持预定工艺窗口中的浴液,如果还原剂浓度,金属离子浓度,和/或PH不在规范内,那么不得不在浴液中加入化学物质。可通过添加所需的PH调节剂,还原剂,和金属离子来保持浴液。除了浓度调整,可以将新鲜的溶液不时地添加到电镀液中,因为当电镀基板从电镀室移出时的带出(drag-out),可能会失去部分溶液。
尽管无电沉积溶液配置(management)的方法和无电沉积溶液是公知的,本发明人认识到需要新的和/或改进的管理无电沉积溶液的方法以及新的和/或改进的覆盖层的无电沉积的无电沉积溶液,该覆盖层用于制造电子设备。
发明内容
本发明涉及加工基板,如用于电子设备制造的基板。本发明的一个方面是加工基板的方法。本发明的一个实施方式是通过无电沉积沉积覆盖层的方法和保持无电沉积浴液的方法。本发明的另一方面包括用于加工基板的溶液和成分。本发明的一实施方式包括用于覆盖层的无电沉积溶液。本发明的另一实施方式是配置为添补用于沉积覆盖层的无电沉积浴液的成分。
应了解,本发明并不局限于详细结构的应用以及下面所描述的成分配置的应用。本发明能用于其他实施方式并且能以不同方式实行和实施。另外,应了解,此处使用的措辞和术语仅是为了描述的目的,不应视为限制。
因此,本领域技术人员应了解,本发明所基于的构思可作为用于实施本发明各方面所设计的其他结构,方法和系统的基础。这一点很重要,所以,权利要求视为包括这种等同的结构范围,因为其没有脱离本发明的精神和范围。
具体实施方式
本发明涉及加工诸如用于电子设备制造的基板之类的基板。本发明实施方式的操作将在下面讨论,主要在加工诸如用于制造集成电路的硅晶片之类的半导体晶片方面。集成电路的金属化层包括形成嵌入式或双嵌入式电介质结构的金属线的铜。可选地,电介质是低k电介质材料,如掺杂氧化硅的碳(SiOC:H)。下面所披露的是针对在铜上包含至少钴的覆盖层的无电沉积的优选工艺和溶液。然而,应了解,根据本发明的实施方式可用于其他半导体设备,铜以外的金属,钴以外的覆盖层,半导体晶片以外的晶片。
下述定义将用于讨论本发明优选的实施方式。副产物是因实施化学反应以在基板上形成覆盖层从而在无电沉积溶液中形成的成分。反应物是在反应形成覆盖层期间消耗的无电沉积溶液中的成分。反应物包括例如,金属离子源和还原剂。补充物是不直接产生副产物的无电沉积溶液中的成分。补充物的示例包括但不局限于,络合剂,稳定剂,表面活性剂及其类似物。添补组分是添加到无电沉积浴液中以保持无电沉积浴液性能符合规范的任一种或一种以上的反应物、任一种或一种以上的副产物、和/或任一种或一种以上的补充物的混合物。
下面给出的是根据本发明优选的实施方式所示的无电沉积溶液。该无电沉积溶液包括反应物,副产物,以及可能包括补充物。在一个实施方式中,无电沉积溶液包括金属离子源,一种或一种以上的还原剂,源自金属离子源和还原剂之间反应的一种或一种以上的副产物,以及可能包括一种或一种以上的PH调节剂,一种或一种以上的络合剂,一种或一种以上的第二元素源,以及如果需要,还包括一种或一种以上的缓冲剂。
金属离子源通常构成覆盖层的最大成分。对于本发明优选的实施方式,该金属离子源是钴或钴合金覆盖层的钴源。该钴源实际上是任何可溶的钴(II)盐。一些示例性的钴盐为硫酸钴和氯化钴。高纯度氢氧化钴(II)的使用更为可取。这种化合物少量可溶于水但是在络合剂或酸存在下易溶解。随着金属氢氧化物取代通用可溶的金属盐的应用,能进一步最小化无电沉积层中的污染水平,该通用可溶的金属盐如金属硫酸盐,金属氯化物盐,或金属硝酸盐。对于本发明的一些实施方式,作为钴的替代,可使用镍源生产基于镍的覆盖层。
还原剂还原溶液中的金属离子以便在基板表面形成覆盖层。优选的还原剂为次磷酸盐,其以如次磷酸,无碱-金属次磷酸盐,以及次磷酸的络合物等化合物的形式引入到浴液中。次磷酸盐也用作沉积层中的磷源。另一使用的还原剂为二甲胺硼烷(DMAB),其也可用作覆盖层的硼源。其他适合用作沉积溶液中的还原剂的硼烷包括但不局限于烷基胺硼烷、二烷基胺硼烷、三烷基胺硼烷。无电沉积溶液中另一可用的还原剂为肼。
一种或一种以上的源自金属离子源和还原剂之间反应的副产物将取决于用于完成无电沉积的工艺化学过程。根据本发明优选的实施方式,该还原剂包括次磷酸盐,其产生作为金属离子源和还原剂之间反应的副产物的亚磷酸盐。这意味着本发明优选的实施方式的无电沉积溶液中包括适量的亚磷酸盐。
