WO2006060520A2 - Membrane-limited selective electroplating of a conductive surface - Google Patents
Membrane-limited selective electroplating of a conductive surface Download PDFInfo
- Publication number
- WO2006060520A2 WO2006060520A2 PCT/US2005/043387 US2005043387W WO2006060520A2 WO 2006060520 A2 WO2006060520 A2 WO 2006060520A2 US 2005043387 W US2005043387 W US 2005043387W WO 2006060520 A2 WO2006060520 A2 WO 2006060520A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- membrane
- electroplating
- conductive surface
- anode
- metal ions
- Prior art date
Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims description 183
- 229910021645 metal ion Inorganic materials 0.000 claims description 42
- 239000012530 fluid Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000554 ionomer Polymers 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002759 woven fabric Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 35
- 238000007747 plating Methods 0.000 description 33
- 239000010410 layer Substances 0.000 description 32
- -1 e.g. Inorganic materials 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000002706 hydrostatic effect Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000010276 construction Methods 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
- 239000008367 deionised water Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003843 chloralkali process Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 229940116906 cupric cation Drugs 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/008—Current shielding devices
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- 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
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/095—Conductive through-holes or vias
- H05K2201/09563—Metal filled via
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0548—Masks
- H05K2203/0557—Non-printed masks
Definitions
- This invention relates to processes and apparati for selectively electroplating a metal layer or layers into recessed topographic features on a conductive surface.
- the processes and apparati of the invention are useful for fabricating metal circuit patterns, for example for creating copper interconnects between integrated circuit elements embedded in a thin layer of dielectric material on the surface of a semiconductor wafer.
- the electrical interconnections are created as patterns of lines and holes etched through a dielectric layer on the surface of the wafer. Such patterns are then filled with metallic copper, and electroplating is commonly used.
- An ideal deposition process would completely fill the recesses in the dielectric layer with copper to a level that is flush with the surrounding plateau surfaces and not deposit any copper on the plateau surfaces.
- conventional electroplating technology can provide control over thickness and uniformity of the plated layer, no practical method has been disclosed that selectively deposits a metal layer into the holes and trenches or the recessed areas in the dielectric layer and simultaneously precludes depositing a metallic layer of comparable thickness on top of the plateaus separating the circuit features.
- One aspect of the present invention is a process of electroplating metal onto a conductive surface, wherein the conductive surface comprises plateaus and trenches, the method comprising: (a) contacting the conductive surface with an electroplating solution comprising platable metal ions;
- Another aspect of the present invention is an apparatus for electroplating metal onto a conductive surface, the conductive surface comprising plateaus and trenches, the apparatus comprising:
- a charge-selective ion-conducting membrane comprising a first surface and an opposing second surface, wherein the membrane is substantially impermeable to the platable metal ions in the electroplating solution, and is adapted for the second surface to be placed in close proximity to or in sensible contact with the conductive surface; (c) an anode in electrical contact with the first surface of the membrane; and
- a power source capable applying a voltage between the anode and the conductive surface to generate a flow of electrical current in an amount sufficient to electroplate at least a portion of the metal ions in the electroplating solution onto the conductive surface.
- Fig. 1 A shows a cross-section of damascene wafer showing copper circuit features 9 embedded in dielectric layer 10;
- Fig. 1B shows a cross-section showing deposition of copper layer 17 onto sub-mircon topographic features under conventional transport-limited electroplating conditions
- Fig. 2A shows a schematic illustration of membrane-limited electroplating into a topographic recess employing an anion-conducting membrane with an acidic copper sulfate plating solution;
- Fig. 2B shows a schematic illustration of membrane-limited electroplating into a topographic recess employing a cation-conducting membrane with a basic cyanocu prate plating solution
- Fig. 3 shows a schematic cross-section of a membrane-limited electroplating apparatus employing hydrostatic pressure to seal the membrane 13 against the substrate;
- Fig. 4 shows a schematic cross-section of a membrane-limited electroplating apparatus employing mechanical force from a porous anode 18 with smooth flat surface to seal the membrane 13 against the substrate;
- Fig. 5 shows a schematic cross-section of a membrane-limited electroplating apparatus employing mechanical force from a porous spacer 19 with smooth flat surface to seal the membrane 13 against the substrate;
- Fig. 6 shows a schematic cross-section of a membrane-limited electroplating apparatus employing a low conductivity fluid 20 as the anolyte and mechanical force from a porous anode 18 with smooth flat surface to seal the membrane 13 against the substrate.
