CN101405436A - 电解镀铜的方法 - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000007747 plating Methods 0.000 title claims abstract description 22
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 50
- 238000009713 electroplating Methods 0.000 claims description 43
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 16
- 238000007781 pre-processing Methods 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- HCVGTTAKFXBGGX-UHFFFAOYSA-N OS(CCC[Na])(=O)=O.SS Chemical class OS(CCC[Na])(=O)=O.SS HCVGTTAKFXBGGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- -1 ketones compound Chemical class 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 2
- 230000001715 anti-suppressor Effects 0.000 abstract 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 1
- ZDRYDSJMVRRAAF-UHFFFAOYSA-N 2-fluoro-6-(trifluoromethyl)benzoyl chloride Chemical compound FC1=CC=CC(C(F)(F)F)=C1C(Cl)=O ZDRYDSJMVRRAAF-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- QKZYBTJZHCOXSY-UHFFFAOYSA-N [K].OS(=O)(=O)CCCS Chemical compound [K].OS(=O)(=O)CCCS QKZYBTJZHCOXSY-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 229940093495 ethanethiol Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- H05K2203/03—Metal processing
- H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明涉及电解镀铜的方法，提出了一种包含两步的电解镀铜方法，此方法特别适于电镀非常狭窄的空间。第一步包括含有抗抑制剂的预处理溶液，该抗抑制剂包含含硫有机化合物，优选具有一个或数个烷基磺酸盐基和/或烷基磺酸。第二步包含基于烷基磺酸的电解铜电镀溶液。
Description
技术领域
本发明涉及一种在表面上电解镀铜的方法，特别是在非常狭窄的区域如印刷电路板上的通孔或过孔上电镀的方法。本发明的方法特别适于电镀非常小的印刷电路过孔。
背景技术
电解铜电镀是一种方法，其在导电性基底上用外部电流沉积铜。众所周知的商业电解铜电镀溶液包括硫酸铜、氟硼酸铜或氰化铜与改善铜沉积物性质的各种添加剂的水溶液。最广泛应用的商业镀铜电解液基于硫酸铜、硫酸和各种电镀添加剂的水溶液。关于常规的铜电解电镀浴和添加剂，请参考第5,068,013号、第5,174,886号和第5,051,154号美国专利，它们中每一个的教示在此全部并入作为参考。
烷基磺酸在电解铜电镀中的应用也是公知的。第6,605,204号美国专利(其教示在此全部并入作为参考)讨论了应用包含铜的烷基磺酸盐和游离的烷基磺酸的溶液在电子装置上电解沉积铜。
小型化和增加的功能化需求已经使得需要被电镀的电子部件的尺寸充分地降低了。例如，许多电路板设计需要直径为约25至约250微米、厚径比为约1∶1到约1.5∶1的盲孔的有效电镀，并且同时电镀厚径比为约8∶1的通孔。许多电解铜电镀浴不能电镀如此狭窄的空间。在一些情况下可湿性是个问题，在其他情况下大量迁移(transport)出现问题，以及在其他区域电效应导致困难。在历史上，结合混合技术设计，同时镀通孔的可靠性未能满足工业要求。
因此，有对能有效在狭窄空间电镀的电解铜电镀溶液和方法的需求。在此提出的电解铜电镀溶液和方法是特别设计并适于电子应用的，对这些电子应用而言在狭窄空间中有效电镀是必须的。