类似地,本发明使用胺硼烷作为还原剂的优选的实施方式中将有作为副产物的胺类。这意味着本发明优选的实施方式的无电沉积溶液中包括适量的胺类。更具体地,本发明使用二甲胺硼烷作为还原剂的实施方式中将产生作为金属离子和还原剂之间反应的副产物的二甲胺。所以,本发明使用二甲胺硼烷作为反应物的实施方式同样也包括在本发明优选实施方式的无电沉积溶液中的反应副产物二甲胺。
可能包含在本发明优选的实施方式中的其他可能的副产物可能是由中和在无电沉积期间生成的酸而形成的盐。
对于本发明优选的实施方式,PH调节剂包括季铵碱以调节溶液的PH。此处描述的用于无电沉积溶液中调节溶液PH的季铵碱可选自多种化合物。示例性的PH调节剂包括但不局限于四氢氧化铵、四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、甲基三乙基氢氧化铵、乙基三甲基氢氧化铵、苄基三甲基氢氧化铵,以及其他适合保持溶液PH的更长的烷基链氢氧化铵。
优选地,一种或一种以上的络合剂保留溶液中甚至PH值下的金属离子,否则该金属离子将形成不溶的金属氢氧化物。通常适用的络合离子包括但不局限于柠檬酸盐、酒石酸盐、甘氨酸、焦磷酸盐,以及乙烯四乙酸(EDTA)。该络合剂作为酸引入到浴液中。具体地,柠檬酸盐作为柠檬酸引入,酒石酸盐作为酒石酸引入,或者焦磷酸盐作为焦磷酸引入。本发明优选的实施方式使用柠檬酸作为络合剂,但是也可使用其他络合剂或其组合。
可能包括第二金属离子源以便改进覆盖层的耐腐蚀性。对于钴钨合金,这种离子优选地是钨(VI)化合物,如钨(VI)的氧化物(WO3)或磷酸钨H3[P(W3O10)4],然而也可使用其他氧化形式的钨,如V或IV。上述的第二金属可选自周期表的第4周期,周期表的第5周期,以及周期表的第6周期。优选的选自元素表的第4周期的第二金属为Cr和Ni。优选的选自元素表的第5周期的第二金属为Mo、Ru、Rh和Pd。优选的选自元素表的第6周期的第二金属为W、Re、Os、Ir和Pt。本发明优选的实施方式使用钨作为钨源。
如上所述,本发明的一些实施方式可能不需要缓冲剂。缓冲剂的需求取决于用于形成覆盖层的工艺化学过程。本发明实施方式优选的缓冲剂包括硼酸盐,其可以作为硼酸并入到溶液中。更具体地,在PH为8到10的范围内用于缓冲溶液的最常见的化合物是硼酸。作为选择,硼酸盐/硼酸以外的缓冲剂也可用于本发明的实施方式中。
如果需要,也可在浴液中加入其他非必要的成分,以便达到如改变沉积薄膜的属性,沉积速率,溶液稳定性,以及提高耐腐蚀性等目的。这些辅助成分及其功能对本领域技术人员来说是公知的;详见例如Kolics等人的美国专利6,911,067。Kolics等人的美国专利6,911,067在此作为参考完全并入本发明中。
本发明的一个实施方式是覆盖层无电沉积的溶液。更具体地,配置该溶液以便支持无电沉积反应进而形成覆盖层。该溶液包括确定为无电沉积反应副产物的适量胺类和/或确定为无电沉积反应副产物的适量亚磷酸盐。对于本发明优选的实施方式,该胺类包括二甲胺。对于一具体应用的本发明实施方式使用浓度约0.01摩尔每升的二甲胺。对于本发明优选的实施方式,该亚磷酸盐浓度约0.01摩尔每升。在另一实施方式中,该胺类包括浓度约0.01摩尔每升的二甲胺并且亚磷酸盐的浓度约为0.01摩尔每升。在本发明优选的实施方式中,覆盖层包括钴以便形成钴覆盖层。作为本发明其他实施方式的选择,覆盖层可包括金属,如镍。
根据本发明更优选的实施方式,配置无电沉积溶液以沉积包含钴,钨,磷和硼的覆盖层。该无电沉积溶液包括适量钴,适量硼烷,适量次磷酸盐,适量钨,适量柠檬酸盐,适量硼酸盐,适量胺类,以及适量亚磷酸盐。对于无电沉积溶液中的每种成分,其量相当于完成沉积的有效量。根据一个实施方式,无电沉积溶液包括约0.012摩尔每升的钴浓度,约0.015摩尔每升的硼烷浓度,约0.083摩尔每升的次磷酸盐浓度,约0.023摩尔每升的钨浓度,约0.123摩尔每升的柠檬酸盐浓度,约0.077摩尔每升的硼酸盐浓度,浓度约0.01摩尔每升的二甲胺,以及浓度约0.01摩尔每升的亚磷酸盐。
本发明另一方面包括添补沉积包含金属的覆盖层的无电沉积浴液的组分。作为选择,该无电沉积浴液可包含上述的本发明实施方式中的无电沉积溶液。在本发明的一个实施方式中,添补沉积覆盖层的无电沉积浴液的组分包括从无电沉积浴液的数学模型中得出的金属浓度。作为选择,该金属浓度从无电沉积浴液操作的物质平衡中得出。在本发明的一个实施方式中,金属的浓度高于无电沉积浴液中金属反应物浓度的约3倍到约10倍。根据本发明的另一实施方式,金属的浓度高于无电沉积浴液中金属反应物浓度的约5倍到约10倍。在本发明的另一实施方式中,金属的浓度高于无电沉积浴液中金属反应物浓度的约5.1倍。