- One embodiment of this invention is an apparatus for electroplating metal onto a conductive surface, the conductive surface comprising plateaus and trenches, the apparatus comprising:
- a charge-selective ion-conducting membrane comprising a first surface and an opposing second surface, wherein the membrane is substantially impermeable to the platable metal ions in the electroplating solution, and is adapted for the second surface to be placed in close proximity to or in sensible contact with the conductive surface;
- a power source capable applying a voltage between the anode and the conductive surface to generate a flow of electrical current in an amount sufficient to electroplate at least a portion of the metal ions in the electroplating solution onto the conductive surface.
- recessed features on the substrate or conductive surface.
- recessed features recessed features
- holes recessed trenches
- topographic recesses recessed trenches
- vias may be used alternatively, in conjunction, selectively, or interchangeably. Unless otherwise specified, usage of any of these terms includes every type of recessed feature that is not a plateau and the meaning is construed to comprehensively include all types of features.
- plateau is meant the generally flat area of the substrate or conductive surface that is at the level of the top of the trenches and/or vias.
- a "conductive" fluid or solution has conductivity greater than about 5 mS/cm, preferably equal to or greater than about 30 mS/cm, more preferably equal to or greater than about 100 mS/cm.
- a "conductive surface” has a sheet resistance no greater than about
- a "low-conductivity" fluid or solution has conductivity below about 1000 ⁇ S/cm.
- Non-platable metal ions are known to those skilled in the art and include, for example, Na and K.
- the electroplating solution may contain, in addition to the platable metal ions, other electrolytes, surfactants, and/or other additives well known in the art and variously designated as “brighteners”, “levelers”, or “accelerators”. Any apparatus or device suitable for supplying electroplating solution to an area between a membrane and a substrate is useful, including, for example, baths and sprayers.
- the electroplating solution can be supplied at any pressure, and the supply can be intermittent or continuous.
- the electroplating solution can be of one composition, or can change composition during the plating process.
- a source of DC electrical power is connected between the conductive surface (which functions as the cathode) and the anode.
- the source of DC power can be steady or can advantageously provide pulses and/or variable DC power.
- a typical damascene wafer comprises a barrier layer that may not provide sufficient electrical connection to a power source and thus cannot by itself serve as a cathode. For this reason a seed layer of metal, for example copper, covers the barrier layer to provide the electrical connection to the power source.
- the anode is an electrically conductive material such as a metal or alloy (e.g., stainless steel, platinum, palladium or the dimensionally stable anodes commonly used in the chlor-alkali process) or carbon. Electrical contact between the anode and the first surface of the membrane can beneficially be through an anolyte contacting the anode and the first surface of the membrane, wherein preferably the anolyte is a conductive solution, fluid, or composition.
- the anolyte also acts as a source and/or sink for ions passing through the membrane.
- the anolyte solution may comprise water, a polar organic solvent, or a combination of such solvents and beneficially also includes solutes such as acids, bases or salts.
- the anolyte can contain one or more non-plating metal ions, e.g., Na, K, or such,
- the anolyte should not contain any readily reducible negatively charged anions.
- the anolyte should not contain any readily reducible positively charged cations.
- the membrane-limited selective electroplating process can be used for deposition of a wide variety of platable metals and metal alloys.
- Suitable metals include silver, nickel, cobalt, tin, aluminum, copper, lead, tantalum, titanium, iron, chromium, vanadium, manganese, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, hafnium, tungsten, rhenium, osmium, iridium, and combinations thereof.
- Preferred metals include silver, nickel, cobalt, tin, aluminum, copper, lead and combinations thereof. The method is particularly suitable for electroplating copper and/or copper-containing alloys on damascene wafers.
- Membrane-limited selective electroplating may employ conventional electroplating solutions comprising salts of metal ions or complex metal ions and other ingredients, for example acids or bases, buffers, surfactants and/or other additives known in the electroplating art. Any or all adjuvants known for use in electroplating solutions can be used in the processes herein.
- the platable metal in the electroplating solution either has a positive charge or a negative charge.
