TW200413573A - Insoluble anode loop in copper electrodeposition cell for interconnect formation - Google Patents
Insoluble anode loop in copper electrodeposition cell for interconnect formation Download PDFInfo
- Publication number
- TW200413573A TW200413573A TW092121579A TW92121579A TW200413573A TW 200413573 A TW200413573 A TW 200413573A TW 092121579 A TW092121579 A TW 092121579A TW 92121579 A TW92121579 A TW 92121579A TW 200413573 A TW200413573 A TW 200413573A
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- Prior art keywords
- anolyte
- anode
- chamber
- solution
- compartment
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- 239000010949 copper Substances 0.000 title description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 20
- 229910052802 copper Inorganic materials 0.000 title description 20
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000004070 electrodeposition Methods 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000012937 correction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 10
- 239000005751 Copper oxide Substances 0.000 claims abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 34
- 238000009713 electroplating Methods 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- -1 hydrogen ions Chemical class 0.000 claims description 9
- 238000005341 cation exchange Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 5
- 238000000909 electrodialysis Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052778 Plutonium Inorganic materials 0.000 claims 1
- 238000001139 pH measurement Methods 0.000 claims 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 claims 1
- 239000010970 precious metal Substances 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 57
- 239000010408 film Substances 0.000 description 34
- 229910000831 Steel Inorganic materials 0.000 description 20
- 239000010959 steel Substances 0.000 description 20
- 238000003860 storage Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 10
- 230000005611 electricity Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001481710 Cerambycidae Species 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000005906 menstruation Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000010 osteolytic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/22—Regeneration of process solutions by ion-exchange
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
狄、發明說明： 【發明所屬之技術領域】 發明之具體實施例廣義上關於在一電化學電鑛系統 中移除與減低氧。 【先前技術】D. Description of the invention: [Technical field to which the invention belongs] The specific embodiments of the invention broadly relate to the removal and reduction of oxygen in an electrochemical power mining system. [Prior art]
深次微米尺寸特徵之金屬化是用於現今與未來世代之 積體電路製程的基本技術。在譬如超大尺寸積體化型式震 置（即具有包含百萬邏輯閘之積體電路裝置）中，置於此等 凌置〜臟部位之多層互連線，大體上係藉由以導電材料（譬 如鋼或鋁）填充高深寬比互連線特徵而形成。習知譬如化學 乳相沈積（CVD)與物理氣相沈積（PVD)之沈積技藝業經使 用於填充此等互連線特徵。然而，隨著互連線尺寸降低與 深寬比增加，經由習知金屬化技藝之無空洞互連特徵漸形 困難。結果，（例如）已出現譬如電化學電鍍（Ecp)與無電極 電鍍之電鍍技藝，作為在積體電路製程中填充深次微米尺 寸之高深寬比互連特徵的可實行製程。Metallization of deep sub-micron size features is a fundamental technology used in integrated circuit manufacturing processes for today and future generations. For example, in a super-large-scale integrated type seismic installation (that is, an integrated circuit device including a million logic gates), the multilayer interconnection lines placed in these locations are generally made of conductive materials ( (Such as steel or aluminum) filled with high aspect ratio interconnect features. Conventional deposition techniques such as chemical emulsion deposition (CVD) and physical vapor deposition (PVD) have been used to fill these interconnect features. However, as interconnect sizes decrease and aspect ratios increase, void-free interconnect features become increasingly difficult through conventional metallization techniques. As a result, electroplating techniques such as electrochemical plating (Ecp) and electrodeless plating have emerged as feasible processes for filling high-aspect-ratio interconnect features with deep sub-micron dimensions in integrated circuit manufacturing processes.
在形成於基材表面的一 ECP製程次微米尺寸高深究比 特徵中，可用導電材料（譬如銅）有效地予以填充。Ecp電 鍍製程大體上為二階段製程，其中會先於基材之表面特徵 上形成一晶種層，隨後會曝露該基材之表面特徵於一電^ 質溶液中’同時會施加一電性偏壓至該基材與位於電解質 溶液中之陽極間。該電解質溶液大體上富含待電鍍於該基 材表面上之離子。目此，電性偏壓之應用造成此等離子： 3 200413573 推動離開電解f溶液且電鍍於該晶種層上成為金屬。所電 鍍之金屬（其可能為銅）例如可成長至一定厚度且形成一填 充形成於基材表面上該等特徵的鋼層。 為了有助於且控制此電鍍製程，可使用數種添加劑於 電解質電鍍溶液中。例^，用於鋼電鍍之典型電解質溶液 可由具有添加硫酸與銅氯化物於其中之銅硫酸鹽溶液組成 (以提供待電鍍之銅）。大體上可操作該硫酸以改良該溶液 之酸性與導電率。電解質溶液大體上也含有各種有機分 子，包括加速劑、抑制劑、均染劑、光亮劑等。添加此等 有機刀子大體上疋為了有助於無空洞超填充高深寬比特徵 與平坦化銅沈積。 再者，習知系統可使用一可溶金屬陽極以連續供應金 屬離子用於補充電解液。然而，陽極溶解會有譬如不符需 求之副產品（如形成沉澱物與銅球）、不符需求之副作用（如 陽極鈍化層、不均一陽極溶解與有機添加物消耗/崩散）之 缺點。因此，可於電化學電鍍系統中使用不可溶陽極。然 而’施加於該陽極之電性偏壓可能會造成氧化，因此會因 氧或氧氣泡而使電鍍溶液飽和。氧氣泡可造成不符需求之 副效應，譬如銅沈積分佈不均一、在基材上形成氣泡及阻 隔電鍍槽中之陽極與薄膜。因此，需求使半導體電鍍槽内 氧之形成與影響最小之方法與設備，其中該方法與設備能 克服習知裝置之缺點。 【發明内容】 4 200413573 本 電化學 解液室 極及一 基材支 括一置 膜，及 陽極電 約5(M 本 與該陰 統，該 化學電 修正裝 多餘之 本 法。該 電解液 體上以 電解液 液溶液 液室係 陽極電. 包括鋼. 發明具體實施例 電鍍系統大體上 之電鍍槽，該陽 陽極電解液。該 樓構件與一陰極 於該陽極電解液 一以流體與該陽 解液至陽極電解 >分之線性速度 廣義上有關一電化 包括一具有陽極電 極電解液室在其内 陰極電解液室大體 電解液。此外，該 室與陰極電解液室 極電解液室連接之 液室之該果具有介 學電錢系統。該 解液室與陰極電 具有一不可溶陽 上在其内包括一 電鍍槽大體上包 間之離子交換薄 泵，經配置提供 於每秒約〇 · 5至In an ECP process with a submicron size-to-depth ratio feature formed on the substrate surface, it can be effectively filled with a conductive material such as copper. The ECP electroplating process is generally a two-stage process, in which a seed layer is formed on the surface features of the substrate, and then the surface features of the substrate are exposed in an electrical solution, and an electrical bias is applied. Press between the substrate and the anode in the electrolyte solution. The electrolyte solution is substantially rich in ions to be plated on the surface of the substrate. For this reason, the application of electrical bias results in this plasma: 3 200413573 Push away from the electrolytic f solution and electroplated on the seed layer to become a metal. The electroplated metal (which may be copper), for example, can grow to a certain thickness and form a steel layer that fills these features formed on the surface of the substrate. To assist and control this plating process, several additives can be used in the electrolyte plating solution. Example ^ A typical electrolyte solution for steel electroplating may consist of a copper sulfate solution with sulfuric acid and copper chloride added thereto (to provide the copper to be electroplated). The sulfuric acid can generally be manipulated to improve the acidity and conductivity of the solution. The electrolyte solution also generally contains various organic molecules, including accelerators, inhibitors, leveling agents, brighteners, and the like. The addition of these organic knives has generally been used to facilitate void-free superfill high aspect ratio features and flatten copper deposition. Furthermore, the conventional system can use a soluble metal anode to continuously supply metal ions for replenishing the electrolyte. However, anodic dissolution has disadvantages such as undesirable by-products (such as the formation of deposits and copper balls), and undesirable side effects (such as anodic passivation layer, uneven anodic dissolution, and organic additive consumption / disintegration). Therefore, insoluble anodes can be used in electrochemical plating systems. However, the