CN106232869B - 铁硼合金涂层及其制备方法 - Google Patents
铁硼合金涂层及其制备方法 Download PDFInfo
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- CN106232869B CN106232869B CN201580020986.1A CN201580020986A CN106232869B CN 106232869 B CN106232869 B CN 106232869B CN 201580020986 A CN201580020986 A CN 201580020986A CN 106232869 B CN106232869 B CN 106232869B
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- plating bath
- substrate
- ferroboron
- coating
- aqueous plating
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XQBCZVOLPUGXRL-UHFFFAOYSA-N methanesulfonic acid;nickel Chemical compound [Ni].CS(O)(=O)=O XQBCZVOLPUGXRL-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 238000003380 quartz crystal microbalance Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- 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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- 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
-
- 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
- C23C18/1675—Process conditions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1682—Control of atmosphere
-
- 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
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
Abstract
本发明提供了用于无电沉积铁硼合金涂层的含水镀浴,特征在于它包含至少一种铁离子源、至少一种硼基还原剂、至少一种复合剂、至少一种pH缓冲剂和至少一种碱,其中它的pH值是11或更高并且所述含水镀浴中的硼基还原剂相对于铁离子的摩尔比是至少6:1。还有,公开了使用所述含水镀浴的方法。本发明的含水镀浴显示良好的稳定性和镀敷速率并在各种基底上产生光泽而均匀的铁硼合金涂层。所述镀浴的优点是它不需要任何牺牲阳极。
Description
技术领域
本发明涉及在表面上形成铁硼合金涂层的无电沉积方法、用于此的镀浴和以此形成的涂层以及通过所述方法得到的涂层在电子工业中的示例性应用。
背景技术
通过无电沉积方法沉积的由镍和磷构成的涂层(NiP涂层)在电子工业中普遍用作例如耐腐蚀涂层。然而,因为镍对环境有害并且对消费者的健康有危险,所以最近关注点转向新材料。在过去其他材料主导的领域中,像例如作为涂料的基质,铁变得越来越受重视,因为它是普遍存在的,比较便宜并且无毒。
然而,由于形成不想要的副产物并且缺乏镀浴稳定性,铁基涂层的无电沉积被证明是困难的。本领域中众所周知,在适合其他金属无电沉积的条件下,无电铁沉积容易发生铁氧化物、铁氢氧化物和铁氧氢氧化物或其他沉淀物的形成。
因此,迄今,常见的是在沉积二元铁合金(例如铁硼)涂层的镀液中使用牺牲阳极(例如由铝制成)。N.Fujita等,Applied Surface Science 1997,113/114卷,61-65页示教了这样的沉积二元铁硼合金的方法,但报告了一旦基底和牺牲阳极之间的电连接断开,合金沉积就停止。牺牲阳极通常是以例如线或条形式的基质金属基材,其可用作外部电子源。这些牺牲阳极因此与所述基底电连接(同时它们可以浸在镀浴中)并提供必要的电子来还原所述基底表面上的铁。这样的镀法本质上是电镀方法,因为牺牲阳极充当了局部电池。电连接的这种需要使得这些电镀浴需要牺牲阳极,这与当今电子工业中小型化的要求不相容,在这种情况下许多小基底必须同时涂层(它们全部将必须与牺牲阳极电连接)。还有,非导电基底不能使用,因为它们不允许任何电子穿过它们到达它们的表面。这种技术的另一个例子是Hu Wangyu,Zhang Bangwei,Physica B 1991,175卷,396-400页。还有,中国专利CN 100562603C涉及利用牺牲阳极在铜箔上无电沉积三元稀土-铁-硼合金。在其中公开的镀浴还需要在镀敷发生之前用催化剂活化金属基底。W.Lingling等(在Metal Finishing2001,99(6)卷,92-96页中)报告了利用这样的牺牲铝阳极可沉积的三元铁-锡-硼合金。
