JP2015151581A - Electroformed article and method for manufacturing the same - Google Patents
Electroformed article and method for manufacturing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 246
- 229910052751 metal Inorganic materials 0.000 claims abstract description 154
- 239000002184 metal Substances 0.000 claims abstract description 154
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 230000004888 barrier function Effects 0.000 claims abstract description 55
- 238000000151 deposition Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 19
- 229910000531 Co alloy Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 191
- 238000005323 electroforming Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 239000011229 interlayer Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- -1 for example Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Abstract
Description
本発明は、電鋳分野に属し、積層構造を有する電鋳品及びその製造方法に関する。 The present invention belongs to the field of electroforming, and relates to an electroformed product having a laminated structure and a manufacturing method thereof.
近年、電子部品や精密部品等の各種の工業製品の小型化が進んでおり、微細且つ複雑な形状を有する精密部品のニーズが一層高まっている。このような精密部品は、微細な形状が容易に形成できるという点から、電鋳を用いて製造されているものが多い。 In recent years, various industrial products such as electronic parts and precision parts have been miniaturized, and the need for precision parts having fine and complicated shapes has further increased. Many of such precision parts are manufactured using electroforming because a fine shape can be easily formed.
これまでの電鋳品は、製造コストを抑える点からも、主に一段（一層）の金属めっき層のみから成るものが製造されてきた。すなわち、該製造方法によれば、鋳型として基板（母型）上にレジストを用いて、該レジストが除去された部分に金属めっき層を堆積させることによって、金属めっき層を型取り、その後、該レジスト及び基板（母型）を取り除くことによって、所望の形状に成形された金属めっき層を得るものである。 Conventional electroformed products have been manufactured mainly consisting of only one (one) layer of metal plating from the viewpoint of reducing manufacturing costs. That is, according to the manufacturing method, a metal plating layer is deposited by depositing a metal plating layer on a portion from which the resist is removed using a resist on a substrate (matrix) as a mold. By removing the resist and the substrate (matrix), a metal plating layer formed into a desired shape is obtained.
しかし、現状では、より微細且つ複雑な形状が要求されていることから、このような一段の金属めっき層のみから成る電鋳品を製造する方法では、品質的に限界となってきている。そのため、金属めっき層を積層することにより、これまでよりも微細且つ複雑な形状を形成できる多段（多層）の金属めっき層から成る電鋳品を製造することが、電鋳品の製造方法の主流となりつつある。 However, under the present circumstances, since a finer and more complicated shape is required, the method for producing an electroformed product composed of only one metal plating layer has been limited in quality. For this reason, it is a mainstream method for producing electroformed products to produce electroformed products composed of multi-stage (multilayer) metal plated layers that can form a finer and more complex shape than before by laminating metal plated layers. It is becoming.
その一方で、このような電鋳品は、多層構造の金属めっき層から成ることから、各金属めっき層間の密着力が不十分である場合には、結果的に脆い材料となる虞があるという問題点がある。そのため、現在では、各金属めっき層間の密着力（層間密着力）を向上させるための各種の方法が案出されている。特に、層間密着力を高めるために、金属めっき層間に薄膜状のストライクめっきを介在させる手法がよく知られている。ストライクめっきとは、基板素地の不動態皮膜を除去、活性化し、めっきの密着を良くするために行われる下地のめっきであり、通常、高電流密度で短時間に行われる。 On the other hand, since such an electroformed product is composed of a metal plating layer having a multilayer structure, if the adhesion between the metal plating layers is insufficient, there is a possibility that the material becomes a brittle material as a result. There is a problem. Therefore, various methods for improving the adhesion between the metal plating layers (interlayer adhesion) have been devised at present. In particular, a technique of interposing a thin-film strike plating between metal plating layers is well known in order to increase interlayer adhesion. The strike plating is a base plating performed to remove and activate the passive film on the substrate substrate and improve the adhesion of the plating, and is usually performed in a short time at a high current density.
例えば、配線基板の製造方法として、基板上にめっきされる金属めっき層の層間に銅ストライクめっきまたはニッケルストライクめっきを介在させて、金属めっき層の層間の密着力を向上させるものがある（特許文献１参照）。また、めっき部材の製造方法として、金属部材上にめっき層を形成する際に、金属部材上とめっき層との間に、銀ストライクめっき層を形成するものがある（特許文献２参照）。 For example, as a method of manufacturing a wiring substrate, there is a method of improving the adhesion between the metal plating layers by interposing copper strike plating or nickel strike plating between the layers of the metal plating layer plated on the substrate (Patent Document). 1). Moreover, when manufacturing a plating layer on a metal member as a manufacturing method of a plating member, there exists a method of forming a silver strike plating layer between a metal member and a plating layer (refer patent document 2).