electrical bias applied to the anode may cause oxidation, and therefore the plating solution may be saturated by oxygen or oxygen bubbles. Oxygen bubbles can cause undesired side effects, such as uneven copper deposition distribution, formation of bubbles on the substrate, and blocking of anodes and films in the plating bath. Therefore, there is a need for a method and equipment that minimizes the formation and influence of oxygen in a semiconductor plating bath, wherein the method and equipment can overcome the shortcomings of conventional devices. [Summary of the Invention] 4 200413573 The electrode of the electrochemical solution chamber and a substrate support a film, and the anode electricity is about 5 (M and the vaginal system, the chemical electricity correction is equipped with an excess of this method. The electrolyte body is Electrolyte solution solution chamber is the anode electricity. Including steel. The specific embodiment of the invention is an electroplating tank, the anode and the anode electrolyte. The building component and a cathode are in the anode electrolyte, and the electrolyte is used to dissolve the anode. Liquid-to-anodic electrolysis > linear velocity is broadly related to an electrification including a catholyte chamber having an anode electrode electrolyte chamber therein and a general electrolyte. In addition, the chamber is connected to the catholyte chamber and the electrolyte chamber. The fruit of the chamber has a dielectric electricity system. The decomposing chamber and the cathode have an insoluble ion exchange thin pump including an electroplating tank and a substantially enveloping chamber, which is configured to provide about 0 ·· per second. 5 to
發明具體實施例更包括一具有置於該陽極電解液室 極電解液室間之陽離子交換薄膜的電化學電錄系 陽離子交換薄膜對氫離子與鋼離子具選擇性。該電 鍍系統可更包括一以流體與該陽極電解液室連接之 置，該修正裝置包括經配置以中和該陽極電解液中 酸的銅氫氧化物、銅氧化物與其組合物中至少之一。 發明具體實施例更包括用於在基材上電鍍金屬之方 方法大體上包括供應陽極電解液溶液至一具有陽極 室與陰極電解液室之電鍍槽。該陽極電解液溶液大 介於每秒約0.5至約50公分之線性速度通過該陽極 室。該方法更包括以置於陰極電解液室之陰極電解 在該基材上電鍍金屬（該陽極電解液室與陰極電解 由一離子交換薄膜隔離）、從該電鑛槽移走使用過之 解液且傳送一部份已使用之陽極電解液溶液通過一 氡化物、銅氫氧化物與其組合物中至少之一的修正A specific embodiment of the invention further includes an electrochemical recording system having a cation exchange membrane disposed between the anolyte compartment and the anolyte compartment. The cation exchange membrane is selective for hydrogen ions and steel ions. The electroplating system may further include a fluid connection to the anolyte chamber, and the correction device includes at least one of a copper hydroxide, a copper oxide, and a composition thereof configured to neutralize an acid in the anolyte. . Embodiments of the invention further include a method for electroplating a metal on a substrate. The method generally includes supplying an anolyte solution to a plating bath having an anode chamber and a catholyte chamber. The anolyte solution passes through the anode chamber at a linear velocity of about 0.5 to about 50 cm per second. The method further includes electroplating metal on the substrate by catholyte placed in a catholyte chamber (the anolyte chamber and the catholyte are separated by an ion exchange membrane), and removing the used solution from the electric ore tank And transmit a portion of the used anolyte solution through the correction of at least one of a halide, copper hydroxide and its composition
5 200413573 裝置。 【實施方式】 第1圖示 電鍍系統100 超填充電鍍之 之另一電鍍槽 待電鍍之基材 11 2，在流動上 或電鍍槽101 置以提供一第 1 0 8 (即，介於 積），及一第 110(即，位於衰 更包括一經配 解液進口 105 液之陽極電解 經配置以 轉頭1 26，大骨 溶且在電鍍製 積，藉以增加 多孔線網、一 品、燒結金屬 由鈦或固體白 摩巳用於本發明具體實施例之一電鍍系統。該 大體上包括一電鍍槽1〇1，其可為一用於銅 電化學電鍍（ECP)槽或在半導體技藝中已知 配置。ECP槽101大體上經配置以藉由位於 123與電鍍槽101之陽極122間的一薄膜 隔離電鍍槽ιοί的一陽極122與一陰極124 之電鍍電極。此外，ECP槽1〇1大體上經配 一電鍵溶液（陽極電解液）予一陽極電解液室 陽極122上表面與薄膜112下表面間之容 二流體溶液（陰極電解液）予一陰極隔室 I膜上表面上之流體容積）。此外，電鍍槽 置以傳輸陽極電解液至電鍍槽101之陽極電 ，及一經配置以從電鍍槽i 〇丨移走陽極電解 液出口或排放口 106。 將一基材沉積表面曝露於該電鍍溶液的一旋 堂上會支撐陰極124。陽極122大體上係不可 程中不會消耗。陽極122可具有一較大表面 與電鍍溶液之接觸。例如，陽極丨22可為一 筛籃、或由碳纖維形成之金屬格柵、碳毛織 或金屬化鈦氮化物纖維。陽極丨22也可為〜 金箔形成之薄碟或環。陽極122可更包括〜 6 200413573 可在氧電禱之酸性媒介中穩定之鍍鉑、鉑銥、鉑合金或其 他責重金屬的塗層。 薄膜11 2大體上經配置以防止陽極副產品進入陰極電 解液110中’因此可藉由降低出現在所電鍍基材上之缺陷 數置而增加電鍍效能。此外，薄膜11 2大體上可防止有機 添加物從陰極電解液室110擴散進入陽極電解液室108。 防止添加物移動至陰極電解液室110可避免添加物崩散及 大體上因添加物接觸陽極1 22造成污染。薄膜i i 2可包括 離子父換薄膜，譬如一陽離子交換薄膜或一陰離子交換 薄膜。 這些薄膜可為許多市售薄膜中之一。例如，kUyama 公司製造與以註冊商標“ Ne〇Septa，，供應用於電滲析與相 關應用之各種碳氫化合物薄膜。能在氧化中穩定且當需要 以陽離子薄膜隔離不可溶陽極隔室時可用之過氟酸陽離子 薄膜，大體上可用杜邦（DuPont)公司Nation薄膜n_U7、 N-450 ’或朝日（Asahi)玻璃公司（日本）註冊商標中 之Fx-50、F73 8、F893型薄膜。朝曰玻璃公司也在相同之 註冊商標Selemion下生產一系列以聚苯乙烯為主之離子 交換薄膜，其對於電解液之集中/去鹽作用與有機物移除特 別有效（陽離子薄膜、CMV、CMD與CMT及陰離子薄膜 AMV、AMT與AMD)。另有些公司製造類似離子交換薄膜 (Solvay(法國）、Sybron化學公司（美國），I〇nics(美國）與 FuMA科技（德國）等）。再者，為了使穿入陰極隔室之銅離 子最少，可藉著一5 200413573 device. [Embodiment] The first illustrated electroplating system 100 is super-filled with another electroplating tank. The substrate 11 2 to be electroplated is placed on the flow or electroplating tank 101 to provide a first 10 8 (ie, between products). , And a 110th (that is, the anode electrolysis located in the decay solution including a solution solution inlet 105 liquid is configured to turn the head 1 26, large osteolytic and electroplating product, thereby increasing the porous wire network, a product, sintered metal by Titanium or solid white capricorn is used in one of the embodiments of the present invention. The plating system generally includes a plating bath 101, which may be a copper electrochemical plating (ECP) bath or is known in semiconductor technology. Configuration. The ECP tank 101 is generally configured to isolate a plating electrode of an anode 122 and a cathode 124 by a thin film located between 123 and the anode 122 of the plating tank 101. In addition, the ECP tank 101 is generally An electric bond solution (anolyte) is assigned to a volume of fluid between the upper surface of the anode 122 and the lower surface of the membrane 112 of the anolyte chamber (cathode electrolyte) to the volume of the fluid on the upper surface of the cathode compartment I membrane) . In addition, the plating tank is configured to transfer the anolyte to the anode of the plating tank 101, and is configured to remove the anode electrolytic solution outlet or discharge port 106 from the plating tank io. The cathode 124 is supported by exposing a substrate deposition surface to a spiral of the plating solution. The anode 122 is generally not consumed in the process. The anode 122 may have a larger surface in contact with the plating solution. For example, the anode 22 may be a sieve basket, or a metal grid formed of carbon fibers, carbon wool, or metallized titanium nitride fibers. The anode 22 can also be a thin plate or ring formed of gold foil. The anode 122 may further include a coating of platinum, platinum iridium, a platinum alloy, or other heavy metals that is stable in an acidic medium of oxygen electricity. The thin film 112 is generally configured to prevent anode by-products from entering the cathode electrolyte 110 'and thus can increase the plating efficiency by reducing the number of defects occurring on the plated substrate. In addition, the thin film 112 can substantially prevent organic additives from diffusing from the catholyte chamber 110 into the anolyte chamber 108. Preventing the additives from moving to the catholyte chamber 110 can prevent the additives from disintegrating and causing contamination due to the contacts of the additives from the anode 12. The membrane