- Common commercial aqueous electroplating solutions fall into two general categories, depending upon whether the dissolved metal ions are positively charged cations or negatively charged anions.
- Membrane-limited selective electroplating may use either type of plating solution depending on the type of membrane that is employed.
- the electroplating solution for copper plating is commonly either an acid solution containing, for example CuSO 4 in aqueous H 2 SO 4 , or a solution containing basic cyanide or other nitrogen-containing-ligand, for example CuCN and NaCN in aqueous NaOH or Na 2 OO 3 .
- the platable copper species is the hydrated cupric cation Cu(H 2 O) n +2
- the platable copper species is the complex cyanocuprate anion Cu(CN) 3 "2 .
- the ion-conducting membrane serves two functions.
- the first function of the ion-conducting membrane is to displace plating solution from the plateau areas of the conductive surface while trapping plating solution within the recessed areas.
- the second function of the membrane is to serve as a gate that allows certain ions to carry electrical current through the membrane, but specifically prevents electrochemically active metal ions from contacting or plating onto the plateau areas.
- Suitable charge-selective ion-conducting membranes include film- forming ionic polymers that are stable under the conditions of the electroplating process. Ionic polymer membranes useful in electro- coating, electro-dialysis, the chloralkali process and fuel-cells may also be useful in the electroplating process herein.
- the ion-conducting membrane can be of any thickness, but advantageously the membrane thickness is greater than the width of trenches to be filled with electroplated metal. In practice, the membrane thickness is typically at least 2 times the largest width of trenches to be filled with electroplated metal. Exemplary thickness of the membrane is in the range of from about 40 microns to about 500 microns, or alternatively about 3 to about 120 mils.
- the reason for having appreciable thickness is that the thickness will resist bending and, coupled with the stiffness of the membrane, should be sufficient so that the membrane does not conform to the topography of the conductive surface.
- the distribution of charged moieties in the pores need not be uniform, and the membrane can comprise one or more separate membranes laminated one to another.
- the membrane is advantageously sufficiently stiff and incompressible so that the active portion of the membrane does not conform to the topography of the conductive surface.
- the stiffness and compressibility of the membrane can vary with degree of saturation as well as the ion content in the membrane, but generally, most commercially available Nafion ® and Flemion ® cation-exchange membranes, or Fumatech FAP and PCA60 anion-exchange membranes have the requisite stiffness and incompressibility when the saturation level is near 100%.
- Suitable ion-conducting membranes are substantially impervious (impermeable) to the platable metal ions in the electroplating solution.
- substantially impermeable to the metal ions in the electroplating solution we mean firstly, that for cation-exchange membranes, the transference number for cations is at least 0.9, and secondly, that at least 80% of the platable metal ions are anions.
- the transference number for anions is at least 0.9, and at least 80% of the platable metal ions are cations. Under conditions where electroplating requires transfer of a cation, a cation-conducting membrane is used.
- An exemplary cation-conducting membrane comprises a polymeric ionomer functional ized with at least one type of acidic moiety.
- Cation-selective ion- conducting membranes also called cation-exchange membranes
- the cation-conducting membranes are formed from polymeric ionomers functionalized with strong acid groups that have a pKa of less than about 3. Sulfonic acid groups are preferred strong acid groups.
- Preferred polymeric ionomers are copolymers of fluorinated and/or perfluorinated olefins and monomers containing strong acid groups.
- An exemplary cation-selective membrane may have 1.0 to 4.0 milli- equivalents of strong acid groups per cubic centimeter of membrane.
- Suitable membranes include polytetrafluorethylene polymer-based membranes, perfluorocarboxylic acid/PTFE copolymers, polymeric ionomers functionalized with both sulfonic acid groups and carboxylic acid groups, and perfluorosulfonic acid/ polytetrafluorethylene copolymer membranes.
- acid moieties can be attached to the membrane as an alternative to, or in addition to, the carboxylic acid moieties and/or the sulfonic acid moieties, including for example a sulfanilamide moiety, a phosphonate moiety, a sulfonyl moiety, or any combination thereof, wherein the acidic moieties can independently be substituted with, for example, a Ci to C 4 alkyl group.