本发明优选的实施方式使用钴作为金属。具体应用的优选的实施方式使用钴作为金属以及组分包含有约0.0612摩尔每升的钴浓度。当然,本发明的其他实施方式可使用钴以外的金属。其他优选的实施方式使用镍以形成镍层。
根据本发明另一优选的实施方式,添补无电沉积浴液的组分进一步包括确定为无电沉积反应副产物的适量胺类和/或确定为无电沉积反应副产物的适量亚磷酸盐。优选的胺是二甲胺,其作为在溶液中的金属离子和诸如二甲胺硼烷之类还原剂之间的无电沉积反应的副产物出现。因为亚磷酸盐作为通过包含在由无电沉积溶液中的次磷酸盐还原的在无电沉积溶液中的金属离子之间反应的副产物出现,所以亚磷酸盐包含在组分中。作为选择,二甲胺的浓度约为0.038摩尔每升,以及亚磷酸盐浓度约为0.037摩尔每升。
本发明更优选的实施方式包括添补沉积具有钴,钨,磷,以及硼的覆盖层的无电沉积浴液的组分。添补无电沉积浴液的组分包括适量钴,适量次磷酸盐,适量钨,适量柠檬酸盐,适量硼酸盐,适量二甲胺,以及适量亚磷酸盐。对于添补无电沉积溶液的组分中的每一成分,其量相当于完成浴液添补的有效量,以便基本上保持无电沉积浴液的性能。
组分的一些具体属性可取决于操作浴液的环境。可能重要的环境包括但不局限于无电电镀浴液的组分,浴液中溶液的量,每个基板带出的量,以及每个基板带入的量。对于如在300mm直径基板上(如硅晶片)的钴钨磷硼覆盖层沉积的应用,每基板有20毫升的带入并且每基板有100毫升的浴液带出,以及10升体积的无电沉积溶液,添补无电沉积浴液的组分的优选的实施方式包含有:对于金属而言约0.0612摩尔每升的钴浓度,约0.325摩尔每升的次磷酸盐浓度,约0.09摩尔每升的钨浓度,约0.481摩尔每升的柠檬酸盐浓度,约0.287摩尔每升的硼酸盐浓度,约0.038摩尔每升的二甲胺浓度,以及约0.037摩尔每升的亚磷酸盐浓度。类似地,对于60毫升每基板的物质带出的应用,本发明优选实施方式的组分包含有:对于金属而言约0.061摩尔每升的钴浓度,约0.32摩尔每升的次磷酸盐浓度,约0.077摩尔每升的钨浓度,约0.414摩尔每升的柠檬酸盐浓度,约0.240摩尔每升的硼酸盐浓度,约0.032摩尔每升的二甲胺浓度,以及约0.031摩尔每升的亚磷酸盐浓度。
本发明的另一方面是加工基板的方法,如加工用于制造电子设备的基板。该方法涉及无电沉积,无电沉积溶液,以及无电沉积浴液的保持。在一个实施方式中,该方法是在具有铜和电介质结构的基板上的含有金属的覆盖层无电沉积的方法。该方法包括(i)提供具有用于无电沉积反应以便沉积覆盖层的反应物以及用于无电沉积反应的副产物的无电沉积浴液,以及(ii)使用该无电沉积浴液在基板上沉积覆盖层。该无电沉积浴液可能是之前没有使用过的起始浴液,或者是已经使用过并翻新到与起始浴液属性实质相同的浴液。该方法进一步包括(iii)通过添加计算出的一种或一种以上反应物的有效量与计算出的一种或一种以上副产物的有效量来添补无电沉积溶液。优选地,实施添补无电沉积浴液,使得能用该无电沉积浴液在附加基板上沉积覆盖层,该无电沉积浴液具有与(i)中的无电沉积浴液实质相同的属性。更具体地,配置该添补无电沉积浴液以保持无电沉积浴液的性能,从而延长无电沉积浴液的使用。
根据本发明优选的实施方式,该计算出的一种或一种以上反应物的有效量与计算出的一种或一种以上副产物的有效量都是从无电沉积浴液的数学模型得出。作为选择,该计算出的一种或一种以上反应物的有效量与计算出的一种或一种以上副产物的有效量都是从无电沉积浴液操作的物料平衡(mass balance)得出的。对于本发明的一个实施方式,该计算出的一种或一种以上反应物的有效量包括金属反应物的浓度,其高于无电沉积浴液中金属反应物浓度的约3倍到约10倍。在本发明的另一实施方式中,该计算出的一种或一种以上反应物的有效量包括金属反应物的浓度,其高于无电沉积浴液中金属反应物浓度的约5倍到约10倍。根据本发明优选的实施方式,该计算出的一种或一种以上反应物的有效量包括金属反应物的浓度,其高于无电沉积浴液中金属反应物浓度的约5.1倍。