i i 2 may include an ion-exchange membrane, such as a cation exchange membrane or an anion exchange membrane. These films can be one of many commercially available films. For example, kUyama Corporation manufactures and supplies a variety of hydrocarbon films for electrodialysis and related applications under the registered trademark "Ne〇Septa." It is stable in oxidation and can be used when cationic films are required to isolate insoluble anode compartments. Perfluoric acid cationic films can generally be used as DuPont's Nation film n_U7, N-450 'or Fx-50, F73 8, F893 type films in the registered trademark of Asahi Glass Company (Japan). Chaoyue Glass The company also produces a series of polystyrene-based ion exchange membranes under the same registered trademark Selemion, which is particularly effective for electrolyte concentration / desalting and organic matter removal (cationic membranes, CMV, CMD and CMT, and anions Thin film AMV, AMT, and AMD). Other companies make similar ion exchange films (Solvay (France), Sybron Chemical Company (USA), Ionics (USA), FuMA Technology (Germany), etc.). The minimum amount of copper ions entering the cathode compartment can be obtained by
集在一起之雙 200413573 極離子交換薄膜而有助於隔離。譬如型號 AQ-BA AQ-BA-04之雙極薄膜可來自Aqualitics(美國）與朝 公司之市售品。 操作時，薄膜112大體上不接觸陽極122。與陽 接觸大體上會影響電鍍效能與陽極1 22操作。因此 112離陽極122之距離大體上大於〇.1亳米。較佳 薄膜112離陽極122之距離從約〇·5毫米至約10毫 在某些具體實施例中，電鍍槽101可更包括一 極電解液進口 11 6與陰極1 24間之擴散器1 28。流 器128提供電鍍溶液越過流體擴散器128上電鍍槽 度時之實質均一速度。橫越基材123之電鑛情況均 此將因更均勻的流動情況而增強。流體擴散器1 2 8 實質上很堅固。在此揭露書中，名詞‘‘堅固，，指擴散 理槽之正常操作條件下，具有結構上之堅固性以限 體擴散器充分變形或彎曲（其將改變陽極與沉積於 積表面之晶種層間的電阻）此變形會使攘散器1 2 8 以致比擴散器128周邊較接近在基材123上之最靠 的擴散器128中心是在最靠近基材ι23之位置。流 器128最好是由微觀上大體圓狀、陶瓷微粒所形成 球狀接觸點處被燒結至流體擴散器丨28的鄰接球狀 陶瓷疋一天然親水性材料。其他適當的（實質上堅g 料均可使用。空洞或空間會形成於相鄰之陶瓷微粒 政器128經設計為具有尺寸從约〇·丨微米至约5〇〇 細孔。因為該流體通過流體擴散器128之流動阻抗 -06與 曰玻璃 極122 ，薄膜 的是， 米。 置於陰 體擴散 101寬 一性因 之構造 器在處 制該流 基材沉 彎曲， 近位置 體擴散 ，其在 微粒。 3)之材 間。擴 微米之 是流體 200413573 行經流體擴散器1 28之距離的函數，田比1 ^ , . , , + 因此可改變擴散器128 之垂直冋度以提供需求之流體流動特 令徵例如，具有相同 細孔尺寸的一較厚流體擴散器128， 會經由流體擴散器128 增加流體之阻抗，以提供比經由且右 ，、有相同細孔尺寸之流體 擴散器128更受限制之流動。雖然在 ·、、在此描述的是一流體擴 散器，任何熟習此項技藝人士已知緩 方、、&配置以提供均勻流動 之結構均可使用。Bunch of double 200413573 polar ion exchange membranes to aid isolation. For example, the bipolar film of model AQ-BA AQ-BA-04 can be obtained from the commercial products of Aqualitics (USA) and North Korea. In operation, the film 112 does not substantially contact the anode 122. Contact with anodes generally affects plating performance and anode 1 22 operation. Therefore, the distance between 112 and anode 122 is generally greater than 0.1 mm. The distance between the preferred film 112 and the anode 122 is from about 0.5 mm to about 10 millimeters. In some embodiments, the plating tank 101 may further include a diffuser 1 between the electrolyte inlet 11 6 and the cathode 1 24. . The flow 128 provides a substantially uniform velocity of the plating solution as it passes over the plating bath on the fluid diffuser 128. All the electric ore conditions across the substrate 123 will be enhanced by more uniform flow conditions. The fluid diffuser 1 2 8 is substantially strong. In this disclosure, the term "sturdy" refers to the structural rigidity of the diffuser tank under normal operating conditions to limit the body diffuser's full deformation or bending (which will change the anode and the seed crystals deposited on the product surface). The resistance between layers) This deformation will cause the diffuser 1 2 8 so that the center of the diffuser 128 closest to the substrate 123 is closer to the substrate 123 than the periphery of the diffuser 128. The flow device 128 is preferably made of a generally circular micro-shaped, ceramic particles formed at a spherical contact point and sintered to the adjacent spherical ceramic of the fluid diffuser 28, a natural hydrophilic material. Other suitable (substantially hard materials) can be used. Cavities or spaces will be formed in the adjacent ceramic microparticles 128. They are designed to have pores with a size from about 0.00 micron to about 5000. Because the fluid passes The fluid resistance of the fluid diffuser 128 is -06 and the glass pole is 122. The thickness of the thin film is 100 meters. The structure is placed on the diffuser of the vaginal body and the structure of the diffuser is bent and diffused in the near position. Among the particles. 3). The micron expansion is a function of the distance of the fluid 200413573 passing through the fluid diffuser 1 28. The field ratio 1 ^,.,, + Can therefore change the vertical angle of the diffuser 128 to provide the required fluid flow special features. For example, with the same fineness A thicker fluid diffuser 128 with a pore size will increase the resistance of the fluid through the fluid diffuser 128 to provide a more restricted flow than a fluid diffuser 128 with the same fine pore size passing through and to the right. Although a fluid diffuser is described herein, any structure known to those skilled in the art as a relief, & configuration to provide uniform flow can be used.
第1圖所示代表性電鍍系統1GGA體上包括—陽離子 交換薄膜U2。陽離子交換薄膜112大體上係對正電荷離 (如氫離子（H + )與銅離子（Cu2 + ))具選擇性；因此h +與π2 — 會從陽極電解液室108移動至陰極隔室ιι〇。大體上，從 陽極電解液室108移動至陰極隔室"〇之離子應包括從约 95%至約98%之Cu2、子。該Cu2 +之移動大體上是需要用 以補償因銅電鍍在陰極電解液溶液中損失之銅。銅移動之 結果會使該陽極電解液銅濃度降低且隨時間酸性更強。A representative electroplating system 1GGA shown in FIG. 1 includes a cation exchange film U2. The cation exchange membrane 112 is generally selective for positively charged ions (such as hydrogen ions (H +) and copper ions (Cu2 +)); therefore, h + and π2 — will move from the anolyte chamber 108 to the cathode compartment. 〇. In general, the ions moving from the anolyte chamber 108 to the cathode compartment " 0 should include Cu2 from about 95% to about 98%. This Cu2 + movement is generally needed to compensate for the copper lost in the catholyte solution due to copper plating. As a result of copper migration, the copper concentration of the anolyte decreases and becomes more acidic over time.
當使用一陽離子交換薄膜112時，該陽極電解液大體 上L括從約〇 〇5莫耳（M)至約i莫耳硫酸鋼及一最低量之 酉文（如’一足夠供陽極電解液從約2至6之pH值的量），且 更佳是提供從約2.5至約4之PH值。該酸可包括硫酸、磷 文及/或其衍生物。除了銅硫酸鹽外，電鍍溶液可包括其他 、s u^類 4如氟删酸鋼、葡萄糖酸銅、續酸銅、石風酸銅、 焦鱗酸鋼、氣化鋼、氰化銅。然而，本發明之具體實施例 並不限制於這些參數。該陽極電解液可進度包括鹽類，譬 如金屬配位劑或錯合劑，以避免陽極鈍化或減低陽極沉渣 9 200413573 之形成。 陰極電解液大體上包括銅硫搜鹽、硫酸及少量之銅氯 化物（如，從約20ppm至約8〇ppm)。該電鍍溶液可更包栝 一或多數添加物。添加物（其可以是例如均染劑、限制劑、 抑制劑、光亮劑、加速劑或此技藝中其他已知之添加物） 通常會吸附於被電鍍基材123之表面上。有用之抑2劑（吸 附於基材表面）大體上包括之聚醚（譬如聚乙烯二醇”或其 他聚合物（譬如聚乙烯-聚丙烯氧化物），可減緩鋼沉積於該 吸附區域上。有用之加速劑（與抑制劑競爭吸附位置）大體 上包括硫化物或二硫化物（譬如雙（3-磺酸丙基）二硫化 物）’加速銅沉積於吸附區域上。有用之均染劑大體上包栝 噻二唑（thiadiazole)、咪唑（imidaz〇le)或其他含氮有機物。 有用之限制劑通常包括安息香酸鈉與硫酸鈉。在電鑛時， 添加物會消耗於基材表面處，但會固定地由電錢溶液重新 補充。然而，各種添加物之擴散速率差異造成特徵之頂部 與底部表面處濃度不同，因此在基材123之特徵内須設定 不同之電鍍速率。理論上，在由底向上填充時，這些電鍍 速率在底部應較高。因此，在電鍍溶液中需要適當組成之 添加物以使特徵達到一無空洞填充。 陽極電解液會經由陽極電解液進口 1 0 5 (其係藉流體 連接至一陽極電解液儲存單元102)傳送進入電錢槽1〇1。 一流體泵104大體上是位於陽極電解液儲存單元ι〇2與電 錢槽1 0 1間’且係配置以尚線性流動率傳送陽極電解液至 電鍍槽101。大體上，陽極電解液是藉由使陽極電解液駐 10 200413573 留在陽極電解液室1 08時間最少，以足夠防止陽極電解液 氧飽和之流動率進入陽極電解液室1 〇8。例如，陽極電解 液之流動率可介於約0.5公升/分鐘至約2〇公升/分鐘間， 且更特別是介於約1公升/分鐘至約1 〇公升/分鐘間。陽極 電解液流動速率大體上會根據陽極電解液進口 之直 徑。例如，進口愈大，需要之陽極電解液流動速率愈低。 此外，該陽極電解液流動速率大體上會導致從約〇5 公分/秒至約50公分/秒之需求線性速度。在陽極122表面 處之線性速度係該陽極電解液流動速率、陽極直徑與陽極 122與薄膜112間距離的一函數。因此，2〇0公分基材與 300公分基材之陽極電解液流動速率將會不同。可操作一 較高陽極電解液流動速率，以減低形成在陽極丨22處之氧 氣泡及該陽極過度酸化，結果可縮短靠近陽極丨22處之陽 極電解液駐留時間，（如，陽極電解液會以比氧飽和所需更 短時間通過電鍍槽101)。再者，任何形成在陽極之氧會由 南速經其間之極電解液從陽極電解液室1 〇 8移走。 