- cation-conducting membranes useful in the processes of this invention include Flemion ® perfluorocarboxylate ionomer membranes (Asahi Glass Co., Ltd, Yokahama, Japan) and/or Nafion ® perfluorosulfonate ionomer membranes (E.I. du Pont de Nemours, Inc., Wilmington, DE), which are composed of fluorocarbon chains bearing highly acidic carboxylic and sulfonic acid groups, respectively. On exposure to water, the acid groups of Nafion® ionize, leaving fixed sulfonate anions and mobile hydrated protons. The protons may be readily exchanged with various metal cations. Nafion® is particularly well- suited for use in membrane-limited selective electroplating due to its strong common-ion exclusion, high conductivity, strong acidity, chemical stability and robust mechanical properties.
- the membrane is layered, and comprises a fluoropolymer membrane comprising at least two integrally laminated layers including a first layer made of a perfluorocarbon polymer having carboxylic acid groups as its ion exchange groups, and a second layer comprising perfluorocarbon polymer having sulfonic acid groups as its ion exchange groups.
- the layers can be separated by a fluid layer.
- a suitable membrane can be a single layer having both sulfonic and carboxylic groups made, for example, by the copolymerization of a carboxylic acid type monomer with a sulfonic acid type monomer, or by the copolymerization of a carboxylic acid type monomer with a sulfonic acid type monomer, or by impregnating a sulfonic acid type fluoropolymer membrane with a carboxylic acid type monomer, followed by polymerization.
- Suitable membranes include those formed from a blend comprising a sulfonic acid group-containing polymer and a carboxylic acid group-containing polymer, which is laminated on a sulfonic acid group membrane, as described in U.S. 4,176,215, and herein incorporated by reference.
- an anion-conducting membrane comprises a polymeric ionomer functionalized with at least one type of basic moiety, for example quaternary ammonium groups. Tertiary or lower amino groups are also suitable functional groups.
- Anion-selective ion- conducting membranes (also called anion-exchange membranes) generally comprise organic polymer films with positively charged covalently bound functional groups such as ammonium ions -NH 3 + , NH 2 R + , -NHR 2 + , or -NR 3 + , or basic salts such as -NRH 2 OH, NR 2 HOH, or NR 3 OH, where R is an organic radical.
- anion-conducting membrane may have 5 to 200 microequivalents of basic moieties per cm 2 of membrane area.
- anion-selective ion-conducting membranes include the PC amine-functionalized epoxide polymers (PCA -Polymerchemie Altmeier GmbH, Heusweiler, Germany).
- Strongly basic styrenic anion-conductive membranes can be formed from a cross-linked poly-styrene-divinylbenzene that is chloromethylated using a Lewis acid and further functionalized by addition of a tertiary amine.
- Methods for making anion-conducting membranes can be adapted from methods to make anion-exchange membranes described in U.S. 6,646,083, which is incorporated by reference herein.
- a process for electroplating metal onto a conductive surface wherein the conductive surface comprises plateaus and trenches, the method comprising:
- Electroplating occurs when a portion of the external surface of the ion-conducting membrane is brought into sensible contact with a portion of the conductive surface that is covered by the electroplating solution, with the substrate held at a voltage more negative than the open circuit voltage.
- the term "sensibly contact” means there may be a thin layer of fluid disposed between the membrane and the wetted plateaus; preferably there is none. Some solution remains trapped within the recessed features. The trapped electroplating solution within the recesses serves as a source of metal ions in an electroplating step.
- the continuous or intermittent exchange of the plating solution within the recessed features with fresh plating solution is usually achieved by moving the membrane with respect to the conductive surface, where the exposed portions of the surface not contacting the membrane are subject to a rinse of fresh electroplating solution.
- a membrane moving along a surface may not displace all the electroplating solution from the plateaus, and controlling the velocity of the membrane and the pressure exerted on the membrane can influence the thickness of any layer of electroplating solution disposed between the plateaus and the membrane.
- the conductive surface typically comprises a metal such as copper, but other metals may be used as long as they provides suitable electrical contact to the power source and adhesion to the plated copper.
- the distance between the membrane and the plateaus desirably provides an electroplating solution layer between the plateaus and the membrane that is less than twice the depth of the trenches preferably much less than twice the depth of the trenches.