与利用外部电子源的这些电解金属沉积方法相反,无电方法在形成许多金属的膜中是已知的。无电镀是在没有外部电子供应的帮助下,连续金属膜的受控自催化沉积。无电金属镀浴的主要组分是金属离子源、复合剂、还原剂、和作为任选成分的稳定剂、晶粒细化剂和pH调节剂(酸,碱,缓冲剂)。复合剂(本领域中也称为螯合剂)用于螯合待沉积的金属并防止所述金属从溶液中沉淀(即作为氢氧化物等等)。螯合金属致使所述金属可被还原剂利用,还原剂将所述金属离子转化为它们的金属形式。金属沉积的另一种形式是浸镀。浸镀是在没有外部电子供应的帮助和没有化学还原剂下的另一种金属沉积。机制依靠用来自下伏基底的金属取代存在于浸镀溶液中的金属离子。在本发明的环境下,无电镀应被理解为借助于化学还原剂(在本文中称为“还原剂”)的自催化沉积。
通过无电方法形成含铁沉积物的可能性是沉积镍、铁和磷或硼的三元合金。这样的方法已经在US 3,385,725和US 3,483,029中报导。在其中描述的沉积物主要由镍组成并含有2%或更少的磷或硼。虽然US 3,385,725示教了含有同等高的镍和铁量的镀浴,但形成的沉积物主要由镍组成。所公开的方法因此不适合于形成铁含量高的沉积物。
US 3,150,994涉及在金属表面上无电镀金属硼合金的方法。它还公开了在所述基底上特定地从由大量过量的氨、可溶性铁盐和离子性氢硼化物组成的镀浴形成铁硼合金的方法。然而,所公开的镀敷不可避免地伴有所形成的合金在浴自身中的沉淀,并因此,导致浴的寿命受限。所公开的方法特别不利的是所述沉淀物本身是促进进一步沉积的活跃的催化部位。
英国专利申请号GB 1339829公开了在窗玻璃上沉积由铁硼合金制成的透明涂层的方法。然而,这种方法必要的先决条件是在镀浴中使用肼衍生物。由于所述化合物的毒性和致癌潜力,这与现今的安全要求不相容。还有,所述基底在镀敷之前需要活化步骤。
英国专利申请号GB 1365172示教了前面提到的英国专利申请的镀浴通过在其中使用羰基化合物来延长寿命。然而,使用肼作为进一步还原剂和使用活化步骤仍然是必需的。
US 2009/0117285公开了铁硼合金在预先活化的纤维素纤维上的无电沉积方法。然而,这种方法需要使用很窄的pH操作窗。还有,在其中公开的浴缺乏稳定性和镀敷速率(参见实施例1)。
发明目标
因此本发明的一个目标是提供在基底上以高镀敷速率无电沉积铁硼合金涂层的方法,所述方法不需要使用任何牺牲阳极(或任何其他外部电子源)。
本发明的另一个目标是提供用于所述方法中的稳定的镀浴组成。
本发明的又一个目标是提供在基底上通过所述方法形成的铁硼合金涂层。
本发明的再一个目标是提供在基底上通过所述方法得到的耐腐蚀的铁硼合金涂层。
发明内容
上述目标通过根据本发明的镀浴和它的使用方法解决。本发明的用于无电沉积铁硼合金涂层的含水镀浴,特征在于它包含
(i)至少一种铁离子源;
(ii)至少一种硼基还原剂;
(iii)至少一种复合剂;
(iv)至少一种pH缓冲剂;和
(v)至少一种碱,
其中所述含水镀浴的pH值是11或更高并且所述含水镀浴中硼基还原剂相对于铁离子的摩尔比是至少6:1。
本发明的在基底上无电沉积铁硼合金涂层的方法,特征在于所述方法包括以下步骤
(a)提供基底,和
(b)将所述基底与用于无电沉积铁硼合金涂层的含水镀浴接触,其特征在于所述含水镀浴包含
(i)至少一种铁离子源;
(ii)至少一种硼基还原剂;
(iii)至少一种复合剂;
(iv)至少一种pH缓冲剂;和
(v)至少一种碱,
其中所述含水镀浴的pH值是11或更高并且所述含水镀浴中硼基还原剂相对于铁离子的摩尔比是至少6:1,从而将铁硼合金涂层沉积在所述基底上。
本发明的含水镀浴及其应用的本发明的方法允许铁硼合金涂层的稳定镀敷条件。所述方法还允许在基底上以高镀敷速率形成铁硼合金涂层。以此形成的铁硼合金涂层在基底的厚度分布和覆盖度上是光泽而均匀的。还有,它们是非晶的并显示出充分的耐腐蚀性以用于电子工业中,例如在印刷电路板(PCB)或集成电路基板(IC基板)的制造中。
附图说明
图1:通过本发明的方法形成的铁硼合金涂层的x-射线光电子谱(XPS)(参见实施例4)。
图2:通过本发明的方法形成的铁硼合金涂层的x-射线衍射测量(XRD)(参见实施例4)。
具体实施方式
本发明的目标是通过在下文中更详细描述的本发明方法中使用本发明的含水镀浴而解决的。
本发明的用于无电沉积铁硼合金涂层的含水镀浴特征在于它包含