雖然高流動速率大體上可消除氧形成，使用低陽極電 解液流動速率之系統可能會需要額外的處理。因此，陽極 電解液出口 106大體上可與一管柱13〇(其具有一出口）之 入口以流體連接，該管柱與一過濾器丨34以流體連接。管 柱130可不只包括一管柱，其中一管柱含有氧化銅（Cu〇) 而另一管柱含有氫氧化鋼（CWOH)2))。當使用不只一管杈 時’可使用闊控制陽極電解液流動，以致陽極電解液可根 據槽102中陽極電解液之pH值程式流經任一管柱。第1 圖顧示單 需求使用 包括將陽 1 3 0間之 分開且由 會傳送至 柱130之 電解液的 最好是從 130° 200413573 一管柱（較佳是包括Cu(0H)2)，然而可根據 任何數量之管柱。大體上’第1圖所示系統 極電解液傳送至置於陽極電魅访 电鮮液出口 106與 閥132。流到管柱13〇之陽極 勿位電解液可由閥 閥132與140加以控制，其餘流動之陽極電 陽極電解液健存槽1〇2。決定陽極電解液經 流動包括監測在陽極電解液儲存槽丨〇2内之 PH。當該陽極電解液之ph增加（陽極電解夺 約2至約6)時，較大量之陽極電解液可流經 管柱130大體上包括一其内置有粉體或固體型式 或Cu(OH)2之殼體。該粉體可置於一匣中，由一網狀 構件支撐’或由熟習此項技藝人士已知之另一^冓件支 在操作時，將陽極電解液傳送通過含有氧化鋼或 化銅之管柱1 3 0會導致下列反應：When a cation exchange membrane 112 is used, the anolyte generally includes from about 0.05 mol (M) to about 1 mol sulfuric acid steel and a minimum amount of scripture (such as' a sufficient supply of anolyte From about 2 to 6), and more preferably provides a pH from about 2.5 to about 4. The acid may include sulfuric acid, phosphorus and / or derivatives thereof. In addition to copper sulfate, the electroplating solution may include other types such as fluoroacid steel, copper gluconate, copper sulphate, copper rheinite, pyroscale steel, gasified steel, and copper cyanide. However, the specific embodiments of the present invention are not limited to these parameters. The anolyte can include salts, such as metal complexes or complexing agents, to avoid anodic passivation or reduce the formation of anodic deposits 9 200413573. The catholyte generally includes copper sulfur search salt, sulfuric acid, and a small amount of copper chloride (e.g., from about 20 ppm to about 80 ppm). The plating solution may contain one or more additives. Additives (which may be, for example, leveling agents, limiters, inhibitors, brighteners, accelerators, or other known additives in the art) are generally adsorbed on the surface of the substrate 123 to be plated. Useful polyethers (such as polyethylene glycol) or other polymers (such as polyethylene-polypropylene oxide) that are generally included in the inhibitor (adsorbed on the surface of the substrate) can slow down the deposition of steel on the adsorption area. Useful accelerators (competing with adsorption sites for inhibitors) generally include sulfides or disulfides (such as bis (3-sulfopropyl) disulfide) to accelerate copper deposition on the adsorption area. Useful levelling agents Generally, thiadiazole, imidazole, or other nitrogen-containing organic compounds are included. Useful limiting agents usually include sodium benzoate and sodium sulfate. In the case of power mining, additives are consumed at the surface of the substrate. However, it will be fixedly replenished by the electricity solution. However, the difference in the diffusion rate of various additives causes the concentration at the top and bottom surfaces of the feature to be different, so different plating rates must be set within the feature of the substrate 123. In theory, When filling from bottom to top, these plating rates should be higher at the bottom. Therefore, an additive of the appropriate composition is needed in the plating solution to achieve a void-free filling feature. Anode The solution is transferred to the electric money tank 101 via the anolyte inlet 105 (which is fluidly connected to an anolyte storage unit 102). A fluid pump 104 is generally located in the anolyte storage unit. 2 and the electric money tank 1 0 1 'and are configured to transfer the anolyte to the plating tank 101 with a still linear flow rate. Generally, the anolyte is left in the anolyte chamber 1 by leaving the anolyte 10 200413573 The 08 time is the minimum to prevent the oxygen saturation of the anolyte from flowing into the anolyte chamber 108. For example, the anolyte flow rate can be between about 0.5 liters / minute to about 20 liters / minute, and More particularly between about 1 liter / minute to about 10 liters / minute. The anolyte flow rate will generally be based on the diameter of the anolyte inlet. For example, the larger the inlet, the lower the anolyte flow rate required In addition, the anolyte flow rate generally results in a required linear velocity from about 0.05 cm / s to about 50 cm / s. The linear velocity at the surface of the anode 122 is the anolyte flow rate , The anode diameter and the distance between the anode 122 and the thin film 112. Therefore, the anolyte flow rate will be different for a 200 cm substrate and a 300 cm substrate. A higher anolyte flow rate can be manipulated to The oxygen bubbles formed at the anode 22 and the excessive acidification of the anode can be reduced. As a result, the residence time of the anode electrolyte near the anode 22 can be shortened (for example, the anode electrolyte can pass through the plating tank in a shorter time than that required for oxygen saturation). 101). Furthermore, any oxygen formed in the anode will be removed from the anolyte chamber 108 by Nansu through the polar electrolyte in between. Although a high flow rate substantially eliminates oxygen formation, use a low anolyte flow Rate systems may require additional processing. Therefore, the anolyte outlet 106 may generally be fluidly connected to the inlet of a column 13 (which has an outlet) that is fluidly connected to a filter 34 . The tubing column 130 may include more than one tubing column, wherein one tubing column contains copper oxide (Cu0) and the other tubing column contains steel hydroxide (CWOH) 2)). When more than one pipe branch is used, the anolyte flow can be controlled so that the anolyte can flow through any column according to the pH formula of the anolyte in the tank 102. Figure 1 shows the requirements for the use of the electrolyte, which includes the separation between the anode and the anode, and is transmitted to the column 130. It is preferably a column from 130 ° 200413573 (preferably including Cu (0H) 2). However, any number of columns can be used. Generally, the system shown in Fig. 1 transmits the electrolyte to the anode outlet 106 and the valve 132. The anode electrolyte flowing to the column 13 is controlled by the valves 132 and 140, and the rest of the anode current is stored in the anode electrolyte storage tank 102. Determining the flow of anolyte includes monitoring the pH in the anolyte storage tank. When the ph of the anolyte is increased (about 2 to about 6 for anolyte), a larger amount of anolyte can flow through the column 130. Generally, the anolyte contains a powder or solid type or Cu (OH) 2, case. The powder can be placed in a box and supported by a mesh member 'or another piece known by those skilled in the art. During operation, the anolyte is transferred through a tube containing oxidized steel or copper. Column 1 3 0 causes the following reactions:
CuO + H2S〇4 = H20 + CuS04 (1)CuO + H2S〇4 = H20 + CuS04 (1)