- the "depth of the trenches" is the difference in height between the floor of trenches and vias to be filled and the top of the surrounding plateaus. For example, if the membrane contacts and electroplates material onto a damascene wafer where the depth of the trench to be filled is about 1 micron, then the average height of the electroplating solution disposed between a membrane and a nearby plateau is less than 0.5 microns, and may preferably be less than 10 nanometers. When the membrane is being moved relative to the conductive surface, this layer may provide lubrication between the membrane and the conductive surface.
- the pressure exerted by the membrane on the conductive surface is sufficient to reduce the thickness of the layer of electroplating solution disposed between the top of plateaus and the membrane to the desired thickness.
- the pressure can range from about 0.03 to about 30 psi.
- the velocity of the membrane relative to the conductive surface may range from about 0 to about 200 cm/sec or more, but is typically from about 1 cm/sec to about 30 cm/sec.
- the membrane is held in sensible contact with the conductive surface and a suitable voltage is applied between the anode and cathode under these conditions, metal ions of the electroplating solution are reduced to elemental metal and are deposited into the trenches of the conductive surface.
- a disproportionately large portion of the electrical current flows through small volumes of the electroplating solution trapped within the topographic recesses (trenches) of the surface.
- the entrapment of the electroplating solution is achieved by holding the conductive surface in intimate contact with a first surface of a charge-selective ion-conducting membrane.
- the conductive surface can be held stationary and the membrane moved, or the membrane can be held stationary and the surface moved, or both the surface and the membrane can be in motion.
- the relative motion may be parallel or perpendicular to the conductive surface or some combination of the two.
- the rate of depletion of platable metal ions in the electroplating solution is typically not constant, and the rate of plating from a trapped volume of electroplating solution can slow over time as the concentration of platable ions in the electroplating solution is depleted.
- the amount of time for which a given portion of electroplating solution is trapped without being refreshed is at least sufficient to lower the average concentration of platable metal ions by at least 30% in the layer of fluid disposed between the membrane and the recessed areas. As the recessed areas become filled with copper, they retain progressively less electroplating solution, so that metal ion depletion occurs more rapidly. There is no advantage in allowing the concentration to fall to less than 90% of its original value.
- the amount of time to electroplate before replenishing or replacing the electroplating solution disposed in a trench can in some cases beneficially be changed as an endpoint is approached.
- electroplating solution is supplied to the area between the membrane and the surface. Since electroplating solution is typically disposed on the conductive surface prior to the membrane passing over that surface, it is important to prevent current flowing to the plateau areas outside the area where the membrane sensibly contacts the surface. Once the membrane contacts the surface, then electroplating solution is displaced from the plateaus, and the electroplating process can beneficially proceed.
- the electrical circuit in order to avoid plating metal onto the plateau areas the electrical circuit is temporarily opened or the voltage is set to the open-circuit voltage during disengagement, movement, and re- engagement of the membrane.
- different areas of the surface may be systematically engaged and disengaged from the membrane by continuously moving the membrane across the conductive surface. In that way fresh plating solution is continuously provided to the recessed areas without need to interrupt the current. Moreover, since at any given time the current flows only to a localized area of the surface, which contacts the membrane, the uniformity of deposition in recesses over the entire surface can be systematically optimized by regulating the integrated residence times in localized areas. The rate or velocity at which the membrane moves across the surface determines the rate at which fresh plating solution is supplied to the recessed areas: the greater this velocity, the greater the rate of supply.
- the composition of the anolyte changes as various reagents are either consumed or generated by anodic reactions and other reagents may accumulate or be lost through the membrane.
- it is advantageous to maintain substantially stable compositions for the anolyte and electroplating solutions. Therefore, it may be advantageous to remove and replace used solutions from the anode compartment and from the conductive surface, or to otherwise affect the composition to maintain stable concentrations in the anolyte and electroplating solution.
- the process of the invention is self-limiting in the sense that the plating process automatically slows as the recessed volumes have been filled with metal to a level approaching or comparable with the plateau areas.
- the corresponding decrease in plating current may be used as a diagnostic indication of the process end-point.
- FIG 2A illustrates one embodiment of a process of the present invention wherein an anion-conducting membrane is employed in conjunction with an acidic CuSO 4 plating solution.