これらの従来の方法は、ストライクめっきを用いて、金属めっき層の表面を粗化させることによって、該金属めっき層の表面における他の金属めっき層との密着力を強化させようとするものである。しかし、実際には、電鋳品の製造過程で使用されるレジストの残膜が、被めっき層の表面に残存することにより、該金属めっき層間の密着力（層間密着力）が低下してしまう虞がある。また、ストライクめっきによりめっきされる金属めっき層の表面が活性化されて水素ガスが発生することによって、該金属めっき層を形成するために存在するレジストに対して予期しない強いアタックが生じてしまい、該レジストが損傷または剥離されて電鋳品自体の形状が損なわれてしまうという虞もある。 These conventional methods attempt to reinforce the adhesion between the surface of the metal plating layer and another metal plating layer by roughening the surface of the metal plating layer using strike plating. . However, in reality, the residual film of the resist used in the manufacturing process of the electroformed product remains on the surface of the layer to be plated, so that the adhesion between the metal plating layers (interlayer adhesion) is reduced. There is a fear. In addition, the surface of the metal plating layer to be plated by strike plating is activated and hydrogen gas is generated, resulting in an unexpectedly strong attack on the resist present to form the metal plating layer, There is also a possibility that the resist is damaged or peeled off and the shape of the electroformed product itself is damaged.
本発明の目的は、上記課題を解決すべく、多層構造の電鋳品において、各金属めっき層間の密着力を高める新しい技術を提供することにある。 An object of the present invention is to provide a new technique for increasing the adhesion between metal plating layers in a multi-layered electroformed product in order to solve the above problems.
本発明者らは、金属めっき層の表面に対して、該金属めっき層の構成元素に応じて選定された金属から成るバリアめっき層を一旦めっきし、その後に該バリアめっき層を除去した上で、さらに金属めっき層をめっきすることにより該金属めっき層間に堅牢な層間密着力が得られることを見出した。 The inventors once plated a barrier plating layer made of a metal selected according to the constituent elements of the metal plating layer on the surface of the metal plating layer, and then removed the barrier plating layer. Further, it has been found that a strong interlayer adhesion can be obtained between the metal plating layers by further plating a metal plating layer.
ここで、基板上の金属めっき層の各層は、レジストを用いて成形される。該レジストは、各層の金属めっき層における所望の形状に応じて、その一部が除去された部分（レジストにより被覆された層にとってはレジストに覆われていない部分）を有する。該除去された部分に金属めっき層が堆積され、所望の形状の金属めっき層が得られる。 Here, each layer of the metal plating layer on the substrate is formed using a resist. The resist has a portion from which a part thereof is removed (a portion not covered by the resist for a layer covered with the resist) in accordance with a desired shape in the metal plating layer of each layer. A metal plating layer is deposited on the removed portion to obtain a metal plating layer having a desired shape.
すなわち、このように積層された上下に連続する金属めっき層について、下層の金属めっき層（以下、第１の金属めっき層という）は、その所望とする形状に応じたレジスト（以下、第１のレジストという）により成形される。また、該第１のめっき層の上にめっきされる金属めっき層（以下、第２の金属めっき層という）は、その所望とする形状に応じたレジスト（以下、第２のレジストという）により成形される。 That is, for the metal plating layers that are stacked in this manner, the lower metal plating layer (hereinafter referred to as the first metal plating layer) is a resist (hereinafter referred to as the first metal plating layer) according to the desired shape. Called a resist). In addition, a metal plating layer (hereinafter referred to as a second metal plating layer) plated on the first plating layer is formed with a resist (hereinafter referred to as a second resist) corresponding to the desired shape. Is done.
かくして、本発明に従えば、基板上の第１のレジストに覆われていない部分に第１の金属めっき層を堆積させ、その上に第２のレジストを被覆させ、該第１の金属めっき層上の該第２のレジストに覆われていない部分に第２の金属めっき層を堆積させ、該第１および第２のレジストを剥離して電鋳品を製造する方法において、第１の金属めっき層の上に、該金属めっき層と異種の金属から成るバリアめっき層をめっきする工程、および前記バリアめっき層を選択的に除去する工程を含むことを特徴とする電鋳品の製造方法が提供される。また、金属めっき層を積層させて成る電鋳品であって、該金属めっき層間に、該金属めっき層以外のめっき層が残存していないことを特徴とする電鋳品も提供される。 Thus, according to the present invention, the first metal plating layer is deposited on a portion of the substrate that is not covered with the first resist, and the second resist is coated on the first metal plating layer. In the method of manufacturing an electroformed product by depositing a second metal plating layer on a portion not covered with the second resist and peeling off the first and second resists, the first metal plating Provided is a method for producing an electroformed product, comprising: a step of plating a barrier plating layer made of a metal different from the metal plating layer on the layer; and a step of selectively removing the barrier plating layer. Is done. There is also provided an electroformed product formed by laminating metal plating layers, wherein no plating layer other than the metal plating layer remains between the metal plating layers.
