CN1222636C - 化学镀镍的预处理溶液及预处理方法 - Google Patents
化学镀镍的预处理溶液及预处理方法 Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 title claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 42
- 238000007781 pre-processing Methods 0.000 claims description 21
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 16
- 238000002203 pretreatment Methods 0.000 claims description 10
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical group O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 238000010129 solution processing Methods 0.000 claims 2
- 239000012267 brine Substances 0.000 claims 1
- 230000002779 inactivation Effects 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 abstract description 12
- 239000010931 gold Substances 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000008139 complexing agent Substances 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 3
- 239000000758 substrate Substances 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- HBOQGLPIIBWNMC-UHFFFAOYSA-K tetrasodium 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HBOQGLPIIBWNMC-UHFFFAOYSA-K 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
本发明提供一种阻止在铜图案间的化学镀镍或金形成的“桥接”。具有铜图案的电路板被浸入用于化学镀镍含有硫代硫酸盐的预处理溶液中，或预处理溶液被喷射到电路板上。预处理溶液可与添加剂，如pH调节剂、络合剂、表面活性剂或腐蚀抑制剂混合。
Description
技术领域
本发明涉及化学镀镍的预处理溶液、预处理方法和化学镀镍的方法。
背景技术
许多印刷电路板最后一道工序是靠化学镀镍/金来完成。这一步骤之前是铜电路蚀刻和阻焊剂的涂覆，以及在暴露的铜部分选择性地进行化学镀以沉积镍和金膜。
化学镀镍是接在一些预处理步骤之后，这些预处理步骤中电路板被浸入一系列的预处理溶液中。预处理步骤之一是激活剂，其中Pd催化剂附着在暴露的铜部分上以便引发化学镀镍的沉积，其后面是化学镀金。
然而，这样一种化学镀镍步骤经常伴随着镍不仅在铜电路上而且还在接近绝缘体的区域沉积的现象。
这种现象被叫做“桥接”、“过度镀敷”或“渗镀”，这取决于界(communities)和区(organization)。
近来，日益要求印刷电路板具有最窄的线路宽度和空间。因为这一点对由桥接引起的缺陷如短路的出现显著增加有影响。
桥接现象的出现在由熔接(build-up)法制备的电路板中增长显著，该法涉及Pd催化剂附着在树脂表面上，化学镀铜，电解镀铜以及通过蚀刻沉积的铜层形成电路。Pd催化剂基本上溶解在用作电路图形蚀刻剂的氯化铜和氯化铁溶液中。然而，如果局部剩余的话，化学镀镍的桥接很容易在剩余的Pd催化剂上出现。结果，引起了严重的问题，因为即使一次短路也能损坏整个的图案。
为了防止这种现象的发生，必须非常严格的控制化学镀镍溶液的组成和搅拌条件。
本发明的目的在于建立一种能防止在铜图案之间的化学镀镍/金产生“桥接”的技术。
本发明的发明人，在为了解决上述问题进行广泛的研究之后，发现“桥接”现象能有效地通过电路板在用于化学镀镍的预处理之前直接浸入含硫代硫酸盐溶液中而被阻止，包括脱脂、软蚀刻、酸处理以及激活剂处理一系列的步骤。
此外，发明人还发现当Pd催化剂沉积在孔的侧壁上，而孔是通过钻孔法或其它方法在电路板上制成时，硫代硫酸盐处理之前先用高锰酸盐处理和中和步骤是有效的。
发明内容
基于上述发现，本发明提供：
1.用于化学镀镍的预处理溶液，其特征在于含有硫代硫酸盐。
2.用于化学镀镍的预处理溶液，其特征在于含硫代硫酸盐，具有蚀刻铜图案的电路板浸于所述溶液中或者在电路板化学镀镍前先将所述溶液喷射在所述电路板上，
3.上述1或2所述用于化学镀镍的预处理溶液，其特征在于含有选自pH调节剂、络合剂、表面活性剂和腐蚀抑制剂中至少一种。