对于本发明的一些实施方式,优选地通过具有不同组分的至少两个储液器将反应物和副产物添加到沉积浴液中来完成添补无电沉积浴液。对于使用钴作为所述金属的本发明的实施方式,该添补无电电镀浴液包括从第一储液器添加钴到浴液中以及从第二储液器添加其他反应物和副产物。包括使用无电沉积浴液沉积的钴,钨,磷和硼的覆盖层能使用本发明实施方式通过从第一储液器添加钴到浴液中以及从第二储液器添加钨,磷,硼和副产物来翻新。本发明使用两个储液器提供组分以翻新无电沉积浴液的实施方式提供了调整金属量与其他反应物和副产物比例的更多选择,该金属如钴。
根据本发明的另一实施方式,该方法包括使用添补组分,其包含有对于金属而言高于无电沉积浴液中钴浓度约5.1倍的钴浓度,适量无电沉积反应的胺类副产物,以及适量无电沉积反应的亚磷酸盐副产物。本发明优选的实施方式使用胺类副产物如二甲胺。作为本发明的一些实施方式的选择,该方法包括使用添补组分,其包含有对于金属而言高于无电沉积浴液中钴浓度约5.1倍的钴浓度,0.038摩尔每升的二甲胺浓度,以及0.037摩尔每升的亚磷酸盐浓度。
根据本发明另一实施方式的方法包括使用添补组分,其包含有对于金属而言高于无电沉积浴液中钴浓度约5.1倍的钴浓度,适量次磷酸盐;适量钨;适量柠檬酸盐;适量硼酸盐;适量二甲胺;以及适量亚磷酸盐。
对于如在300mm直径基板(如硅晶片)上的钴钨磷硼覆盖层沉积的应用,每基板具有20毫升的带入和每基板100毫升的浴液带出,以及10升体积的无电沉积溶液,该方法优选的实施方式包括使用添补组分,其包含有对于金属而言约0.0612摩尔每升的钴浓度,约0.325摩尔每升的次磷酸盐浓度,约0.09摩尔每升的钨浓度,约0.481摩尔每升的柠檬酸盐浓度,约0.287摩尔每升的硼酸盐浓度,约0.038摩尔每升的二甲胺浓度,以及约0.037摩尔每升的亚磷酸盐浓度。类似地,对于60毫升每基板的浴液带出的应用,本方法包括使用添补组分,其包含有对于金属而言约0.061摩尔每升的钴浓度,约0.32摩尔每升的次磷酸盐浓度,约0.077摩尔每升的钨浓度,约0.414摩尔每升的柠檬酸盐浓度,约0.240摩尔每升的硼酸盐浓度,约0.032摩尔每升的二甲胺浓度,以及约0.031摩尔每升的亚磷酸盐浓度。
在上述说明中,本发明通过参考的具体实施方式来描述。然而,本领域技术人员应了解,在不脱离本发明下述权利要求范围的前提下能进行不同的修改及变化。因此,说明书和附图是说明性的而不是限制性的,并且所有的这种修改包含在本发明的范围内。
优点,其他优势,和解决方案已经通过上述的具体实施方式描述。然而,该优点,其他优势,解决方案,以及可能引起任何优点,优势,或解决方案发生或变得更加明显的任何元素不应理解为是任一或所有权利要求的关键的,需要的,或必要的特征或元素。
本文使用的术语“包括”,“包含”,“包含有”,“有”,“具有”,“含有”,“至少一个”,或这些的其他变化旨在涵盖无排他性的包含。例如,包括一系列元素的工艺,方法,物品,或仪器并不局限于这些元素,其可能包括其他没有特别列举的元素或这种工艺,方法,物品,或仪器固有的其他元素。进一步的,除非有相反的明确的陈述,“或”指的是包含在内的或而不是排除在外的或。例如,条件A或B为满足以下的任何一项:A是真的(或存在的)以及B是假的(或不存在的),A是假的(或不存在的)以及B是真的(或存在的),以及A和B都是真的(或存在的)。
Claims (32)
1.在具有铜和电介质结构的基板上的包含金属的覆盖层无电沉积的方法,所述方法包括:
(i)提供具有用于无电沉积反应以便沉积覆盖层的反应物,并具有用于无电沉积反应的副产物的无电沉积浴液,其中,所述无电沉积反应的副产物包括浓度为0.01摩尔每升的二甲胺和浓度为0.01摩尔每升的亚磷酸盐;
(ii)使用所述无电沉积浴液在基板上沉积所述覆盖层;以及
(iii)通过添加计算出的一种或一种以上反应物的有效量与计算出的一种或一种以上副产物的有效量来添补所述无电沉积溶液,使得能用与(i)中的所述无电沉积浴液具有实质相同属性的无电沉积浴液在附加基板上沉积覆盖层。
2.根据权利要求1所述的方法,其中所述计算出的一种或一种以上反应物的有效量与所述计算出的一种或一种以上副产物的有效量都是从所述无电沉积浴液的数学模型得出。
3.根据权利要求1所述的方法,其中所述计算出的一种或一种以上反应物的有效量与所述计算出的一种或一种以上副产物的有效量都是从所述无电沉积浴液的物料平衡得出的。