Cu (OH)2 + H2S〇4 = 2H2〇 + CuS〇4 (2) 該氧化銅或氫氧化鋼在接觸過量酸時會分解，因 將在陽極電解液中出現之過量酸轉變成硫酸銅。雖然 一管柱加以說明，陽極電解液中過量之酸矸用任何熟 項技藝人士所知之方法加以中和。陽極電解浪接著可 一經配置以移除餘留在陽極電解液溶液中之氧化鋼^ 化銅的過濾器1 3 4。例如，該陽極電解液4通過一過 134。在處理時，該陽極電解液大體上具有約2·6至乡 系統 100 管柱 132 解液 過管 陽極 t pH 管柱 CuO 支撐 氫氧 此會 是以 習此 通過 氫氧 濾器 ]3.6 12 200413573 之pH值。； 單元102連 存單元1 02 移除裝置， 以在該陽極 液移除至少 此外， 一輸出的電 至陰極電解 電解液進口 大體上 101至陰極 接受部份之 存陰極電解 11 8供後續. EDC是接受 可只接受一 實施，如經 第2匮 圖。代表性 體基材上之 一配置以容 200之第一 二端大體上 愚渡器134大體上是以流體與陽極電解液儲存 接。再者，在將該陽極電解液從陽極電解液儲 傳送至電鍍槽101前，該陽極電解液可通過一 譬如一除氣器136。除氣器136大體上經配置 電解液進入陽極電解液室1〇8前，從陽極電解 · 部份溶解氣體（譬如氧與氮）。 · 一陰極電解液出口 114可以流體連接至具有一 參析槽{EDC}之輸入處，該EDC可以流體連接 籲 液储存單元118。該陰極電解液係經由一陰極 11 6再循環至該陰極電解液室。 ，EDC室1 3 8是經配置以接受一部份從電鍍槽 電解液儲存單元118之已使用陰極電解液。所 已使用陰極電解液會在EDC 130内中和產生儲 液，其接著可被再導入陰極電解液儲存單元 在電鍍操作中使用。雖然第1圖所示之代表性 經由出口 11 4傳送之整個陰極電解液，可預期 部份已使用陰極電解液之各種EDC配置均可 鲁 由一分流型式配置。 丨顯示一代表性陰極電解液ED C 1 3 8之線路簡 EDC 138(例如）可在一經配置以電鍍銅至半導 ECP系統内實施。代表性EDC 138大體上包括 置或限制EDC 138基本元件之殼體2〇〇。殼體 端大體上包括一鋼陽極源2〇2,而殼體2〇〇之第 包括一陰極源204。陽極源2〇2與陰極源2〇4 ’ 13 200413573 大體上是位於殼體200之相反/相對端。殼體2〇〇内介於陽 極源202與陰極源2〇4間之容積大體上包括複數個隔室， 其中該等隔室大體上包括對應於分別位於殼體2〇〇各端之 陽極202或陰極204的一陽極隔室206與一陰極隔室2〇8。 已使用之陰極電解液會經由導管210供應至EDC槽138。 導管210供應已使用之陰極電解液進入edC槽138内的一 輸入室212。具選擇性之滲透薄膜會個別分隔各自的隔室。 一陰離子薄膜2 1 4(其較佳是對特別是硫酸根之單價 陰離子具選擇性且可穿過）大體上會隔開陽極隔室2〇6與 輪入室212。一雙極薄膜216會隔開輸入室212與陰極隔 室 通 室 顯 208。可經由導管218與22〇(其經操作以循環該酸溶液 過各自的隔室）供應硫酸溶液至陰極隔室2〇8與陽極隔 2 06。該硫酸大體上是經稀釋。因此，一額外之導管（未 示）可供應去離子水至各個隔室或至導管218與22〇。 橫 是 操作中，會經由陽極2〇4與陰極2〇2施加一電性偏壓 5 EDC槽128大體上陽極2〇2與陰極2〇4間之電壓降 從約0·4伏特至約1·5伏特。應用於edc槽之電性 偏壓的作用是推動在已使 1之用险極電解液溶液中之離子朝向 各自的電極，即正離子會祜 r被:推向陰極204，而負離子會被 推向陽極202。因此，p你m L 、 已使用陰極電解液中已分解之硫酸 鹽離子（大體上如第2圖戶斤- 2 斤不之S〇4 )會朝陽極202之方向 被推離已使用之陰極電解 鮮液。冋理，已分解之氫氧化物離 子（大體上顯示為OH·)會拙從 7玲破推向陽極202方向，而已分解 之氫離子（大體上顯示為Η+、合、 Η )會被推向陰極204方向。再 14 ‘UU413573 者’雖然Cu2 +也會穿過薄膜216，其量則可忽略，因為移 動至陰極隔室208之H+的流率約是銅離子移動的i〇〇倍。 該氣氧化物離子會中和出現在陰極電解液中過量之酸。此 外’雙極薄膜2 1 6允許從已使用陰極電解液中移除H+以進 、步中和過量之酸。所形成之酸性硫酸銅溶液接著可經由 導s 222從輸入室212移動，且再循環進入電鍍系統（或一 電解溶液槽等）中，因為CuS〇4/H2S〇4是用於銅電鍍系統之 電解办液中的主要元素。因此，EDc 138大體上可操作以 從電鍍系統接收已使用電解液且從已使用電解液中分離 2各種成份（硫酸銅與硫酸）供該電鍍系統再使用。雖然過 量之酸已在處理時中和，在陰極電解液中之銅可能會耗 盡因此可添加硫酸鋼與添加物至陰極電解液儲存槽 此外，無水硫酸銅可在先前計量加人陰極電解液料 早70 11 8或儲存後加入該陰極電解液。此外，彳實施 138之替代性具體實施例以進一步修正該銅濃度。該替代 t刪可”—陽離子薄膜而非陰離子薄膜，且通過陽極 隔至206循％ 一濃硫酸銅溶液以提供ah移動通過該薄膜 且進入已使用之陰極電解液。 、 第3圖顯示納入一陰離早植胳 電鐘系統3。0舆第1圖所-不；^3°2之電鑛系統3〇°。 不不同在於，該陽極電解液大體 上疋了之酸溶液(如，從約。·〇5μ至約Ο·。該酸大 體上疋硫酸。該陽極電 更 .^ 了更包括一有機或無機成份之 還原劑。例如，該陽極電解 —^ ^ . 电解及T包括已溶解之氣體氫、對 本一酴、蟻I '鐵離子（2 + 丁 )碘化鉀、錳離子（Mn2 + )或其 15 200413573 等之組合物。當氣體氫包含於該陽極電解液中時，在陽極 電解液儲存槽102中之陽極電解液大體上是飽含氫。該成 份還原劑大體上是經由下列反應於陽極1 2 2還原，因而限 制氧之生成： H+ = H2 + 2e. (3) 當使用陰離子薄膜302時，陽極電解液中過量之酸大 體上會被中和。因此，系統3 00可包括一以流體與陽極電 解液出口 106連接之EDC 3 04。第4圖顥示一代表性陽極 電解液EDC 304之具體實施例。EDC 304係與EDC 138類 似構造’其特徵在於EDC 304包括一陽極隔室400與陰極 隔室402。如EDC 138之相同方式，進口 4 〇 4連接已使用 或老化陽極電解液從一電鑛槽（譬如一銅ECP槽）進入 ELDC 304之輸入室406。在此配置中，一稀釋（如，從約 0.01M至約0.1M)之硫酸溶液可經由導管41〇通過位於輸 入室404之陽極方向的隔離室408。 該薄膜結構大體上依照一交替順序（即，從左到右為一 陰離子溥膜，接著為一陽離子薄膜，接著為一陰離子薄膜， 接著為一陽離子薄膜等）。操作中，ELDC 304類似於第2 圖中所示ELDC 138之操作，會施加一電性偏壓至陰極2〇4 與陽極202間。所重新補充之陽極電解液可接著經由導管 4i2從輪入室404擷取用於補充。所應用之電性偏壓造成 在已使用陽極電解液溶液中正電荷離子向陰極2〇4移動， 而負電荷離子會被推向陽極2〇2移動。陽離子與陰離子薄 膜之配置可操作在各自的薄膜間推動正氫根離子、貞氮氧 16 電锻措500之框架構件503大體上包 籌件5〇3上之圓形基座構件504。因為框 一邊提高，基座構件504之上表面大體上 角度(相當於框架構件5〇3相對於水平位 200413573 根離子與負電荷硫酸鹽離子，且進入如第 需^之隔至。該正氫根離子會與負硫酸鹽 過量之馱，且形成一稀釋硫酸溶液，其隨名 萃取出於鋼電鍍系統中再使用。 第5圖顯不-使用在上述具體實施例 于電鍍槽5 00之立體與部份斷面圖。電鍍 括一外凹槽501與一位於外凹槽内之内凹 體上經配置以包含一在電化學電 金屬(如鋼)於基材上之電鑛溶液。在電 溶液大體上b $ ,太， 上疋連續供應至内凹槽502(制 槽而言是以每分鐘约 爾、1加侖），且因此該 出内凹槽5 〇2夕畀古田, υ 2之最尚點且流入外凹槽5, 錢溶液接著合士 & ^ 者會由外部凹槽501收集且從 至凹槽5〇2。如第 乐3圖所不，電鍍槽5! 置即電鍍系統500之框架5〇3部 θ 使彳于電鍍槽5 0 0之組件會傾斜約 因此為了電鍍作業時在内凹槽502内含 溶液，之最高部份在電鐘槽5 伸些’使得内凹槽502之最高點大體上 應之電链溶液沿凹槽5Q2之周邊連續地 4圖中所示符合 離子結合以中和 I 可從 ELDC 304 中之代表性電化 槽500大體上包 槽502 。内凹槽 製程中用以電鍍 製程中，該電鍍 對1 0公升電鍍 鍍溶液連續溢流 中。所溢流之電 處排放以再循環 大體上是在一斜 大體上是有一邊 变至約3 0度間。 適當深度之電鍍 之一侧可向上延 水平且允許所供 流。 括一固設於框架 架構件503係在 .是從水平傾斜一 置之失角）。基座 17 200413573 構件504包括一形成於其内之圓形或碟狀凹處，該圓形凹 處經配置以接受一碟狀陽極構件5〇5。基座構件更包 括複數個位於其一底面上之流體進口 /排放口 5〇9。各流體 進口 /排放口 5 09大體上是經配置以個別地將液體供應炱 或排放自電鑛槽500之陽極隔室或陰極隔室。電鑛槽5〇〇 更包括一薄膜支撐組件506。薄膜支撐組件5〇6大體上是 在其外部周邊處固設於基座構件5〇4，且包括一配置以允 許流體經過一序列在相對位置之細縫與孔流經其中的内部 區508。該薄膜支樓組件可包括一位置靠近該薄膜周界之 0形環型式之密封，其中該密封是配置以防止流體從固設 於薄膜支撐5 06上之薄膜的一側流向該薄膜的另一側。 在操作中，本發明之電鑛槽5 0 0提供一可用於（例如） 鋼電化學電鍍製程之小容積（電解液容積）處理槽。電鍍槽 5 0 0可水平定位或定位於一傾斜方向（即，該槽之一側垂直 ^鬲於該槽之相對側），如第5圖所示。如果電鍍槽5 0 0 是以一傾斜配置實施，則可使用一傾斜之頭部組件與基材 支樓構件以一固定浸泡角度浸泡該基材（即，浸泡該基材 時’使得該基材與該電解液上表面之角度在浸泡製程中不 會改變）。再者，該浸入製程可包括一變化之浸泡速度（即， 當該基材浸泡在電解液溶液中時增加速度）。可操作該固定 浸泡角度與變化浸泡速度之組合以消除在基材表面之空氣 泡。 假設是使用傾斜的一實施例，基材首先是浸入包含在 内凹槽5 02内的一電鍍溶液中。一旦該基材浸入該電鍍溶 18 200413573 液（其大體上含有經配置以控制電鑛參數之硫酸銅、氣及一 或以上之複數有機添加物（均染劑、抑制劑、加速劑等））， 則會施加一電性電鍍偏壓於該基材上之晶種層與位於電鍍 槽5 00底部之陽極505間。該電性電鍍偏壓大體上是操作 以造成該電鍍溶液中之金屬離子沈積於該陰極基材表面 上。供應至内凹槽502之電鐘溶液是經由流體進口 /出口 5 09通過内凹槽5 02持續地循環。該溶液可行經基座構件 5 04之下表面且向上通過流體開口 2〇6之一。於是可經由 一形成於電鍍槽5 00内而在薄膜支撐5 06上一點連接至該 陰極隔室之通道，將該電鍍溶液導入該陰極隔室内。同理， 可經由一位於薄膜支撐506上之流體排出口（其中該流體 排出口是以流體連接至基座構件5 0 4下表面上之流體排出 口 5 0 9中之一），將該電鍍溶液從該陰極隔室中移走。例 如，基座構件504可包括位於基座構件504相對二側上之 第一與第二流體開口 206。可操作在相對位置之流體開口 206以一預定方向從該陰極隔室個別導入與排出電鍍溶液 (其也提供流動方向控制）。該流動方向控制提供之控制是 在較低之薄膜表面移動輕質流體，從陽極隔室移走氣泡， 及協助從陽極表面經由通道202移走形成於基座504内之 稠密與重質流體。 一旦電鍍溶液被導入該陰極隔室中，該電鍍溶液會向 上行經擴散板510。大體上為一陶瓷或其他有孔碟狀構件 之擴散板5 1 〇的作用為一流體流動限制器，使橫越基材表 面之流動模式均一。再者，可操作擴散板5丨〇以在阻抗上 19 200413573 降低在陽極或陽離子薄膜表面電化學作用區域之電性變異 (已知其會減低電錢之均一性）。此外，本發明之具體實施 例預期該陶瓷擴散板5 1 0可由一親水性塑料構件（即，一經 處理之PE構件、一 PVDF構件、一 pp構件或其他習知為 多孔且有由陶瓷所具備之阻抗阻尼特徵的材料）。然而，導 入該陰極隔室之電鍍溶液（其大體上是一電鍍陰極電解液 溶液），將不被允許向下行經位於薄膜支撐組件5 〇6下表面 404上之薄膜（未顯示）而進入陽極隔室，因為該陽極隔室 是由該薄膜與該陰極隔室之流體隔離。該陽極隔室包括經 配置以供應陽極電解液溶液至陽極隔室之分隔的個別流體 供應與排放源。供應至該陽極隔室之溶液（其在一鋼電化學 電鍍系統中大體上可為硫酸鋼）單獨地循環通過陽極隔室 且並未擴散或以其他方式進入該陰極隔室，因為位於薄膜 支撐構件506上之薄膜在任何方向均不使流體滲透。 此外，可方向性控制流體溶液（電解液）進入陽極隔室 内之流動以使電鐘參數最大。❹，陽極電解液可經由一 個別之流體進口 509連接至陽極隔室。流體進口 5〇9係以 流體連接-形成於基座構件5〇4底部之流體通道，且該流 體通道連接該陽極至開σ 2〇5中之一。之後，該陽極電解 液大體上會行經陽5〇5之上表面，，月向基座構件 相對側（其在傾斜配置時大體上是電鍍槽5〇〇之較高側） 該陽極電解液會橫越陽極表面（其纟緊靠陽極之上方薄膜 下）。-旦該陽極電解液到達陽極5G5之相對側，其會被容 置於對應之流體通道内且後續從電链槽5⑽用於再循環: 20 200413573 在電鍍操作中，在陽極與陰極間之電鍍偏壓的應用， 大體上會在陽極上造成一化學反應，而在陽極電解液中導 致氧氣泡。然而，該高陽極電解液流動速率之作用可使該 陽極電解液在陽極駐留之時間最短，因而防止氧飽和。再 者，該移除裝置與該管柱之作用可移除任何在該陽極電解 液中形成之氧。 雖然前述說明是關於本發明之具體實施例，可預期本 發明有其他與進一步具體實施例而不脫離其基本範_，且 其範疇是由下列申請專利範圍所決定。 【圖式簡單說明】 為詳細暸解以上引述之本發明特徵，將（綜合上述）藉 由參考具體實施例（某些將示範於附圖中）對本發明進行一 更特別之說明。應注意該附圖僅示範本發明之典型具體實 施例，因此不應視為對其範疇之限制，因為本發明可容納 其他同等有效之具體實施例。 第1圖示範用於本發明具體實施例的一電鐘系統。 第2圖示範一代表性陽極電解液EDC之線路概要圖。 第3圖示範納入一陰離子薄膜之電鍍系統。 第4圖示範一代表性陽極電解液EDC之具體實施例。 第5圖示範一代表性電化學電鍵槽之立體與部份斷面 圖。 【元件代表符號簡單說明】 21 200413573Cu (OH) 2 + H2S〇4 = 2H2〇 + CuS〇4 (2) The copper oxide or steel hydroxide will decompose when exposed to excess acid, because the excess acid present in the anolyte is converted to copper sulfate. Although illustrated by a column, excess acid in the anolyte is neutralized by any method known to those skilled in the art. The anode electrolytic wave can then be configured to remove the copper oxide filter 134 remaining in the anolyte solution. For example, the anolyte 4 passes through 134. In processing, the anolyte generally has about 2 · 6 to the rural system 100 column 132 solution to pass through the tube anode t pH column CuO to support hydrogen and oxygen. This will pass through the hydrogen and oxygen filter] 3.6 12 200413573 pH. Unit 102 is connected to the unit 102 removal device to remove at least the anolyte. In addition, an output of electricity to the cathode electrolytic electrolyte inlet is generally 101 to the cathode receiving portion of the cathode electrolytic 11 8 for subsequent. EDC Yes, you can accept only one implementation, as shown in the second picture. One of the representative body substrates is configured to contain the first two ends of the 200, and the substantially cross-over device 134 is generally stored and connected to the anolyte with a fluid. Further, before the anolyte is transferred from the anolyte reservoir to the plating tank 101, the anolyte may be passed through a deaerator 136, for example. The deaerator 136 is generally configured to electrolyze · partially dissolve gases (such as oxygen and nitrogen) from the anode before the electrolyte enters the anolyte chamber 108. • A catholyte outlet 114 may be fluidly connected to an input having an analysis tank {EDC}, and the EDC may be fluidly connected to the liquid storage unit 118. The catholyte is recycled to the catholyte chamber through a cathode 116. The EDC chamber 1 38 is a used catholyte configured to receive a portion of the electrolyte storage unit 118 from the plating tank. All catholyte used will be neutralized within the EDC 130 to produce a storage solution, which can then be reintroduced into the catholyte storage unit for use in electroplating operations. Although the representative catholyte as shown in Figure 1 is transmitted through the outlet 114, it can be expected that various EDC configurations that have used catholyte can be configured in a split type.