4.用于化学镀镍的预处理方法，其特征在于电路板浸入含硫代硫酸盐的预处理溶液中或将含硫代硫酸盐的预处理溶液喷射在电路板上，和
5.用于化学镀镍的预处理方法，其特征在于电路板用高锰酸盐处理、中和再浸入含硫代硫酸盐的预处理溶液中，或用含硫代硫酸盐的预处理溶液喷射在上述电路板上。
实施方案
用于化学镀制镍合金，如Ni-P和Ni-B和纯镍的方法均在本发明所述的化学镀镍的范围内。
用于化学镀镍的本发明预处理溶液含硫代硫酸盐为主成分。
硫代硫酸盐的浓度优选在0.01-500g/L的范围内。如果硫代硫酸盐存在的浓度过低，则硫代硫酸盐不能足以显示其固有的作用。硫代硫酸盐浓度的上限由溶解度确定。用于本发明的硫代硫酸盐包括硫代硫酸钠、硫代硫酸钾和硫代硫酸铵。这些化合物使留在电路之间空间内的Pd催化剂失活，从而阻止了“桥接”化学镀镍的沉积。
本发明的预处理溶液可与作为pH调节剂的柠檬酸盐、磷酸盐、焦磷酸盐、四硼酸盐或硼酸混合。溶液的pH值尽管没有限制，但就硫代硫酸盐的稳定性来说，溶液的pH值适于保持在4或以上，11或以下(即在弱酸性到碱性区域内)。
浸渍铜图案电路板的本发明预处理溶液能溶解铜离子，因此使其与络合剂，如EDTA混合以稳定它们。
预处理溶液还可进一步与其它的添加剂混合，例如，改进电路板对溶液润滑性的表面活性剂，和抑制铜腐蚀的腐蚀抑制剂，例如苯并三唑。
本发明的预处理溶液在5-50℃，优选15-30℃下使用是合适的。
使用本发明的预处理方法，可在一系列用于化学镀镍预处理步骤之前，直接通过浸渍与溶液接触的电路板，通过浸渍电路板于本发明处理溶液中或喷射本发明处理溶液于电路板上，所使用的这些方法均可采用喷淋的方式。用于化学镀镍的一序列预处理步骤，一般是用于化学镀镍之前的那些步骤，并且化学镀镍前一般包括脱脂、软蚀刻、酸处理和激活剂一系列处理。
当Pd催化剂留在电路板内已制成的孔侧壁时，受硫代硫酸盐处理之前，先用高锰酸盐处理和中和的步骤将影响预处理更加有效。
对于高锰酸盐处理，电路板被浸入酸性的高锰酸盐水溶液中，高锰酸盐的浓度在0.5-50g/L范围内，且pH为2或以下。为了中和处理，把电路板浸于溶解还原剂，例如硫酸羟胺的水溶液中。
中和处理时，电路板浸入溶解还原剂，例如硫酸羟胺的水溶液中。水溶液的实施例之一是溶解0.5-50g/L硫酸羟胺和0.1-30ml/L的96％硫酸的溶液。
实施例
本发明借助于实施例进行说明，但决不是对本发明的限制。
(实施例和对比例)
通过蚀刻一些铜包层层合板(尺寸为100mm×100mm)制备铜电路图案(线路/空间＝100μm/100μm)。
电路板浸入具有下列组成的溶液5分钟以再现Pd催化剂留于图案之间的条件，然后用水洗涤和干燥。
氯化钯(按Pd计)：100mg/L
氯化铵：10g/L
用盐酸调节pH为2
上述电路板浸入下列组成的预处理溶液中，然后用水洗涤再干燥。
实施例1：
硫代硫酸钾：50g/L
pH：6
pH调节剂：柠檬酸钠
实施例2：
硫代硫酸钠：30g/L
pH：9
pH调节剂：焦磷酸钾
实施例3：
硫代硫酸钾：30g/L
pH：6
pH调节剂：柠檬酸钾
腐蚀抑制剂：苯并三唑
实施例4：
硫代硫酸钠：50g/L
pH：9
pH调节剂：焦磷酸钠
络合剂：EDTA·2Na
表面活性剂：聚氧乙烯壬基苯基醚
上述各板浸入下列条件下的预处理溶液中：
溶液温度：25℃
浸渍时间：5min
实施例5
按与实施例1所用相同程序重复进行，只是在预处理之前进行高锰酸盐处理和中和，使用下列高锰酸盐处理和中和溶液：
高锰酸盐处理溶液
高锰酸钾：5g/L
硫酸(96％)：10ml/L
中和溶液
硫酸羟胺：10g/L
硫酸(96％)：0.5ml/L
从另一方面说，制备未预处理的电路板(对比例1)，和浸入下列代替实施例预处理的溶液中的电路板(对比例2)。
对比例2
碳酸钾：50g/L
pH：10
通过实施例和对比例制备的各电路板，借助于浸入连续不断的步骤，即，脱脂、软蚀刻、酸处理、激活剂处理的溶液中。然后再把电路板浸入化学镀镍溶液和化学镀金溶液中。
对每块电路板都要用显微镜观察其“桥接”程度。结果列于表1中。
表1
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对比例1 | 对比例2 | ||
| 高锰酸盐处理和中和 | - | - | - | - | 有 | - | - | |
| 预处理溶液 | 主成分 | 硫代硫酸钾50g/L | 硫代硫酸钠30g/L | 硫代硫酸钾30g/L | 硫代硫酸钠50g/L | 硫代硫酸钾50g/L | - | 碳酸钾50g/L |
| pH调节剂 | 柠檬酸钠 | 焦磷酸钾 | 柠檬酸钾 | 焦磷酸酸钠 | 柠檬酸钠 | - | - | |
| 络合剂 | - | - | - | EDTA·2Na | - | - | - | |
| 表面活性剂 | - | - | - | 聚氧乙烯壬基苯基醚 | - | - | - | |
| 腐蚀抑制剂 | - | - | 苯并三唑 | - | - | - | - | |
| 预处理 | pH | 6 | 9 | 6 | 9 | 6 | - | 10 |
| 温度(℃) | 25 | 25 | 25 | 25 | 25 | - | 25 | |
| 时间(min) | 5 | 5 | 5 | 5 | 5 | - | 5 | |
| 条件 | 方法 | 浸渍 | 浸渍 | 浸渍 | 浸渍 | 浸渍 | - | 浸渍 |