4.根据权利要求1所述的方法,其中所述计算出的一种或一种以上反应物的有效量包含有高于所述无电沉积浴液中所述金属反应物浓度的3倍到10倍的金属反应物浓度。
5.根据权利要求1所述的方法,其中所述计算出的一种或一种以上反应物的有效量包含有高于所述无电沉积浴液中所述金属反应物浓度的5倍到10倍的金属反应物浓度。
6.根据权利要求1所述的方法,其中所述计算出的一种或一种以上反应物的有效量包含有高于所述无电沉积浴液中所述金属反应物浓度的5.1倍的金属反应物浓度。
7.根据权利要求1所述的方法,其中,通过具有不同组分的至少两个储液器将所述反应物添加到所述沉积浴液中。
8.根据权利要求1所述的方法,其中,所述无电电镀浴液包括用于钴覆盖层的钴;所述添补无电电镀浴液包括从第一储液器添加钴到浴液中以及从第二储液器添加其他反应物和所述副产物。
9.根据权利要求1所述的方法,其中,所述无电电镀浴液包括钴,钨,磷和硼;所述添补无电电镀浴液包括从第一储液器添加钴到浴液中,以及从第二储液器添加钨,磷,硼和所述副产物。
10.根据权利要求1所述的方法,其中,(iii)包括使用添补组分,该组分包含有:
对于金属而言高于所述无电沉积浴液中钴浓度5.1倍的钴浓度;
适量所述无电沉积反应的胺类副产物;以及
适量所述无电沉积反应的亚磷酸盐副产物。
11.根据权利要求1所述的方法,其中,(iii)包括使用添补组分,该组分包括:
对于金属而言高于所述无电沉积浴液中钴浓度5.1倍的钴浓度;
适量二甲胺;以及
适量亚磷酸盐。
12.根据权利要求1所述的方法,其中,(iii)包括使用添补组分,该组分包含有:
对于金属而言高于所述无电沉积浴液中钴浓度5.1倍的钴浓度;
0.038摩尔每升的二甲胺浓度;以及
0.037摩尔每升的亚磷酸盐浓度。
13.根据权利要求1所述的方法,其中,(iii)包括使用添补组分,该组分包含有:
对于金属而言高于所述无电沉积浴液中钴浓度5.1倍的钴浓度;
适量次磷酸盐;
适量钨;
适量柠檬酸盐;
适量硼酸盐;
适量二甲胺;以及
适量亚磷酸盐。
14.根据权利要求1所述的方法,其中,所述浴液带出为100毫升每基板,以及(iii)包括使用添补组分,所述组分包含有:
对于金属而言0.0612摩尔每升的钴浓度;
0.325摩尔每升的次磷酸盐浓度;
0.09摩尔每升的钨浓度;
0.481摩尔每升的柠檬酸盐浓度;
0.287摩尔每升的硼酸盐浓度;
0.038摩尔每升的二甲胺浓度;以及
0.037摩尔每升的亚磷酸盐浓度。
15.根据权利要求1所述的方法,其中浴液带出为60毫升每基板,以及(iii)包括使用添补组分,所述组分包含有:
对于金属而言高于所述无电沉积浴液中钴浓度5.1倍的钴浓度;
0.061摩尔每升的钴浓度;
0.32摩尔每升的次磷酸盐浓度;
0.077摩尔每升的钨浓度;
0.414摩尔每升的柠檬酸盐浓度;
0.240摩尔每升的硼酸盐浓度;
0.032摩尔每升的二甲胺浓度;以及
0.031摩尔每升的亚磷酸盐浓度。
16.用于覆盖层无电沉积的溶液,其包括:
确定为无电沉积反应副产物的适量胺类,其中,所述胺类包括浓度为0.01摩尔每升的二甲胺;以及
确定为无电沉积反应副产物的适量亚磷酸盐,其中,所述亚磷酸盐的浓度为0.01摩尔每升。
17.根据权利要求16所述的溶液,其中所述覆盖层包括钴。
18.根据权利要求16所述的溶液,其中所述覆盖层包括镍。
19.根据权利要求16所述的溶液,其中所述覆盖层包括钴,钨,磷和硼;所述无电沉积溶液进一步包括:
适量钴;
适量硼烷;
适量次磷酸盐;
适量钨;
适量柠檬酸盐;以及
适量硼酸盐。
20.根据权利要求16所述的溶液,其中所述覆盖层包括钴,钨,磷和硼;所述无电沉积溶液进一步包含有:
0.012摩尔每升的钴浓度;
0.015摩尔每升的硼烷浓度;
0.083摩尔每升的次磷酸盐浓度;
0.023摩尔每升的钨浓度;
0.123摩尔每升的柠檬酸盐浓度;以及
0.077摩尔每升的硼酸盐浓度。
21.添补用于包括金属的覆盖层沉积的无电沉积浴液的组分,所述用于覆盖层沉积的无电沉积浴液包括根据权利要求16所述的溶液,所述组分包含有:
从所述无电沉积浴液的数学模型中得出的所述金属的浓度;
浓度为0.038摩尔每升的适量的二甲胺;以及,
浓度为0.037摩尔每升的适量的亚磷酸盐。