本発明に係る電鋳品の製造方法は、基板上にレジストを用いて形成された金属めっき層の表面に、該金属めっき層と異種の金属から成るバリアめっき層をめっきする工程と、該バリアめっき層を選択的に除去する工程を含み、金属めっき層を積層させる。 The method for producing an electroformed product according to the present invention includes a step of plating a surface of a metal plating layer formed using a resist on a substrate with a barrier plating layer made of a metal different from the metal plating layer, and the barrier. A step of selectively removing the plating layer is included, and the metal plating layer is laminated.
このように、本発明では、一旦、該金属めっき層と異種の金属から成るバリアめっき層をめっきした後に、該バリアめっき層を選択的に除去するという特徴を有する。従来では、上述したように、多層構造の電鋳品を構成する金属めっき層間の層間密着力を向上させるために、ストライクめっき（例えば、銅）等を中間層として金属めっき層（例えば、ニッケル）の層間に介在させることで、層間密着力を高めようという手法は知られてはいた。 As described above, the present invention is characterized in that the barrier plating layer is selectively removed after the barrier plating layer made of a metal different from the metal plating layer is once plated. Conventionally, as described above, in order to improve the interlayer adhesion between metal plating layers constituting an electroformed product having a multilayer structure, a metal plating layer (for example, nickel) using strike plating (for example, copper) or the like as an intermediate layer There has been known a technique for increasing the interlayer adhesion by interposing between the layers.
しかし、本発明者らは、金属めっき層（例えば、ニッケル）の層間に、一旦、バリアめっき層（例えば、銅）を中間層として形成させた後に、敢えて、該バリアめっき層（中間層）を選択的に除去するという２つの工程を組み合わせることによって、強度特性等に優れた電鋳品が得られることを見出し、本発明を導出するに至った。また、本発明者らは、可及的にバリアめっき層を選択的に除去するために、該バリアめっき層としては、金属めっき層と異種の金属から成るものであることが重要であることも見出した。 However, the inventors of the present invention once formed a barrier plating layer (for example, copper) as an intermediate layer between metal plating layers (for example, nickel), and then dared to form the barrier plating layer (intermediate layer). By combining the two steps of selective removal, it was found that an electroformed product having excellent strength characteristics and the like was obtained, and the present invention was derived. In addition, in order to selectively remove the barrier plating layer as much as possible, the present inventors may consider that it is important that the barrier plating layer is made of a metal different from the metal plating layer. I found it.
このような点から、本発明に係る電鋳品は、１つの側面では、少なくとも２つの金属めっき層間に、該金属めっき層以外のめっき層（例えば、本発明に係るバリアめっき層や上記従来のストライクめっきなど）が残存していないことを特徴とするものでもある。 From such points, the electroformed product according to the present invention has, in one aspect, a plating layer other than the metal plating layer (for example, the barrier plating layer according to the present invention or the conventional one) between at least two metal plating layers. It is also characterized in that no strike plating or the like remains.
このような本発明の製造方法により得られる電鋳品は、従来の電鋳品に比べて、高い層間密着力等をはじめとする優れた効果を奏するものである（後述の実施例２参照）。本発明に係る電鋳品の製造方法では、バリアめっき層を一旦形成した後に除去することによって、該バリアめっき層上に存在するレジスト残渣が除去されることとなり、当該バリアめっき層がめっきされ除去された金属めっき層と、当該金属めっき層の表面（上面）に積層される金属めっき層との層間において、従来では得られない層間密着力が得られることとなる。
さらに、本発明に係る電鋳品の製造方法では、当該バリアめっき層の形成および除去の工程の組み合わせによって、バリアめっき層のめっき対象である金属めっき層の表面に、従来のストライクめっきなどを用いることを不要としたことから、次の利点がある。すなわち、従来のストライクめっきなどを用いる場合に生じていた所望としない反応（例えば、予期しない水素ガスの発生によるレジストへのアタック）などが抑制されることとなり、該レジストの損傷または剥離による電鋳品形状の変形を抑制することができる。
The electroformed product obtained by the production method of the present invention exhibits excellent effects including high interlayer adhesion and the like as compared with the conventional electroformed product (see Example 2 described later). . In the method for producing an electroformed product according to the present invention, once the barrier plating layer is formed and then removed, the resist residue existing on the barrier plating layer is removed, and the barrier plating layer is plated and removed. Between the metal plating layer thus formed and the metal plating layer laminated on the surface (upper surface) of the metal plating layer, an interlayer adhesion force that cannot be obtained conventionally is obtained.