(i)至少一种铁离子源;
(ii)至少一种硼基还原剂;
(iii)至少一种复合剂;
(iv)至少一种pH缓冲剂;和
(v)至少一种碱,
其中所述含水镀浴的pH值是11或更高并且所述含水镀浴中硼基还原剂相对于铁离子的摩尔比是至少6:1。
本发明人已经发现,通过使用pH为11或更高并且其中含水镀浴中的硼基还原剂相对于铁离子的摩尔比为至少6:1的用于沉积铁硼合金涂层的含水镀浴,可以省略至今使用的牺牲阳极。这样的镀浴是稳定的并且允许100nm/小时或更高的高镀敷速率,例如100至500nm/小时之间。
本发明的含水镀浴包含至少一种铁离子源。所述至少一种铁离子源优选是水溶性亚铁盐,例如卤化亚铁、硫酸亚铁、硫酸亚铁铵、硝酸亚铁、和/或亚铁盐的相应水合物。
在所述含水镀浴中由至少一种铁离子源提供的铁离子的浓度范围从10mmol/l至120mmol/l,优选从25mmol/l至75mmol/l,最优选从40mmol/l至60mmol/l。铁离子浓度超过120mmol/l,由于在镀浴本身中形成铁沉淀物,可能导致镀浴不稳定。
本发明的含水镀浴中所述至少一种硼基还原剂是水溶性硼基还原剂。这些水溶性硼基还原剂选自碱金属硼氢化物例如硼氢化钠、硼氢化钾和氨基硼烷例如二甲基氨基硼烷。碱金属硼氢化物根据本发明是优选的。所述含水镀浴优选不含肼基还原剂,因为它们是致癌的。
所述含水镀浴包含相对于铁离子的摩尔过量的硼基还原剂。在所述含水镀浴中所述硼基还原剂相对于铁离子的摩尔比是至少6:1,并优选所述摩尔比在6:1至10:1的范围内。如果所述硼基还原剂对铁离子的摩尔过量是5:1或更低,则铁硼合金涂层的镀敷发生不活跃或完全不发生。通常,它在短时间镀敷之后停止(实施例6,浴1)。如果所述摩尔比是11:1或更高,所述镀敷持续发生,虽然缓慢(实施例6,浴3)。
本发明的含水镀浴中包括在含水介质中能够与铁离子、优选铁(II)-离子形成复合物的至少一种复合剂或复合剂混合物。
羧酸、羟基羧酸、氨基羧酸和前者的盐或其混合物可以用作复合剂。可用的羧酸包括单、二、三和四羧酸。所述羧酸可以被各种取代基部分例如羟基或氨基取代,并且所述酸可以作为它们的钠、钾或铵盐引入所述含水镀浴中。一些复合剂如乙酸或甘氨酸,例如,还可以充当pH缓冲剂,并且考虑到它们的双重功能性,对任何含水镀浴可优化这样的添加组分的适当浓度。
可用作本发明镀浴中的复合剂的这类羧酸的实例包括:单羧酸例如乙酸、羟基乙酸(乙醇酸)、氨基乙酸(甘氨酸)、2-氨基丙酸(丙氨酸)、2-羟基丙酸(乳酸);二羧酸例如琥珀酸、氨基琥珀酸(天冬氨酸)、羟基琥珀酸(苹果酸)、丙烷二酸(丙二酸)、酒石酸;三羧酸例如2-羟基-1,2,3-丙烷三羧酸(柠檬酸);和四羧酸例如乙二胺四乙酸(EDTA)。在一种实施方式中,本发明的含水镀浴中利用两种或更多种上述复合剂的混合物。使用酒石酸或其盐作为至少一种复合剂是本发明优选的。
所述含水镀浴中存在的所述复合剂与铁离子的摩尔比优选在1:1至10:1的范围内,更加优选在2:1至8:1的范围内,最优选在2:1至4:1的范围内。
本发明的含水镀浴的pH值是11或更高。如果所述含水镀浴的pH值降至低于11,所述含水镀浴变得不稳定(参见实施例2)。优选所述含水镀浴的pH值范围从11至13。更优选所述含水镀浴的pH值范围从11.0至12.5,更加优选所述pH值范围从11.0至12.0或从11.5至12.5,并最优选所述pH值范围从11.0至11.5。
所述pH值可在25℃用pH计测量。所述测量必须持续直到pH值恒定,但至少达1min。所述pH计必须用针对所述pH值范围的至少两个适当的校准用标准进行校准。还有,所使用的电极必须适合于所述pH值范围。用于在所述含水镀浴中测量pH值的合适的pH计是与InLab Semi-Micro-L电极相结合的SevenMulti S40专业pH计(Mettler-Toledo GmbH,参比系统:带有Ag+-肼的ARGENTHALTM,参比电极:3mol/l KCl)。该pH计可优选在使用之前用Merck KGaA供应的三个7.00、9.00和12.00的高pH值标准品校准。
在所述含水镀浴中用于调节所述含水镀浴pH值的至少一种碱没有特别的限制,只要它能够在含水介质中形成氢氧离子并从而增加所述含水镀浴的pH值即可。使用两种或更多种碱的混合物也在本发明的范围内。优选地,所述含水镀浴的pH值可用常用的碱例如氢氧化锂、氢氧化钠、氢氧化钾、四甲基氢氧化铵、四乙基氢氧化铵、氨、烷基胺例如甲胺、三乙胺或其混合物调节。
本发明的含水镀浴还包含至少一种pH缓冲剂。这样的pH缓冲剂可以是例如有机酸或弱酸性无机化合物或前者的盐,例如甲酸、乙酸、丙酸、甘氨酸、碱金属碳酸盐、碱金属碳酸氢盐、铵化合物例如氢氧化铵或三(羟甲基)氨基甲烷、磷酸、亚磷酸、来源于磷酸和亚磷酸的盐和/或硼酸及其盐。此外,基于碱金属氢氧化物作为碱以及甘氨酸或碱金属氯化物作为pH缓冲剂的pH缓冲体系在本发明的范围内。在本发明的含水镀浴中所述至少一种pH缓冲剂的浓度范围从1mmol/l至200mmol/l。优选地,存在于本发明的含水镀浴中的所述至少一种pH缓冲剂是硼酸或前者的盐,并且更加优选使用浓度为40mmol/l至100mmol/l的硼酸或其盐。