| 结果 | 线路间未观察到镀镍或金的“桥接” | 线路间未观察到镀镍或金的“桥接” | 线路间未观察到镀镍或金的“桥接” | 线路间未观察到镀镍或金的“桥接” | 线路间未观察到镀镍或金的“桥接” | 线路间观察到了镀镍或金的“桥接”，部分短路 | 线路间观察到了镀镍或金的“桥接”，部分短路 |
通过实施例制备的各电路板在线路间未显示镀镍或金的“桥接”。从另一方面说，通过各对比例制备的各电路板在线路间显示镀镍或金的“桥接”，并且部分短路。
发明优点
用于化学镀镍的本发明预处理溶液能阻止铜图案间化学镀镍或金形成“桥接”现象，借此解决了由桥接引起的短路问题。对于由熔接法制备的电路板来说，它显示了特别值得注意的效果，这种熔接法易于引起Pd催化剂留在图案间。
Claims (3)
1.用于化学镀镍的预处理方法，其特征在于在对包含铜图案的基材进行化学镀镍时，在化学镀镍过程之前直接使用用于化学镀镍的预处理硫代硫酸盐水溶液以使钯催化剂残留物失活，所述溶液包含选自硫代硫酸钠、硫代硫酸钾和硫代硫酸铵的硫代硫酸盐，所述残留物是在化学镀铜期间形成所述铜图案时就附着上去的。
2.按权利要求1的用于化学镀镍的预处理方法，其特征在于将基材浸入预处理溶液中或把预处理溶液喷射在基材上。
3.按权利要求1或2的用于化学镀镍的预处理方法，其特征在于电路板用高锰酸盐溶液处理、其后中和，然后进行所述的用于化学镀镍的预处理方法。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP363899/97 | 1997-12-18 | ||
| JP36389997 | 1997-12-18 | ||
| JP363899/1997 | 1997-12-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1247577A CN1247577A (zh) | 2000-03-15 |
| CN1222636C true CN1222636C (zh) | 2005-10-12 |
Family
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| Application Number | Title | Priority Date | Filing Date |
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| CNB988025116A Expired - Lifetime CN1222636C (zh) | 1997-12-18 | 1998-12-08 | 化学镀镍的预处理溶液及预处理方法 |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6156218A (zh) |
| JP (1) | JP3387507B2 (zh) |
| CN (1) | CN1222636C (zh) |
| WO (1) | WO1999031293A1 (zh) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6658967B2 (en) * | 2001-03-09 | 2003-12-09 | Aquapore Moisture Systems, Inc. | Cutting tool with an electroless nickel coating |
| JP4168114B2 (ja) * | 2001-09-28 | 2008-10-22 | Ｄｏｗａホールディングス株式会社 | 金属−セラミックス接合体 |
| US6926922B2 (en) * | 2002-04-09 | 2005-08-09 | Shipley Company, L.L.C. | PWB manufacture |
| JP4797777B2 (ja) * | 2005-04-25 | 2011-10-19 | 日立化成工業株式会社 | 無電解ニッケルめっき用前処理液、無電解ニッケルめっきの前処理方法無電解ニッケルめっき方法、並びに、プリント配線板及び半導体チップ搭載用基板の製造方法 |
| US9048088B2 (en) * | 2008-03-28 | 2015-06-02 | Lam Research Corporation | Processes and solutions for substrate cleaning and electroless deposition |
| US8609256B2 (en) * | 2008-10-02 | 2013-12-17 | E I Du Pont De Nemours And Company | Nickel-gold plateable thick film silver paste |
| US8383243B2 (en) * | 2008-12-10 | 2013-02-26 | Xerox Corporation | Composite containing polymer, filler and metal plating catalyst, method of making same, and article manufactured therefrom |