- the surface of the substrate 10 (the conductive surface) is initially covered by the plating solution 12, but a first surface of the membrane 13 is then pressed against the substrate surface so as to displace the plating solution from the plateau surfaces while leaving small volumes of electroplating solution entrapped in the recesses or the trenches 12.
- the membrane may be held or pressed against the surface of the substrate by hydrostatic pressure of the anolyte solution 16.
- FIG. 2B illustrates one embodiment of the invention wherein a cation-conducting membrane is employed in conjunction with a basic plating solution comprised of CuCN and advantageously other salts such as NaCN in aqueous NaOH.
- a basic plating solution comprised of CuCN and advantageously other salts such as NaCN in aqueous NaOH.
- the surface of the substrate is initially covered by the plating solution, and a first surface of the membrane is then pressed against the substrate surface so as to displace the plating solution from the plateau surfaces while leaving plating solution 12 trapped in the recesses.
- Hydrostatic pressure can advantageously be applied to the anolyte solution 16 contacting the second, opposing, surface of the membrane 13 in order to urge the first surface of the membrane 13 against the plateau areas of the substrate.
- the anolyte solution 16 may comprise water, a polar organic solvent, or a combination of such solvents and may include solutes such as bases or salts, but need not contain any electrochemically active metal ions.
- the anode 15 is an electrically conductive material such as a metal or carbon.
- the anodic reaction may comprise oxidation of the anode 15 to yield soluble oxidation products (a sacrificial anode), or may comprise oxidation of some component of the anolyte solutions 16.
- the anode is electrochemically inert and the anolyte contains primarily de-ionized water containing little or no easily oxidized solutes, then the principle anodic reaction will be oxidation of OH " to O 2 .
- the examples illustrated in Figures 2A and 2B and described in the previous paragraphs are only representative examples. Many different types of apparatus, plating solution, anolytes and electrode reactions can be utilized in membrane-limited electroplating, as will be apparent to those skilled in the art.
- the apparatus for membrane-limited electroplating is advantageously designed so that limited or no electrolytic current can flow to plateau areas of the substrate not sealed by the membrane.
- Figures 3- 5 illustrate various methods to restrict the flow of current to areas of the substrate sensibly contacted by the membrane.
- Figure 3 illustrates in cross-section an apparatus for membrane- limited electroplating.
- the seal between plateau areas on the substrate 10 (the conductive surface) and the membrane 13 is maintained by hydrostatic pressure applied to the anolyte solution 16 on the upper (second) surface of the membrane 13.
- the membrane 13 It is therefore advantageous to prevent electrolytic current from flowing to the unsealed areas in order to prevent deposition of metal onto plateaus exposed to plating solution in those areas by providing an electrically insulating barrier mask 14 disposed on or over the membrane to cover those areas of the membrane which do not contact the substrate.
- the mask 14 may comprise a thin, flexible polymeric film bonded, laminated or sealed against either the first or second surface of the membrane 13.
- the mask may comprise any water-immiscible solvent, oil, or grease disposed on the membrane that reduces the electrical conductivity of the membrane by at least factor of 2.
- the masking may be disposed on the exterior of the membrane, as shown, or alternatively, may be disposed on or against the opposite, interior, side of the membrane.
- the ion- conducting membrane is cast on an impermeable web or membrane having openings that define the active area of the membrane. Examples of materials suitable for construction of the mask 14 include, but are not limited to, polyolefins and halogenated polyolefins.
- FIG. 4 Another embodiment of the invention is illustrated in Figure 4.
- the seal between plateaus areas on the substrate and the second surface of the membrane 13 is maintained by mechanical force between the anode 18 and the upper (first) surface of the membrane 13.
- the anode 18 must be a porous structure in order to maintain a layer of anolyte solution or composition 16 adjacent to the anode/membrane interface.
- the anode may be an electrochemically inactive, conductive material such as carbon or a noble metal with at least one smooth, flat surface.
- the anode 18 is immersed in a second fluid (the anolyte 16) and is separated from the plating solution 12 by the membrane 13.
- the lower surface of the anode 18 must be sufficiently smooth and flat to maintain a tight seal between the lower (second) surface of the membrane 13 and the plateau surfaces on the substrate 10.
- materials suitable for construction of the porous anode 18 include, but are not limited to, porous sintered metals, porous carbon or carbon fiber felt or paper.