丨 A circuit diagram showing a representative catholyte ED C 1 3 8 EDC 138 (for example) can be implemented in a system configured to electroplat copper to a semiconductive ECP. The representative EDC 138 generally includes a housing 200 that houses or restricts the basic components of the EDC 138. The housing end generally includes a steel anode source 202, and the housing 200 includes a cathode source 204. The anode source 202 and the cathode source 204 are substantially located at opposite / opposite ends of the case 200. The volume between the anode source 202 and the cathode source 204 in the housing 2000 generally includes a plurality of compartments, and the compartments generally include the anode 202 corresponding to each end of the housing 200 Or an anode compartment 206 and a cathode compartment 208 of the cathode 204. The used catholyte is supplied to the EDC tank 138 through the conduit 210. The conduit 210 supplies the used catholyte into an input chamber 212 in the edC tank 138. Selective permeable membranes separate individual compartments. An anion film 2 1 4 (which is preferably selective and can pass through monovalent anions, especially sulfate), will substantially separate the anode compartment 206 and the wheel-in compartment 212. A bipolar membrane 216 separates the input chamber 212 from the cathode compartment communication chamber 208. The sulfuric acid solution can be supplied to the cathode compartment 208 and the anode compartment 206 via conduits 218 and 220, which are operated to circulate the acid solution through the respective compartments. The sulfuric acid is substantially diluted. Therefore, an additional conduit (not shown) can supply deionized water to each compartment or to conduits 218 and 220. In the horizontal operation, an electrical bias is applied via the anode 204 and the cathode 202. 5 The EDC tank 128 generally has a voltage drop between the anode 202 and the cathode 204 from about 0.4 volts to about 1 5 Volts. The effect of the electrical bias applied to the edc tank is to push the ions in the dangerous electrolyte solution of 1 towards their respective electrodes, that is, the positive ions will be pushed to the cathode 204, and the negative ions will be pushed向阳 202。 To the anode 202. Therefore, the decomposed sulfate ions in the used catholyte (usually as shown in Fig. 2-2 kg S0 4) will be pushed away from the used cathode in the direction of the anode 202 Electrolytic fresh liquid. It is understood that the decomposed hydroxide ions (shown generally as OH ·) will be pushed from 7 Ling to the anode 202, and the decomposed hydrogen ions (shown generally as Η +, compound, Η) will be pushed Toward the cathode 204. 14 ‘UU413573’ Although Cu2 + will also pass through the thin film 216, its amount is negligible because the flow rate of H + moving to the cathode compartment 208 is about 100 times that of the copper ions. The aerosol ions will neutralize excess acid present in the catholyte. In addition, the 'bipolar film 2 1 6 allows the removal of H + from the used catholyte to further neutralize excess acid. The formed acidic copper sulfate solution can then be moved from the input chamber 212 through the guide 222 and recycled into the electroplating system (or an electrolytic solution tank, etc.), because CuS04 / H2S04 is used in copper plating systems. The main element in electrolytic solution. Therefore, EDC 138 is generally operable to receive used electrolyte from the plating system and separate 2 components (copper sulfate and sulfuric acid) from the used electrolyte for reuse in the plating system. Although the excess acid has been neutralized during processing, copper in the catholyte may be depleted, so sulfuric acid steel and additives can be added to the catholyte storage tank. In addition, anhydrous copper sulfate can be added to the catholyte previously The catholyte is added as early as 70 11 8 or after storage. In addition, rhenium implements an alternative embodiment of 138 to further modify the copper concentration. The alternative is "a cationic film instead of an anionic film, and through the anode, it is separated to 206% by a concentrated copper sulfate solution to provide ah to move through the film and into the used catholyte. Figure 3 shows the inclusion of a Yinli early planting electric clock system 3.0 0 Figure 1-no; ^ 3 ° 2 electric mining system 30 °. The difference is that the anolyte is substantially acid solution (for example, from About .05 μ to about 0. The acid is substantially sulfuric acid. The anode electrode also includes a reducing agent that includes an organic or inorganic component. For example, the anode electrolysis— ^ ^. Electrolysis and T include dissolved A combination of gaseous hydrogen, hydrogen, potassium iodide, manganese ion (Mn2 +) or 15 200413573, etc. When gaseous hydrogen is contained in the anolyte, it is electrolyzed at the anode. The anolyte in the liquid storage tank 102 is substantially saturated with hydrogen. The component reducing agent is reduced by the anode 1 2 2 through the following reactions, thereby limiting the generation of oxygen: H + = H2 + 2e. (3) When an anion is used When the film is 302, the excess acid in the anolyte is roughly Will be neutralized. Therefore, the system 300 may include an EDC 304 connected to the anolyte outlet 106 by a fluid. Figure 4 shows a specific embodiment of a representative anolyte EDC 304. EDC 304 and EDC 138 similar structure 'is characterized in that EDC 304 includes an anode compartment 400 and a cathode compartment 402. In the same way as EDC 138, the inlet 404 connects a used or aged anolyte from a power ore tank (such as a copper ECP Tank) into the input chamber 406 of the ELDC 304. In this configuration, a dilute (eg, from about 0.01M to about 0.1M) sulfuric acid solution can pass through the conduit 41 through the isolation chamber 408 located in the anode direction of the input chamber 404. The film structure generally follows an alternating sequence (ie, from left to right is an anion film, followed by a cationic film, then an anion film, then a cationic film, etc.) In operation, ELDC 304 is similar to the first 2 The operation of the ELDC 138 shown in the figure will apply an electrical bias between the cathode 204 and the anode 202. The replenished anolyte can then be retrieved from the wheel room 404 for replenishment via the conduit 4i2. application The electrical bias causes positively charged ions to move to the cathode 204 in the used anolyte solution, while negatively charged ions are pushed to the anode 202. The configuration of the cation