发明内容
发明人在此提出一种电解铜电镀方法，包含：
1.将表面与包含用于铜电化学还原的抗抑制剂的水溶液的预处理溶液接触。抗抑制剂是一种含硫有机化合物，优选包含烷基磺酸盐基和/或烷基磺酸；和然后
2.将所述表面作为阴极与电解铜电镀溶液接触，并施以电镀电流从而将铜电镀在表面上。电解铜电镀溶液包含(i)铜离子和(ii)烷基磺酸、(iii)氯离子和优选的(iv)醛或酮化合物。
优选地，电解铜电镀溶液也包含(i)表面活性剂或湿润剂、(ii)包含含硫有机化合物的光亮剂，优选具有一个或数个磺酸盐基和(iii)包含含氮有机化合物的整平剂。
一种用于电解镀铜的方法被提出，该方法包含预处理步骤和电镀步骤。此方法特别适于在非常狭窄的空间(如印刷电路板上的微过孔)电镀，并同时电镀相同板设计中的通孔。此提出的方法包含：
1.将表面与包含抗抑制剂的水溶液的预处理溶液接触，其中抗抑制剂包含含硫有机化合物，优选具有一个或数个(烷基)磺酸盐基和/或烷基磺酸；和然后
2.将所述表面作为阴极与电解铜电镀溶液接触，此电镀溶液包含(i)铜离子和(ii)烷基磺酸、(iii)氯离子和优选的(iv)醛或酮化合物；并施以电镀电流从而将铜电镀在表面上。
预处理溶液包含用于铜电化学还原的抗抑制剂，该抗抑制剂包含含硫有机化合物，优选包含一个或数个(烷基)磺酸盐基和/或(烷基)磺酸。适用作预处理溶液中的抗抑制剂的化合物的实例包括但不限于4，5-二硫代辛烷-1，8-二磺酸二钠、2-巯基乙烷磺酸钠、3-巯基-1-丙烷磺酸钾、双(3-磺丙基)二硫化二钠、双(3-磺丙基)二硫化二钠四聚丙氧基乙氧基乙二胺磺基琥珀酸酯钠盐或它们的混合物。优选地，预处理溶液抗抑制剂是双(3-磺丙基)二硫化二钠。抗抑制剂在预处理溶液中的浓度优选为约0.1g/l至约10g/l。
非强制选择地，但是优选预处理溶液还包含铜离子。铜离子可以通过硫酸铜、甲磺酸铜或类似的铜盐提供。硫酸铜是优选的铜离子源。如果使用的话，铜离子在预处理溶液中的浓度优选为约0.01至约5.0g/l。在任何情况下，预处理溶液的pH优选为1.0～3.5。
预处理溶液之后的电解电镀溶液包含(i)铜离子和(ii)烷基磺酸、(iii)氯离子和优选地(iv)醛或酮化合物的水溶液。电镀浴优选还包含(i)表面活性剂或湿润剂、(ii)光亮剂添加剂和(iii)整平添加剂。
在电解铜电镀溶液中的铜离子源可以是硫酸铜、氧化铜、甲磺酸铜或类似的铜盐。优选使用甲磺酸铜或氧化铜(溶于烷基磺酸中)。铜离子在电镀溶液中的浓度优选为约20～60g/l，更优选40～55g/l。
用于电镀溶液中的烷基磺酸优选为甲磺酸，由于其相对低的成本。烷基磺酸在电镀溶液中的浓度优选为约40至约200g/l。
氯离子源包括可溶于电镀溶液中的氯化物盐。氯离子源的实例为氯化钠、氯化钾、盐酸或它们的混合物。氯离子浓度优选为0.02ppm～125ppm，优选30ppm～90ppm。
优选包括在铜电镀溶液中的醛或酮化合物的实例包括甲醛、乙醛、丁二醛和甲乙酮或它们的混合物。这些化合物的浓度优选为约0.005至约0.500g/l。
电镀溶液优选还包含表面活性剂或湿润剂。使用表面活性剂或湿润剂以降低电镀溶液的表面张力。这对于使电镀溶液润湿非常小的孔或过孔是特别重要的。可用的表面活性剂或湿润剂包括高分子量聚合物，优选聚二元醇型聚合物和共聚物。优选使用聚乙二醇、聚丙二醇和其共聚物。表面活性剂和/或湿润剂在电镀溶液中的浓度可以为约0.1至约8g/l。
电镀溶液优选包含光亮剂添加剂。通常用于铜电镀的光亮剂添加剂是含硫有机化合物，并还可以具有其他官能团。实例包括3-(苯并噻唑-2-硫代)-丙磺酸钠、亚乙基-二硫代二丙磺酸钠、双(3-磺丙基)二硫化二钠、N，N-二甲基二硫代氨基甲酸(3-磺丙基)酯钠盐或它们的混合物。优选的光亮剂添加剂包含双(3-磺丙基)二硫化二钠。光亮剂添加剂在电镀溶液中的浓度优选为约0.001ppm至约2.00ppm。
电镀溶液还优选包含整平添加剂。用于铜电镀的整平添加剂通常包含含氮有机化合物。通常使用具有氨基或取代氨基的化合物。实例包括聚胺、三异丙醇胺、烷基化聚烯化亚胺和4-巯基吡啶。优选整平添加剂为四聚丙氧基-乙氧基乙二胺磺基琥珀酸酯钠盐。整平添加剂在电镀溶液中的浓度优选为约0.005至约0.100g/l。
将待电镀的表面置于电解铜电镀溶液中，并与电源的负极连接，从而使其成为阴极。同样将金属铜阳极置于电镀溶液中，并与电源的正极相连。产生的电镀电流使铜电镀到表面上。在此说明的方法允许在整个电镀期间应用直流(DC)、脉冲周期电流(PP)、周期脉冲反向电流(PPR)和/或它们的结合。
用于电镀电流的安培可以恒定或如在脉冲电镀中可以变化。通常，可用于此电镀溶液的阴极电流密度为5～30安培每平方英尺的阴极面积，优选阴极电流密度为8～15安培每平方英尺的阴极面积。