本发明的含水镀浴是水基的并且含有至少50重量%的水。另外,可以添加水可混溶的有机溶剂,例如醇、二醇和二醇醚。优选地,所述镀浴只包含水作为溶剂。
本发明的含水镀浴可以包含第二种可还原金属离子源,基于存在于所述含水镀浴中的铁离子的量,其量为0.01至10摩尔%,优选0.1至7.5摩尔%,更优选1至5摩尔%。这样的可还原的金属离子可以是镍离子或钴离子。镍离子是优选的。镍离子源可以是任何水溶性镍盐和镍复合物,优选选自硫酸镍、氯化镍、碳酸镍、甲磺酸镍、乙酸镍、它们相应的水合物和前者的混合物。钴离子源可以是任何水溶性钴盐和钴复合物,优选选自硫酸钴、氯化钴、它们相应的水合物和前者的混合物。
在本发明的另一种且更优选的实施方式中,所述含水镀浴不含任何有意添加的其他可还原的金属离子(普遍存在于技术原料中的任何痕量杂质不计),因而允许沉积二元铁硼合金涂层。这样的二元铁硼合金涂层由铁和硼组成。它们通常含有高硼量,由此可获得这类涂层的非晶形态和耐腐蚀性(实施例4和5)。
本发明的含水镀浴可以包含本领域中已知的其他添加剂,例如润湿剂和/或稳定剂。
本发明的含水镀浴优选不直接或经基底间接接触任何牺牲阳极。
本发明的含水镀浴的制备没有特别的限制。所述至少一种铁离子源、所述至少一种硼基还原剂、所述至少一种复合剂、所述至少一种pH缓冲剂、和任选的任何其他添加剂可在水(或与其溶剂的混合物)中溶解到所需的浓度,并且可用所述至少一种碱以任何顺序调节pH值。然而,在用所述至少碱调节pH值之后添加所述硼基还原剂是有利的。以下描述制备本发明的含水镀浴的优选方法。包括所述至少一种铁离子源、所述至少一种复合剂、所述至少一种pH缓冲剂和任何其他任选的添加剂的水溶液溶解在水中,并且所述溶液的pH值用至少一种碱调节到11或更高。第二水溶液用至少一种碱调节到pH 11或更高,然后向这种第二水溶液添加所述至少一种硼基还原剂。然后,所述两种溶液合并,并且,如有必要,在体积、浓度和pH值方面进行调节。
本发明的方法包括以下步骤
(a)提供基底,和
(b)将所述基底与本发明的含水镀浴接触并从而将所述铁硼合金涂层沉积在所述基底上。
用于本发明方法中的基底选自金属基底、玻璃基底、塑料基底和硅基底(本领域中也称为硅衬底)例如半导体晶片基底。包含一个或多个由金属、玻璃、塑料和硅制成的表面的基底在本发明的环境中也被理解为是金属基底、玻璃基底、塑料基底和硅基底。
它们在形式和功能上不受限制。金属基底或金属表面是优选的。还有,本发明的方法中可使用覆盖至少一个金属层(并因而具有金属表面)的非金属基底。在本发明的方法中更加优选使用铜基底或铜合金基底。尤其是,电子工业中使用的基底如印刷电路板或IC基板在本发明的方法的范围之内。在基底表面的选定部分上沉积所述铁硼合金涂层,也可能在本发明的范围内。
在所述方法中可任选纳入其他步骤。这些任选的步骤是
(c)所述基底的任选预处理步骤,
(d)从本发明的含水镀浴和/或它的周围气氛中除去氧的任选步骤,
(e)在无电沉积所述铁硼合金涂层之后干燥所述基底的任选步骤。
上述步骤(a)和(b)以给出的顺序进行。如果在本发明的方法中包括任选步骤(c),那么它在步骤(a)和(b)之间进行。
如果本发明的方法包括任选步骤(d),它可在所述方法的任何时间进行,优选,在步骤(b)之前和/或同时进行。
如果在所述方法中包括任选步骤(e)0,那么它结束本发明的方法。
所述方法还可以包括在上述步骤之前、之间或之后任选的用水清洗步骤。
本发明的一种实施方式是所述基底经受一个或多个在步骤(a)和(b)之间进行的任选预处理步骤(c)。以下描述所述预处理步骤。本领域技术人员知道,基底有时被来自加工、人类接触或环境的残留物例如油脂、脂肪或蜡残留物污染。可能对所述镀敷有害的残留物是例如氧化产物、油脂或蜡。因此,在那些情况下,为了得到最佳的镀敷结果,通常一个或多个预处理步骤是有利的。这些预处理步骤是本领域中已知的,有时称为蚀刻或清洁。这些步骤尤其包括用有机溶剂、酸性或碱性水溶液或者包含表面活性剂、还原剂和/或氧化剂的溶液除去所述残留物。将前述步骤相结合以求得到干净的基底,也可能在本发明的范围内。在这些预处理步骤之前、之间或之后,也可能包括其他清洗步骤。有时,在所述基底的预处理中包括蚀刻步骤以增加它的表面积。这通常通过用包含强酸如硫酸和/或氧化剂如过氧化氢的水溶液处理所述基底而实现。