22.根据权利要求21所述的组分,其中所述金属的浓度从所述无电沉积浴液的物料平衡中得出。
23.根据权利要求21所述的组分,其中所述金属的浓度高于所述无电沉积浴液中所述金属反应物浓度的3倍到10倍。
24.根据权利要求21所述的组分,其中所述金属的浓度高于所述无电沉积浴液中所述金属反应物浓度的5倍到10倍。
25.根据权利要求21所述的组分,其中所述金属的浓度高于所述无电沉积浴液中所述金属反应物浓度的5.1倍。
26.根据权利要求21所述的组分,其中所述金属包括钴。
27.根据权利要求21所述的组分,其中所述金属的浓度包含有0.0612摩尔每升的钴浓度。
28.根据权利要求21所述的组分,其中所述金属包括镍。
29.根据权利要求21所述的组分,
其中所述适量的二甲胺确定为所述无电沉积反应副产物;并且
其中所述适量的亚磷酸盐确定为所述无电沉积反应副产物。
30.根据权利要求21所述的组分,其进一步包括:
对于金属而言的适量钴;
适量次磷酸盐;
适量钨;
适量柠檬酸盐;以及
适量硼酸盐。
31.根据权利要求21所述的组分,对于具有100毫升每基板浴液带出的钴钨磷硼覆盖层沉积,所述组分包含有:
对于金属而言0.0612摩尔每升的钴浓度;
0.325摩尔每升的次磷酸盐浓度;
0.09摩尔每升的钨浓度;
0.481摩尔每升的柠檬酸盐浓度;以及
0.287摩尔每升的硼酸盐浓度。
32.添补用于包括金属的覆盖层沉积的无电沉积浴液的组分,所述用于覆盖层沉积的无电沉积浴液包括根据权利要求16所述的溶液,所述组分包含有从所述无电沉积浴液的数学模型中得出的所述金属的浓度,对于具有60毫升每基板浴液带出的钴钨磷硼覆盖层沉积,所述组分进一步包含有:
对于金属而言0.061摩尔每升的钴浓度;
0.32摩尔每升的次磷酸盐浓度;
0.077摩尔每升的钨浓度;
0.414摩尔每升的柠檬酸盐浓度;
0.240摩尔每升的硼酸盐浓度;
0.032摩尔每升的二甲胺浓度;以及
0.031摩尔每升的亚磷酸盐浓度。
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CN200980160458.0A Expired - Fee Related CN102471918B (zh) | 2009-07-16 | 2009-07-16 | 无电沉积溶液和工艺控制 |
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US (2) | US8328919B2 (zh) |
EP (1) | EP2454397A1 (zh) |
JP (1) | JP2012533683A (zh) |
KR (2) | KR20120034104A (zh) |
CN (1) | CN102471918B (zh) |
SG (1) | SG176709A1 (zh) |
WO (1) | WO2011008212A1 (zh) |
Families Citing this family (3)
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US8895441B2 (en) * | 2012-02-24 | 2014-11-25 | Lam Research Corporation | Methods and materials for anchoring gapfill metals |
US10731258B2 (en) | 2014-10-27 | 2020-08-04 | Surface Technology, Inc. | Plating bath solutions |
US10006126B2 (en) | 2014-10-27 | 2018-06-26 | Surface Technology, Inc. | Plating bath solutions |
Citations (1)
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US4152164A (en) * | 1976-04-26 | 1979-05-01 | Michael Gulla | Electroless nickel plating |