具体实施方式
实施例1
制备下述预处理和电镀溶液：
预处理
成分 浓度
双(3-磺丙基)二硫化二钠 3mmol/L(1.06g/L)
硫酸铜 10.6mmol/L(0.67g/L)
水 达到1L
电镀溶液
成分 浓度
如甲磺酸铜的铜 45g/L
甲磺酸 110g/L
氯离子 65ppm
甲醛 62ppm
PEG 4000聚乙二醇 1.1g/l
双(3-磺丙基)二硫化二钠 0.5ppm
四聚丙氧基-乙氧基乙
二胺磺基琥珀酸酯钠盐 27ppm
加工两个1.6mm厚的印刷电路板，该电路板具有50、75、100和150微米直径，75和100微米深的过孔和0.2、0.25、0.35和0.5mm直径的通孔。一个通过预处理溶液和电镀溶液加工，另一个仅通过电镀溶液加工。两种情况下，以12ASF的正向阴极电流密度和30ASF(安培每平方英尺)的反向电流密度应用PPR电流。所有的通过预处理溶液加工的板的过孔和通孔被有效电镀，而仅通过电镀溶液加工的板的过孔未被有效电镀。
Claims (10)
1.一种在表面上电解镀铜的方法，所述方法包含：
a)将表面与包含含硫有机化合物的水溶液的预处理溶液接触；和然后
b)将所述表面作为阴极与电解铜电镀溶液接触，此电解铜电镀溶液包含(i)铜离子、(ii)烷基磺酸、(iii)氯离子和优选的(iv)醛或酮化合物；并施以电镀电流从而将铜电镀在表面上。
2.依据权利要求1的方法，其中含硫有机化合物包含磺酸盐基或磺酸基。
3.依据权利要求1的方法，其中电镀溶液还包含至少一种选自光亮剂添加剂、整平添加剂、表面活性剂和湿润剂的添加剂。
4.依据权利要求1或2的任一项的方法，其中预处理溶液还包含铜离子。
5.依据权利要求3的方法，其中光亮剂添加剂包含双(3-磺丙基)二硫化二钠，而整平添加剂包含四聚丙氧基-乙氧基乙二胺磺基琥珀酸酯钠盐。
6.依据权利要求1、3或5的任一项的方法，其中含硫有机化合物包含双(3-磺丙基)二硫化二钠。
7.依据权利要求1的方法，其中电镀电流为恒定直流电。
8.依据权利要求1、2、3或5的任一项的方法，其中电镀电流随时间变化。
9.依据权利要求1的方法，其中阴极的电极性为周期性地反转。
10.依据权利要求1的方法，其中：
a)预处理溶液包含铜离子和双(3-磺丙基)二硫化二钠；和
b)电镀溶液包含双(3-磺丙基)二硫化二钠四聚丙氧基乙氧基乙二胺磺基琥珀酸酯钠盐。
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| US11/398,048 US7575666B2 (en) | 2006-04-05 | 2006-04-05 | Process for electrolytically plating copper |
| US11/398,048 | 2006-04-05 | ||
| PCT/US2007/001716 WO2007126453A2 (en) | 2006-04-05 | 2007-01-19 | Process for electrolytically plating copper |
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| CN104947155A (zh) * | 2015-05-28 | 2015-09-30 | 中南大学 | 基于电化学法从废旧电路板中回收铜制备高纯高强度铜箔的工艺 |
| CN104947155B (zh) * | 2015-05-28 | 2017-04-26 | 中南大学 | 基于电化学法从废旧电路板中回收铜制备高纯高强度铜箔的工艺 |
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| Publication number | Publication date |
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| EP2010698A2 (en) | 2009-01-07 |
| US7575666B2 (en) | 2009-08-18 |
| EP2010698A4 (en) | 2012-06-27 |
| US20070235343A1 (en) | 2007-10-11 |
| JP2009532586A (ja) | 2009-09-10 |
| EP2010698B1 (en) | 2013-07-03 |
| ES2421189T3 (es) | 2013-08-29 |
| WO2007126453A3 (en) | 2007-12-21 |
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