塑料基底在活化之前经常需要以氧化处理进行处理。这些方法是本领域中公知的。这样的处理的实例包括用包含其他氧化剂例如铬酸、硫酸、过氧化氢、高锰酸盐、高碘酸盐、铋酸盐、卤素含氧化合物如亚氯酸盐、亚氯酸、氯酸盐、高氯酸盐、其相应的盐或酸或相应的溴和碘衍生物的酸性或碱性溶液蚀刻。这样的蚀刻溶液的实例公开在例如EP 2 009142 B1、EP 1 001 052 A2和US 4,629,636中。后一文献还公开了包括活化步骤的预处理塑料表面的方法(在其中的实施例I和II)。本发明的环境中的塑料材料选自丙烯腈-丁二烯-苯乙烯共聚物(ABS共聚物)、聚酰胺(PA)、聚碳酸酯(PC)、聚酰亚胺(PI)、环氧树脂、环氧玻璃复合物和ABS共聚物与至少一种其他聚合物的混合物。
在本发明的环境中要镀所述铁硼合金涂层的非金属基底,即玻璃基底、硅基底和塑料基底,特别是非金属表面,还可以通过在本领域中技术内的手段(如例如US 4,617,205第8栏中所述)预处理,使得它们对于所述沉积更能接受或自催化。这种预处理步骤称为活化。全部或选定部分的表面可以被活化。玻璃基底、硅基底和塑料基底被贵金属(例如胶态或离子形式的铜、银、金、钯、铂、铑、铱、和优选钯)的这种活化在步骤(a)和(b)之间进行。有利地,与其他方法(参见CN 100562603 C)相反,在金属基底、尤其是铜基底的情况下,活化步骤不是必需的。
在所述活化之内,有可能在基底上沉积所述铁硼合金涂层之前敏化所述基底。这可以通过将催化金属吸附在所述基底的表面上而达到。
示例性和非限制性的预处理方法,尤其是可用于非金属基底的,可以包含一个或多个以下步骤
-任选地,塑料基底的氧化处理,
-任选地,清洁和调节所述基底以增加吸附。用清洁剂除去有机物和其他残留物。它还可以含有为了后面的活化步骤准备所述表面、即提高所述催化剂的吸附和产生更均匀活化的表面的附加物质(调节剂),
-用过硫酸盐或过氧化物基蚀刻体系蚀刻,
-与预浸溶液、例如盐酸溶液或硫酸溶液接触,任选与也在所述预浸溶液中的碱金属盐例如氯化钠接触,
-与含有胶态或离子性催化金属例如贵金属、优选钯的活化剂溶液接触,造成所述表面变成催化性的。所述预浸起到保护所述活化剂免于夹杂和污染,
-和任选地,特别是如果所述活化剂含有离子性催化金属的话,与还原剂接触,其中离子性活化剂的金属离子被还原成元素金属;
-或者,如果所述活化剂含有胶态催化金属的话,与加速剂接触,其中从所述催化金属中除去胶体、例如保护胶体的组分。
金属基底预处理步骤(c)的组合的非限制性实例在下面的方案中显示
-用丙酮将所述金属基底去油脂,
-用去离子水清洗,
-用含硫酸的水溶液蚀刻,
-用去离子水清洗,和
-干燥所述金属基底。
本发明的优选实施方式是包括任选步骤(d)以从所述含水镀浴和/或它的周围气氛中除去氧,这在下文中更详细地解释。本领域技术人员已知在铁基沉积物的镀敷过程期间存在的氧可以导致铁氧化物、铁氧氢氧化物和铁氢氧化物的形成。因此在无氧或减氧气氛中运行本发明的方法,是所述方法的优选实施方式。在本发明的含水镀浴和/或它的周围气氛中除去氧并因而降低氧浓度的其他步骤因此是本发明的优选实施方式。如何实现除氧,本领域技术人员有许多不同的方法可利用。镀浴可以例如用惰性气体吹扫。或者,通过对所述镀浴(和它的直接环境)减压并然后添加惰性气体来除氧可能是有用的。重复这些步骤特别有用。此外,所述镀敷方法可在罩子或容器中在惰性气氛中进行。然后,所述含水镀浴的周围气氛也将是无氧的或将具有降低的氧浓度。镀浴也可以在这样的气氛中保存。作为惰性气体,可以优选使用氩气或氮气。用惰性气体吹扫是本发明优选的,因为它能容易地实现并且除氧导致浴的稳定性改善和镀覆速率增加(参见实施例3和4的镀敷速率差异)。
所述基底与本发明的含水镀浴接触(步骤(b))。它可以浸泡在所述镀浴中;所述镀浴也可以喷洒或擦拭在其上。通过所述基底与本发明的含水镀浴接触,发生铁硼合金涂层的沉积。优选所述基底不与任何牺牲阳极电连接。还优选本发明的含水镀浴不与任何牺牲阳极接触(例如通过将后者浸泡在所述浴中)。因此优选所述基底或本发明的含水镀浴两者都不与牺牲阳极接触。
在本发明的方法的步骤(b)中,所述基底和本发明的含水镀浴的接触可在水平的、卷对卷的、直立的和直立传送带化的镀敷设备中进行。可用于进行本发明方法的特别合适的镀敷工具在US 2012/0213914 A1中公开。
所述基底与本发明的含水镀浴接触之后,残余量的水和/或其他溶剂可在任选的干燥步骤(e)中除去。这可通过机械除去这些液体(例如擦拭)、通过施加气流(空气或惰性气体)和/或通过升高的温度完成。如果有充分的时间,所述基底可保存在环境条件下直至干燥。或者,所述基底可以在沉积之后直接进一步加工。
在镀敷过程期间所述含水镀浴的温度范围从20℃至90℃,并优选它范围从30℃至70℃。在镀敷过程中所述含水镀浴的最优选温度范围从40℃至50℃。
优选在所述铁硼合金涂层的镀敷过程期间搅拌本发明的含水镀浴。搅拌可以通过例如机械活动所述含水镀浴如振动、搅拌持续泵送液体实现或者通过超声波处理或升高的温度或进气(例如用惰性气体吹扫所述含水镀浴)内在实现。
本发明的方法在它的期限方面没有特别的限制。本发明的方法可以进行为了达到期望的目标例如一定的铁硼合金涂层厚度所需要的时长之久。然而,优选的期限范围从1min至600min并更优选从5min至120min。