and anion films can be pushed between the respective films. The orthohydrogen ions, the nitrogen and oxygen 16 electroformation measures 500, the frame member 503 generally includes the circular base member 504 on the chip 503. Because the side of the frame is raised, the upper surface of the base member 504 is roughly angled ( It is equivalent to the frame member 503 with respect to the horizontal level of 200413573 ions and negatively charged sulfate ions, and enters as far as necessary. The positive hydrogen ions will be in excess of the negative sulfate and form a dilute sulfuric acid solution, which is extracted from the steel plating system for reuse. Fig. 5 shows a three-dimensional and partial cross-sectional view of the plating tank 500 used in the above specific embodiment. The electroplating includes an outer groove 501 and an inner concave body located in the outer groove, and is configured to include an electro-mineral solution on an electro-chemical metal (such as steel) on a substrate. The electric solution is generally b $, too, and the upper continuum is continuously supplied to the inner groove 502 (in terms of grooves, it is about 1 gallon per minute), and therefore the inner groove is 502 畀 畀 畀 田, υ The best point of 2 flows into the outer groove 5, and the money solution is then collected by the outer groove 501 and goes from the groove 502. As shown in Fig. 3, the plating tank 5! The frame 503 of the plating system 500 is placed θ, so that the components placed in the plating tank 5 0 0 will tilt approximately so that the solution is contained in the inner groove 502 for the plating operation. The highest part is extended in the electric clock slot 5 so that the highest point of the inner groove 502 generally corresponds to the electric chain solution along the periphery of the groove 5Q2. A representative electrochemical tank 500 in the ELDC 304 generally includes a tank 502. The inner groove process is used in the electroplating process. The electroplating process continuously overflows 10 liters of electroplating solution. The overflowed electricity is discharged to recirculate. Generally, it is inclined at one side, and it is changed to about 30 degrees on one side. One side of the plating at an appropriate depth can be extended horizontally and allow current to be supplied. Including a frame member 503 fixed to the frame, the angle is a misalignment from the horizontal). Base 17 200413573 The member 504 includes a circular or dish-shaped recess formed therein, the circular recess being configured to receive a dish-shaped anode member 505. The base member further includes a plurality of fluid inlet / outlet ports 509 on one bottom surface thereof. Each fluid inlet / drain 5 09 is generally configured to individually supply or discharge liquid from the anode compartment or cathode compartment of the power pit 500. The electric ore tank 500 further includes a thin film support assembly 506. The membrane support assembly 506 is generally fixed to the base member 504 at its outer periphery, and includes an interior region 508 configured to allow fluid to flow through a series of relatively opposed slits and holes therethrough. The membrane pedestal assembly may include an O-ring type seal located near the perimeter of the membrane, wherein the seal is configured to prevent fluid from flowing from one side of the membrane fixed to the membrane support 506 to the other of the membrane. side. In operation, the electric ore tank 500 of the present invention provides a small volume (electrolyte volume) processing tank that can be used in, for example, a steel electrochemical plating process. The plating tank 5 0 0 can be positioned horizontally or in an inclined direction (that is, one side of the tank is perpendicular to the opposite side of the tank), as shown in FIG. 5. If the plating bath 5 0 0 is implemented in an inclined configuration, the substrate can be immersed at a fixed immersion angle using an inclined head assembly and the substrate supporting member (ie, when the substrate is immersed, 'make the substrate (The angle with the upper surface of the electrolyte will not change during the immersion process). Furthermore, the immersion process may include a variable immersion speed (ie, increase the speed when the substrate is immersed in the electrolyte solution). The combination of fixed soaking angle and varying soaking speed can be operated to eliminate air bubbles on the surface of the substrate. Assume an embodiment using a tilt, the substrate is first immersed in a plating solution contained in the inner groove 502. Once the substrate is immersed in the electroplating solution 18 200413573 (which generally contains copper sulfate, gas, and one or more organic additives (leveling agents, inhibitors, accelerators, etc.) configured to control electrical and mining parameters) , An electrical plating bias is applied between the seed layer on the substrate and the anode 505 at the bottom of the plating tank 500. The electrical plating bias is generally operated to cause metal ions in the plating solution to be deposited on the surface of the cathode substrate. The clock solution supplied to the inner groove 502 is continuously circulated through the inner groove 502 through the fluid inlet / outlet 509. The solution may pass through the lower surface of the base member 504 and upward through one of the fluid openings 206. It is then possible to introduce the electroplating solution into the cathode compartment via a passage formed in the plating tank 500 at one point on the thin-film support 506. Similarly, the electroplating can be performed through a fluid discharge port on the membrane support 506 (where the fluid discharge port is fluidly connected to one of the fluid discharge ports 5 0 9 on the lower surface of the base member 504). The solution was removed from the cathode compartment. For example, the base member 504 may include first and second fluid openings 206 on opposite sides of the base member 504. The fluid openings 206 operable in opposite positions individually introduce and discharge the plating solution from the cathode compartment in a predetermined direction (which also provides flow direction control). This flow direction control provides controls to move the light fluid on the lower film surface, remove bubbles from the anode compartment, and assist in removing the dense and heavy fluid formed in the base 504 from the anode surface via the channel 202. Once the plating solution is introduced into the cathode compartment, the plating solution passes upward through the diffusion plate 510. The diffuser plate 5 10, which is generally a ceramic or other perforated dish-like member, functions as a fluid flow restrictor, making the flow pattern uniform across the surface of the substrate. Furthermore, the diffusion plate 5 can be operated to reduce the electrical variation of the electrochemical action region on the surface of the anode or the cationic film on the impedance 19 200413573 (known to reduce the uniformity of electricity). In addition, the specific embodiment of the present invention contemplates that the ceramic diffusion plate 5 1 0 may be made of a hydrophilic plastic member (ie, a treated PE member, a PVDF member, a pp member, or other