- the anode 18 comprises a porous, electrochemically inactive, conductive material such as carbon or a noble metal with at least one smooth, flat surface.
- an electrically insulating barrier mask 14 is employed in this embodiment to prevent electric current from flowing to areas of the substrate not contacting the membrane.
- Figure 5 illustrates an embodiment in which the membrane is pressed against the surface of the substrate by mechanical force applied by a porous non-conducting spacer or support 19 situated between the membrane and the anode 15.
- a porous non-conducting spacer or support 19 situated between the membrane and the anode 15.
- the porous support 19 must contain pores or channels filled with anolyte solution or composition in order to maintain a substantially uniform distribution of electrolytic current between the anode and the recessed areas of the substrate.
- materials suitable for construction of the porous support 19 include but are not limited to, open-cell polymeric foams or gels, woven or non-woven fabrics, papers, felts, or porous ceramics.
- the seal between plateaus areas on the substrate and the membrane is maintained by mechanical force between a thin, porous, compliant metal sheet anode, and the upper (first) surface of the membrane.
- This force is applied via a porous, elastic structure.
- Such structures may comprise open-cell foams, honeycomb structures, woven or nonwoven papers or cloths.
- Materials suitable for construction of the porous backing material may include, but are not limited to, silicone elastomers and fluoropolymer elastomers.
- the anode must be porous in order to maintain anolyte solution or composition at the interface between the membrane and the anode.
- FIG. 6 illustrates an embodiment in which the anolyte solution has been replaced by a low-conductivity fluid, for example de-ionized water (DIW).
- DIW de-ionized water
- the bottom side of the membrane 13 makes intimate contact with the substrate 10 only in areas opposite the anode 18, whereas in surrounding areas where the membrane 13 is disengaged from the substrate 10 a gap exists between the anode 18 and the disengaged upper side of the membrane 13. Because of the low conductivity of de- ionized water 16, any current passing through this gap will be subject to an ohmic resistance proportional to the width of the gap.
- the voltage applied between the anode 18 and the substrate 10 is maintained just large enough to provide a desired current, for example a current density between 10 and 200 mA/cm 2 , to recessed areas (trenches and vias) 9 sealed by the membrane 13 where no gap is present between the anode 18 and the first (upper) surface of the membrane 13.
- a desired current for example a current density between 10 and 200 mA/cm 2
- the ohmic resistance due to a small gap, for example 0.1 mm, beyond the edge of the anode 18 will be sufficient to reduce the voltage difference and the current density to a negligible value so that little or no electroplating occurs on areas beyond the edges of the anode 18.
- this embodiment need not require an electrically insulating barrier mask.
- the area of contact between the membrane 13 and the substrate 10 may be continuously moved over the surface of the substrate 10 in such way that the area under the anode 18 always remains in contact. In this manner, fresh plating solution can be continuously replaced in the recessed features 9 and plating current can be maintained without interruption until the desired amount of metal has been deposited.
- the low-conductivity anolyte surrounding the anode will gradually become contaminated by ions, especially when using an anion-conducting membrane in conjunction with an acidic plating solution. Therefore, in order to prevent the conductivity of the low-conductivity fluid from increasing to a point where current can flow beyond the edges of the anode, the low-conductivity fluid anolyte advantageously is continuously replaced.
- Embodiments of this invention are not limited to a single area of contact between the membrane and the substrate.
- An apparatus of this invention can comprise a multiplicity of contact areas involving a single large membrane, a multiplicity of membranes and/or a multiplicity of insulating masks, and may further comprise a multiplicity of anodes and a multiplicity of anolyte solutions.
- Such embodiments can provide advantages for increasing the productivity of the process and/or improving the macroscopic uniformity of the process.
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- 2005-11-11 JP JP2007544484A patent/JP2008522040A/en active Pending
- 2005-11-11 KR KR1020077014928A patent/KR20070089975A/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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WO2006060520A3 (en) | 2006-09-14 |
JP2008522040A (en) | 2008-06-26 |
CN101065520A (en) | 2007-10-31 |
KR20070089975A (en) | 2007-09-04 |
US20060175202A1 (en) | 2006-08-10 |
EP1817443A2 (en) | 2007-08-15 |
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