本发明的方法允许沉积铁硼合金涂层。如果在本发明的含水镀浴中存在第二种可还原的金属离子,将会沉积掺杂所述第二种可还原金属的铁硼合金涂层。
本发明的方法特别(并优选)允许形成由10至90原子%铁以及余量(至100原子%)是硼、优选40至80原子%铁以及余量(至100原子%)是硼(参见实施例4)组成的二元铁硼合金涂层。本发明的方法因此允许在不需要牺牲阳极下沉积二元铁硼合金。
本发明的方法的优点是,为了在基底上得到铁硼合金涂层,牺牲阳极不是必需的。这在生产PCB和IC基板中是先决条件,因为小型化要求越来越小的尺度和更复杂的图案并且这些图案不可能以有效的方式与外部电源接触。杜绝任何牺牲阳极需要也是非导电基底用于本发明方法中的必要前提,因为来自任何牺牲阳极的电子不能穿过这样的非导电基底来让铁离子在它们的表面处发生还原。
本发明的方法的另一个优点是所述铁硼合金涂层的沉积以高镀敷速率进行(参见实施例3、4和6)。
本发明的另一个优点是由本发明的方法提供的铁硼合金涂层在所述基底的厚度分布和覆盖度上是光泽而均匀的(参见实施例3)。
在所述金属基底上所形成的铁硼合金涂层由于它们的高硼含量而显示非晶特性,这是耐腐蚀涂层所希望的(参见实施例4)。因此,它们表现出良好的耐腐蚀性(参见实施例5)。
术语镀(敷)和沉积在本文中可互换使用。
以下非限制性实施例将说明本发明。
实施例
所述铁硼合金涂层的表征利用Nova NanoLab 200和Helios NanoLab 650扫描电子显微镜(SEM,二者均为FEI Company)进行。使用X-射线光电子光谱(VersaProbe XPS,Physical Electronics GmbH)测量所述铁硼合金涂层的组成。使用Scintagx-射线衍射仪(XRD)表征所述铁硼合金涂层的结晶性。所述铁硼合金涂层的厚度用石英晶体微量天平(SRS QCM200,Stanford Research Systems,Inc.)从石英晶体中的频率变化来确定。
开路电位测量(OCP)利用4型VersaStat稳压器(Princeton Applied Research)使用饱和甘汞电极(SCE,Radiometer Analytical)作为参比进行。
耐腐蚀性也使用带有SCE参比电极和铂丝对电极(Encompass)的4型VersaStat稳压器在3.5重量%的氯化钠盐溶液中测量。极化扫描以2mV/s的扫描频率在所述盐溶液中经过以所述基底的OCP为中心的600mV窗口。
PH值在25℃下用pH计测量(SevenMulti S40专业pH计,电极:InLab Semi-Micro-L,Mettler-Toledo GmbH,带有Ag+-肼的ARGENTHALTM,参比电解质:3mol/l KCl)。所述测量持续直到pH值变得恒定,但在任何情况下至少达3min。所述pH计在使用之前用Merck KGaA供应的用于7.00、9.00和12.00高pH值的三个标准品校准。
如果没有另外提到的话,溶剂在使用之前用氩气吹扫它们1h脱除氧。
基底的预处理
铜箔用作镀敷试验中的金属基底。各箔样品用丙酮去油脂,然后用去离子水洗涤。尔后,它们用2mol/l的硫酸水溶液蚀刻15秒。用去离子水最后清洗之后,它们准备好供使用。
实施例1:根据US 2009/0117285的方法(比较)
pH值为10.2(用氢氧化钠调节)并含有50mmol/l硫酸亚铁铵、250mmol/l硼氢化钠、150mmol/l柠檬酸钠和49mmol/l硼酸的含水镀浴用于镀敷铜箔。所述预处理的铜基底因此在由玻璃制成的镀池中分别浸泡在24℃的所述含水镀浴中15min和45min。随时间监测所述镀浴的外观和所形成的铁硼合金涂层的厚度(参见表1)。
表1:实施例1(比较)
实施例1的镀浴缺乏稳定性并且在浴本身中和镀敷容器的表面上迅速形成黑色沉淀。通过这种方法得到的铁硼合金涂层是无光泽的并且所述基底的表面被不均匀地涂层。所述铁硼合金涂层的沉积速率很慢。
实施例2:pH值为10.5(比较)
pH值为10.5(用氢氧化钠调节)并含有50mmol/l硫酸亚铁铵、300mmol/l硼氢化钠、49mmol/l硼酸和127mmol/l罗氏(Rochelle's)盐的含水镀浴用于镀敷铜箔。所述预处理的铜基底因此浸泡在41℃的所述镀浴中。随时间监测所述镀浴的外观和所形成的铁硼合金涂层的厚度。
所述镀浴迅速劣化并且太不稳定而不能在镀敷过程中使用。
实施例3:在铜基底上的铁硼合金涂层(本发明)
pH值为11(用氢氧化钠调节)并含有50mmol/l硫酸亚铁铵、300mmol/l硼氢化钠、127mmol/l罗氏盐和49mmol/l硼酸的含水镀浴用于镀敷铜箔。所述含水镀浴没有用氩气吹扫,因此所述镀敷试验在空气下运行。所述预处理的铜基底在由玻璃制成的镀池中分别浸泡在41℃的所述镀浴中15min和45min。随时间监测所述镀浴的外观和所形成的铁硼合金涂层的厚度(参见表2)。
表2:实施例3(本发明).