conventionally porous and provided by ceramics). Material with impedance damping characteristics). However, the electroplating solution (which is generally an electroplated catholyte solution) introduced into the cathode compartment will not be allowed to enter the anode through a thin film (not shown) located on the lower surface 404 of the thin film support assembly 506. Compartment, because the anode compartment is separated from the fluid of the cathode compartment by the film. The anode compartment includes separate individual fluid supply and discharge sources configured to supply an anolyte solution to the anode compartment. The solution supplied to the anode compartment, which can be substantially sulfuric acid steel in a steel electrochemical plating system, circulates through the anode compartment separately and does not diffuse or otherwise enter the cathode compartment because it is located on the membrane support The film on the member 506 is impermeable to fluid in any direction. In addition, the direction of the fluid solution (electrolyte) into the anode compartment can be controlled to maximize the clock parameters. Alas, the anolyte can be connected to the anode compartment via a separate fluid inlet 509. The fluid inlet 509 is fluid-connected-a fluid passage formed at the bottom of the base member 504, and the fluid passage connects the anode to one of the openings σ2. After that, the anolyte will generally pass through the upper surface of the menstruation 505, and the opposite side of the moon base member (which is generally the higher side of the plating bath 500 when in an inclined configuration). Across the surface of the anode (its pinch is directly under the film above the anode). -Once the anolyte reaches the opposite side of the anode 5G5, it will be contained in the corresponding fluid channel and subsequently recirculated from the electrical chain slot 5⑽ for recirculation: 20 200413573 Electroplating between anode and cathode during the plating operation The application of a bias voltage generally causes a chemical reaction on the anode and causes oxygen bubbles in the anolyte. However, the effect of the high anolyte flow rate can minimize the dwell time of the anolyte at the anode, thereby preventing oxygen saturation. Furthermore, the removal device and the string can remove any oxygen formed in the anode electrolyte. Although the foregoing description is about specific embodiments of the present invention, it is expected that there are other and further specific embodiments of the present invention without departing from its basic scope, and its scope is determined by the scope of the following patent applications. [Brief description of the drawings] In order to understand the features of the present invention cited above in detail, the present invention will be described (in combination) with reference to specific embodiments (some will be exemplified in the drawings). It should be noted that the drawings only exemplify typical specific embodiments of the invention, and therefore should not be considered as limiting its scope, as the invention can accommodate other equally effective specific embodiments. FIG. 1 illustrates an electric clock system used in a specific embodiment of the present invention. Figure 2 illustrates a schematic circuit diagram of a representative anolyte EDC. Figure 3 illustrates a plating system incorporating an anion film. FIG. 4 illustrates a specific embodiment of a representative anolyte EDC. Figure 5 illustrates a three-dimensional and partial cross-sectional view of a representative electrochemical keyway. [Simple description of component representative symbols] 21 200413573
100 電鍍系統 101 電鍍槽 102 陽極電解液儲存單元 104 泵 105 陽極電解液進口 106 陽極電解液出 108 陽極電解液室 110 陰極電解液室 112 薄膜 114 陰極電解液出 116 陰極電解液進口 118 儲存單元 122 陽極 123 基材 124 陰極 126 旋轉頭 128 擴散器 130 管柱、EDC 132 閥 134 過濾器 136 除氣器 138 EDC槽 140 閥 200 殼體 202 陽極源 204 陰極源 205 開口 206 陽極隔室 208 陰極隔室 210 導管 212 輸入室 214 陰離子薄膜 216 雙極薄膜 218 導管 220 導管 222 導管 300 電鍍系統 302 陰離子薄膜 304 EDC 400 陽極隔室 402 陰極隔室 404 下表面 406 室 408 隔離室 410 導管 412 導管 500 電鍍槽 501 外凹槽 22 200413573 502 内 504基 506薄 509進 凹槽 座 膜支撐組件 口 /排出口 503框架 505陽極 5 08 内部區 5 1 0擴散板 23100 Plating system 101 Plating tank 102 Anode electrolyte storage unit 104 Pump 105 Anode electrolyte inlet 106 Anode electrolyte outlet 108 Anode electrolyte compartment 110 Catholyte compartment 112 Film 114 Catholyte outlet 116 Catholyte inlet 118 Storage unit 122 Anode 123 Base material 124 Cathode 126 Rotating head 128 Diffuser 130 Tubing, EDC 132 Valve 134 Filter 136 Deaerator 138 EDC tank 140 Valve 200 Housing 202 Anode source 204 Cathode source 205 Opening 206 Anode compartment 208 Cathode compartment 210 conduit 212 input chamber 214 anion membrane 216 bipolar membrane 218 conduit 220 conduit 222 conduit 300 plating system 302 anion membrane 304 EDC 400 anode compartment 402 cathode compartment 404 lower surface 406 compartment 408 isolation compartment 410 conduit 412 conduit 500 plating tank 501 Outer groove 22 200413573 502 Inner 504 base 506 thin 509 into the groove seat membrane support assembly port / exit port 503 frame 505 anode 5 08 inner area 5 1 0 diffuser plate 23
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40126002P | 2002-08-06 | 2002-08-06 | |
| US10/358,781 US20040026255A1 (en) | 2002-08-06 | 2003-02-04 | Insoluble anode loop in copper electrodeposition cell for interconnect formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW200413573A true TW200413573A (en) | 2004-08-01 |
Family
ID=31498257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092121579A TW200413573A (en) | 2002-08-06 | 2003-08-06 | Insoluble anode loop in copper electrodeposition cell for interconnect formation |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20040026255A1 (en) |
| TW (1) | TW200413573A (en) |
| WO (1) | WO2004013381A2 (en) |
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| US10190232B2 (en) | 2013-08-06 | 2019-01-29 | Lam Research Corporation | Apparatuses and methods for maintaining pH in nickel electroplating baths |
| US10954604B2 (en) | 2014-04-18 | 2021-03-23 | Lam Research Corporation | Methods and apparatuses for electroplating nickel using sulfur-free nickel anodes |
| TWI820131B (en) * | 2018-05-09 | 2023-11-01 | 美商應用材料股份有限公司 | Electroplating systems and methods for removing copper contaminants from a tin-containing catholyte within electroplating systems |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10190232B2 (en) | 2013-08-06 | 2019-01-29 | Lam Research Corporation | Apparatuses and methods for maintaining pH in nickel electroplating baths |
| TWI657168B (en) * | 2013-08-06 | 2019-04-21 | 美商蘭姆研究公司 | Apparatuses and methods for maintaining ph in nickel electroplating baths |
| US10954604B2 (en) | 2014-04-18 | 2021-03-23 | Lam Research Corporation | Methods and apparatuses for electroplating nickel using sulfur-free nickel anodes |
| TWI820131B (en) * | 2018-05-09 | 2023-11-01 | 美商應用材料股份有限公司 | Electroplating systems and methods for removing copper contaminants from a tin-containing catholyte within electroplating systems |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040026255A1 (en) | 2004-02-12 |
| WO2004013381A2 (en) | 2004-02-12 |
| WO2004013381A3 (en) | 2005-03-10 |
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