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US2872354A (en) * | 1954-12-31 | 1959-02-03 | Gen Am Transport | Processes of continuous chemical nickel plating |
JPS6016517B2 (ja) * | 1979-12-29 | 1985-04-25 | 上村工業株式会社 | 無電解めつき制御方法 |
US4353933A (en) * | 1979-11-14 | 1982-10-12 | C. Uyemura & Co., Ltd. | Method for controlling electroless plating bath |
JPS6043491A (ja) * | 1983-08-19 | 1985-03-08 | Nippon Denso Co Ltd | 鉄鋼表面に燐酸塩化成被膜を形成する方法 |
JPS61199069A (ja) * | 1985-02-28 | 1986-09-03 | C Uyemura & Co Ltd | めっき液濃度自動連続管理装置 |
CA2052931A1 (en) * | 1991-01-31 | 1992-08-01 | Theodore A. Martin, Jr. | Process and programmable computer controlled system for electroless copper plating |
US5368715A (en) * | 1993-02-23 | 1994-11-29 | Enthone-Omi, Inc. | Method and system for controlling plating bath parameters |
US5993892A (en) * | 1996-09-12 | 1999-11-30 | Wasserman; Arthur | Method of monitoring and controlling electroless plating in real time |
JP2001355074A (ja) * | 2000-04-10 | 2001-12-25 | Sony Corp | 無電解メッキ処理方法およびその装置 |
US6524642B1 (en) * | 2001-04-21 | 2003-02-25 | Omg Fidelity, Inc. | Electroless metal-plating process |
US6645567B2 (en) * | 2001-12-19 | 2003-11-11 | Intel Corporation | Electroless plating bath composition and method of using |
US6821324B2 (en) * | 2002-06-19 | 2004-11-23 | Ramot At Tel-Aviv University Ltd. | Cobalt tungsten phosphorus electroless deposition process and materials |
DE10246453A1 (de) * | 2002-10-04 | 2004-04-15 | Enthone Inc., West Haven | Verfahren zur stromlosen Abscheidung von Nickel |
US6911067B2 (en) * | 2003-01-10 | 2005-06-28 | Blue29, Llc | Solution composition and method for electroless deposition of coatings free of alkali metals |
US6902605B2 (en) * | 2003-03-06 | 2005-06-07 | Blue29, Llc | Activation-free electroless solution for deposition of cobalt and method for deposition of cobalt capping/passivation layer on copper |