镀敷时间[min] | 沉积厚度[nm] | 镀浴的外观 |
15 | 58.2 | 浅绿的澄清溶液,气体放出 |
45 | 116.1 | 颜色转变成黑色,气体放出减少 |
实施例3的含水镀浴显示了良好的稳定性和高镀覆速率。在所述铜基底表面上均匀地形成了光泽的铁硼合金涂层。以此处理的基底均匀覆盖着在所述基底的整个表面上形成的光泽发亮的银一样的铁硼合金涂层。
实施例4:在金属化基底上的铁硼合金涂层(本发明)
用去离子水制备含有50mmol/l硫酸亚铁铵、40mmol/l硼酸和127mmol/l罗氏盐的水溶液。所述溶液的pH值在烧杯中用氢氧化钠调节到pH 11。在第二个烧杯中,第二水溶液通过首先用氢氧化钠调节pH值到11和然后在这种第二溶液中溶解300mmol/l硼氢化钠而制备。合并所述两种溶液,所述混合物的最终体积用去离子水补足到100mL并用氢氧化钠调节pH值到11。所述混合物然后被加热到45℃并在发生镀敷的同时用氩气吹扫。有二氧化硅层阵列、由TaN制成的阻挡层和铜层的Si晶片(后两个层通过PVD沉积)在预处理之后浸泡在所述含水镀浴中30min。
实施例4的含水镀浴显示了良好的稳定性和在所述晶片基底上0.24μm/h的平均铁硼合金涂层镀覆速率。所述铁硼合金涂层经XPS分析由30.8原子-%硼和69.2原子-%铁组成(参见图1)。所述铁硼合金涂层的结晶性由XRD证实是非晶的(参见图2)。发现所述铁硼合金涂层的少量表层氧化(氧化铁和氧化硼分别2θ=45.6和48.4)。
实施例5:铁硼合金涂层的耐腐蚀性(本发明)
制备如实施例3中所述的含水镀浴并用氩气吹扫。预处理的铜基底在连续的氩气吹扫下在所述镀浴中浸泡1h。如此涂层的基底具有用铁硼合金涂层抛光的均匀覆盖表面。该涂层基底在3.5重量%的氯化钠溶液中经受腐蚀试验。极化测量以2mV/s的扫描速率在600mV窗口(从OCP-300mV至OCP+300mV)中进行。极化曲线指出所形成的铁硼合金的腐蚀电位为-0.81V。发现所述铁硼合金涂层的腐蚀电流密度是31.1μA/cm2。
在所述铜基底上形成的铁硼合金涂层的这种耐腐蚀性对于PCB工业中的应用在可接受的范围内。
实施例6:硼基还原剂与铁离子源的摩尔比的变动
三种含水镀浴,各自pH值为11(用氢氧化钠调节)并含有50mmol/l硫酸亚铁铵、127mmol/l罗氏盐、49mmol/l硼酸和在表3中所给出的量的硼氢化钠,用于镀敷被金覆盖、在金上已经沉积了铜层(因而提供铜表面)的石英晶体。在所述含水镀浴构成和使用之前,DI水用氩气吹扫50分钟。所述预处理的铜基底在由玻璃制成的镀池中在41℃的所述镀浴中浸泡70min。随时间监测所述镀浴的外观和所形成的铁硼合金涂层的厚度(参见表3)。
表3:实施例6.
在试验的过程中,所述不同镀浴的外观没有明显改变。在浸泡所述基底之前,所述镀浴加热五分钟,在此时间中,它们全部从中-淡绿改变成它们最终的颜色,但这些颜色没有任何进一步的改变。
浴1(涉及表3中的1a至1d条目,比较)具有浅绿色调并形成许多微小的黑色粒子。可见强烈的气体放出。
浴2(涉及表3中2a至2d条目,本发明,并代表硼基还原剂与铁离子源的优选摩尔比)显示典型的镀浴外观并且很黑且不透明。可见一些气泡,但没有浴1那么多。
浴3(涉及表3中的3a至3d条目,本发明)看上去几乎完全像浴2,但显示明显更强的气体放出。
用含有更低的硼基还原剂(50mmol/l和150mmol/l)的比较浴1的变体重复,15min之后在所述基底上没有产生任何铁硼合金涂层。
能够清楚看出,如果含水镀浴中硼基还原剂与亚铁盐的比率是10摩尔当量比1摩尔当量(表3中名为“还原剂/Fe的摩尔比”的列),则铁硼合金涂层的沉积迅速而稳定地进行。所述镀浴也显示良好的稳定性。
如果像浴1(表3中的1a至1d条目)那样,所述比率是5当量的硼基还原剂比亚铁盐,则镀敷速率以较低的初始值开始而且所述镀敷没有连续进行并在约20min之后几乎完全停止镀敷。还有,形成的黑色粒子(或许是铁或铁盐沉淀物)表明所述镀浴的寿命低。这样的浴因此不适合铁硼合金涂层形成。
如果像浴3(表3中的3a至3d条目)那样,所述比率超过10当量的硼基还原剂比亚铁盐,则镀敷速率以很低的初始值开始并且没有任何进一步的增加。然而,所述镀浴显示良好的稳定性。
Claims (14)
1.用于无电沉积铁硼合金涂层的含水镀浴,其特征在于它包含
(i)至少一种铁离子源;
(ii)至少一种硼基还原剂;
(iii)至少一种螯合剂;
(iv)至少一种pH缓冲剂;和
(v)至少一种碱,
其中所述含水镀浴的pH值是11或更高并且所述含水镀浴中的硼基还原剂与铁离子的摩尔比在6:1至10:1的范围内;
其中所述含水镀浴包含选自镍离子或钴离子的第二种可还原金属离子源,其量基于存在于所述含水镀浴中铁离子的量为0.01摩尔%至10摩尔%,或者其中所述含水镀浴不含任何有意添加的其他可还原金属离子。
2.根据权利要求1所述的含水镀浴,其特征在于所述至少一种铁离子源是水溶性亚铁盐。
3.根据权利要求1或2所述的含水镀浴,其特征在于所述至少一种硼基还原剂选自碱金属硼氢化物和氨基硼烷。
4.根据权利要求1或2所述的含水镀浴,其特征在于所述至少一种螯合剂选自羧酸、羟基羧酸、氨基羧酸或其盐。
5.根据权利要求1或2所述的含水镀浴,其特征在于所述铁离子在其中的浓度范围从10mmol/l至120 mmol/l。
6.根据权利要求1或2所述的含水镀浴,其特征在于所述至少一种pH缓冲剂是硼酸和/或其盐。
7.根据权利要求1或2所述的含水镀浴,其特征在于所述pH值范围从11至13。
8.在基底上无电沉积铁硼合金涂层的方法,其特征在于所述方法包括以下步骤
(a)提供基底,和
(b)将所述基底与根据权利要求1至7任一项所述的含水镀浴接触;并从而将铁硼合金涂层沉积在所述基底上。
9.根据权利要求8所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于所述基底不与任何牺牲阳极电连接。
10.根据权利要求8或9所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于所述方法还包括从所述含水镀浴和/或它的周围气氛除去氧的步骤。
11.根据权利要求10所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于用惰性气体吹扫所述含水镀浴和/或它的周围气氛以从中除去氧。
12.根据权利要求8或9所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于所述基底选自金属基底、玻璃基底、硅基底和塑料基底。
13.根据权利要求12所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于使用铜基底或铜合金基底。
14.根据权利要求12所述的在基底上无电沉积铁硼合金涂层的方法,其特征在于所述玻璃基底、硅基底或塑料基底在步骤(a)和(b)之间通过贵金属活化。
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ES2826441T3 (es) | 2017-06-02 | 2021-05-18 | Atotech Deutschland Gmbh | Baños de metalizado no electrolítico de aleación de níquel, un método de deposición de aleaciones de níquel, depósitos de aleación de níquel y usos de dichos depósitos de aleación de níquel formados |