| JP5428667B2 (ja) | 2009-09-07 | 2014-02-26 | 日立化成株式会社 | 半導体チップ搭載用基板の製造方法 |
| CN104470236B (zh) * | 2013-09-16 | 2017-10-10 | 深圳市兴经纬科技开发有限公司 | 电路板化学镀镍金的后浸液及后浸方法 |
| CN104878422B (zh) * | 2014-02-28 | 2017-12-12 | 比亚迪股份有限公司 | 一种钯活化液及其制备方法及塑料的活化方法 |
| US20160348245A1 (en) | 2015-05-28 | 2016-12-01 | Macdermid, Incorporated | Method of Pretreatment for Electroless Plating |
| JP6340053B2 (ja) * | 2016-10-05 | 2018-06-06 | 小島化学薬品株式会社 | 無電解パラジウム／金めっきプロセス |
| CN108650801B (zh) * | 2018-04-02 | 2020-07-10 | 皆利士多层线路版(中山)有限公司 | 厚铜线路板的沉金方法 |
| CN113151811A (zh) * | 2021-04-13 | 2021-07-23 | 赤壁市聚茂新材料科技有限公司 | 一种非钯活化镀镍液、镀镍方法 |
| US11505867B1 (en) | 2021-06-14 | 2022-11-22 | Consolidated Nuclear Security, LLC | Methods and systems for electroless plating a first metal onto a second metal in a molten salt bath, and surface pretreatments therefore |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3607353A (en) * | 1969-10-16 | 1971-09-21 | Gen Motors Corp | Surface treatment for electroplating |
| US3857724A (en) * | 1971-08-20 | 1974-12-31 | Ibm | Primer for electroless plating |
| US3929483A (en) * | 1971-10-22 | 1975-12-30 | Horizons Inc | Metal-plated images formed by bleaching silver images with alkali metal hypochlorite prior to metal plating |
| US5194367A (en) * | 1986-11-28 | 1993-03-16 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide photographic material |
| JP3175527B2 (ja) * | 1995-03-30 | 2001-06-11 | 上村工業株式会社 | 無電解ニッケルめっき液及びめっき方法 |
| JP3087163B2 (ja) * | 1995-10-23 | 2000-09-11 | 上村工業株式会社 | 無電解金めっきの厚付け方法 |
| US5648125A (en) * | 1995-11-16 | 1997-07-15 | Cane; Frank N. | Electroless plating process for the manufacture of printed circuit boards |
-
1998
- 1998-12-08 JP JP53233799A patent/JP3387507B2/ja not_active Expired - Lifetime
- 1998-12-08 CN CNB988025116A patent/CN1222636C/zh not_active Expired - Lifetime
- 1998-12-08 US US09/355,651 patent/US6156218A/en not_active Expired - Lifetime
- 1998-12-08 WO PCT/JP1998/005537 patent/WO1999031293A1/ja active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP3387507B2 (ja) | 2003-03-17 |
| CN1247577A (zh) | 2000-03-15 |
| WO1999031293A1 (en) | 1999-06-24 |
| US6156218A (en) | 2000-12-05 |
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