JP4965959B2 (ja) * | 2005-10-25 | 2012-07-04 | 株式会社荏原製作所 | 無電解めっき装置 |
US7658790B1 (en) * | 2007-07-03 | 2010-02-09 | Intermolecular, Inc. | Concentrated electroless solution for selective deposition of cobalt-based capping/barrier layers |
US9128493B2 (en) * | 2007-12-12 | 2015-09-08 | Lam Research Corporation | Method and apparatus for plating solution analysis and control |
US20090155468A1 (en) * | 2007-12-17 | 2009-06-18 | Enthone Inc. | Metrology in electroless cobalt plating |
-
2009
- 2009-07-16 KR KR1020127001112A patent/KR20120034104A/ko active Application Filing
- 2009-07-16 WO PCT/US2009/050833 patent/WO2011008212A1/en active Application Filing
- 2009-07-16 JP JP2012520578A patent/JP2012533683A/ja active Pending
- 2009-07-16 EP EP09847439A patent/EP2454397A1/en not_active Withdrawn
- 2009-07-16 KR KR1020167020918A patent/KR20160096220A/ko not_active Application Discontinuation
- 2009-07-16 SG SG2011090396A patent/SG176709A1/en unknown
- 2009-07-16 CN CN200980160458.0A patent/CN102471918B/zh not_active Expired - Fee Related
-
2010
- 2010-03-24 US US12/731,115 patent/US8328919B2/en not_active Expired - Fee Related
-
2012
- 2012-11-19 US US13/681,332 patent/US20130078808A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US4152164A (en) * | 1976-04-26 | 1979-05-01 | Michael Gulla | Electroless nickel plating |
Also Published As
Publication number | Publication date |
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EP2454397A1 (en) | 2012-05-23 |
JP2012533683A (ja) | 2012-12-27 |
US20110014361A1 (en) | 2011-01-20 |
US20130078808A1 (en) | 2013-03-28 |
CN102471918A (zh) | 2012-05-23 |
KR20160096220A (ko) | 2016-08-12 |
KR20120034104A (ko) | 2012-04-09 |
US8328919B2 (en) | 2012-12-11 |
SG176709A1 (en) | 2012-02-28 |
WO2011008212A1 (en) | 2011-01-20 |
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