US20220389588A1 (en) | 2019-11-20 | 2022-12-08 | Atotech Deutschland GmbH & Co. KG | Electroless nickel alloy plating baths, a method for deposition of nickel alloys, nickel alloy deposits and uses of such formed nickel alloy deposits |
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GB1194625A (en) * | 1967-06-19 | 1970-06-10 | Ibm | Boron Containing Composite Metallic Films and Plating Baths for their Electroless Deposition |
US3859130A (en) * | 1971-04-15 | 1975-01-07 | Ibm | Magnetic alloy particle compositions and method of manufacture |
US4181760A (en) * | 1977-06-06 | 1980-01-01 | Surface Technology, Inc. | Method for rendering non-platable surfaces platable |
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US3483029A (en) * | 1966-07-15 | 1969-12-09 | Ibm | Method and composition for depositing nickel-iron-boron magnetic films |
US3723158A (en) * | 1969-06-02 | 1973-03-27 | Ppg Industries Inc | Transparent metal films and wet chemical method of producing the same |
US3889017A (en) * | 1971-02-02 | 1975-06-10 | Ppg Industries Inc | Chemical filming solution and process for plating therewith |
US5897692A (en) * | 1996-09-10 | 1999-04-27 | Denso Corporation | Electroless plating solution |
US20050095855A1 (en) * | 2003-11-05 | 2005-05-05 | D'urso John J. | Compositions and methods for the electroless deposition of NiFe on a work piece |
US7223695B2 (en) * | 2004-09-30 | 2007-05-29 | Intel Corporation | Methods to deposit metal alloy barrier layers |
US20090117285A1 (en) | 2007-08-08 | 2009-05-07 | Dinderman Michael A | ROOM TEMPERATURE ELECTROLESS IRON BATH OPERATING WITHOUT A GALVANIC COUPLE FOR DEPOSITION OF FERROMAGNETIC AMORPHOUS FeB FILMS |
JP5297171B2 (ja) * | 2008-12-03 | 2013-09-25 | 上村工業株式会社 | 無電解ニッケルめっき浴及び無電解ニッケルめっき方法 |
US8632628B2 (en) * | 2010-10-29 | 2014-01-21 | Lam Research Corporation | Solutions and methods for metal deposition |
-
2015
- 2015-03-17 US US15/127,036 patent/US9783891B2/en active Active
- 2015-03-17 CN CN201580020986.1A patent/CN106232869B/zh not_active Expired - Fee Related
- 2015-03-17 KR KR1020167029230A patent/KR102137300B1/ko active IP Right Grant
- 2015-03-17 WO PCT/EP2015/055508 patent/WO2015161959A1/en active Application Filing
- 2015-03-17 MY MYPI2016703648A patent/MY187084A/en unknown
- 2015-03-17 JP JP2016564246A patent/JP6474431B2/ja active Active
- 2015-03-17 EP EP15710183.3A patent/EP3134562B1/en not_active Not-in-force
Patent Citations (3)
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GB1194625A (en) * | 1967-06-19 | 1970-06-10 | Ibm | Boron Containing Composite Metallic Films and Plating Baths for their Electroless Deposition |
US3859130A (en) * | 1971-04-15 | 1975-01-07 | Ibm | Magnetic alloy particle compositions and method of manufacture |
US4181760A (en) * | 1977-06-06 | 1980-01-01 | Surface Technology, Inc. | Method for rendering non-platable surfaces platable |
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EP3134562B1 (en) | 2018-12-26 |
WO2015161959A1 (en) | 2015-10-29 |
US20170121824A1 (en) | 2017-05-04 |
KR20160147752A (ko) | 2016-12-23 |
CN106232869A (zh) | 2016-12-14 |
MY187084A (en) | 2021-08-30 |
EP3134562A1 (en) | 2017-03-01 |
US9783891B2 (en) | 2017-10-10 |
JP6474431B2 (ja) | 2019-02-27 |
JP2017514021A (ja) | 2017-06-01 |
KR102137300B1 (ko) | 2020-07-24 |
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