Furthermore, in the method for producing an electroformed product according to the present invention, a conventional strike plating or the like is used on the surface of the metal plating layer which is a target of plating of the barrier plating layer by a combination of the formation and removal processes of the barrier plating layer. This has the following advantages. That is, an undesired reaction (for example, an attack to the resist due to unexpected generation of hydrogen gas) that occurs when using conventional strike plating or the like is suppressed, and electroforming due to damage or peeling of the resist. Deformation of the product shape can be suppressed.
基板を構成する材料は、一般に金属をめっきする際の基板として使用されている公知の材料であれば、特に限定されないが、導電性金属材を用いることが好ましく、例えば、ステンレス鋼（ＳＵＳ）を用いることができる。このような基板は、通常、洗浄工程を経て使用される。この洗浄工程としては、例えば、アルカリ脱脂、ＲＣＡ洗浄、クリーナー処理など公知の手法の１つまたは複数を組み合わせて用いることができる。 Although the material which comprises a board | substrate will not be specifically limited if it is a well-known material generally used as a board | substrate at the time of metal plating, it is preferable to use a conductive metal material, for example, stainless steel (SUS). Can be used. Such a substrate is usually used after a cleaning process. As this cleaning step, for example, one or a plurality of known methods such as alkali degreasing, RCA cleaning, and cleaner treatment can be used in combination.
金属めっき層を構成する材料は、公知の材料であればよく、特に限定されないが、例えば、ニッケル−コバルト合金を用いることができ、この他にも、金、銀、銅、ニッケル、コバルトなどを用いることができる。めっきの方法は、電気めっき（電鋳）等の公知の方法を用いることができる。例えば、電気めっき（電鋳）を用いる場合には、当該金属めっきを構成する金属または合金を含有させためっき液に、基板または金属めっき層がめっきされた基板を浸漬させ、電圧を印加させることにより、該基板にめっきすることができる。 The material constituting the metal plating layer may be a known material, and is not particularly limited. For example, a nickel-cobalt alloy can be used, and in addition, gold, silver, copper, nickel, cobalt, and the like can be used. Can be used. As the plating method, a known method such as electroplating (electroforming) can be used. For example, when using electroplating (electroforming), the substrate or the substrate plated with the metal plating layer is immersed in a plating solution containing the metal or alloy constituting the metal plating, and a voltage is applied. Thus, the substrate can be plated.
バリアめっき層を構成する材料は、上記の金属めっき層と異種の金属から成るものであればよい。例えば、バリアめっき層としては、コバルト、銅、ニッケル、チタン、または亜鉛のうちの少なくとも１つの元素から構成されるものを用いることができる。例えば、金属めっき層にニッケル−コバルト合金を用いる場合には、バリアめっき層に銅を用いることができる。 The material which comprises a barrier plating layer should just consist of a metal different from said metal plating layer. For example, as the barrier plating layer, a layer composed of at least one element of cobalt, copper, nickel, titanium, or zinc can be used. For example, when a nickel-cobalt alloy is used for the metal plating layer, copper can be used for the barrier plating layer.
バリアめっき層をめっきする際のめっき液の濃度は、ストライクめっきのように比較的低濃度で用いることも可能であるが、本発明に係る金属めっき層と異種の金属であれば十分であることから、通常の金属めっきに使用されるような通常の濃度で（ストライクめっきよりも高濃度で）用いることも可能である。すなわち、本発明に係るバリアめっき層に係るめっき液の濃度については、適用範囲が広いということから、従来のように比較的低濃度且つ一様な濃度で薄膜を形成することが要求されるものではなく、作業の容易性に優れるという利点がある。 The plating solution concentration when plating the barrier plating layer can be used at a relatively low concentration as in strike plating, but a metal different from the metal plating layer according to the present invention is sufficient. Therefore, it is also possible to use at a normal concentration (higher concentration than strike plating) as used in normal metal plating. That is, the concentration of the plating solution related to the barrier plating layer according to the present invention is wide, so that it is required to form a thin film with a relatively low concentration and a uniform concentration as in the prior art. However, there is an advantage that it is excellent in workability.
また、バリアめっき層を選択的に除去するとは、基板上に存在する他の金属めっき層が除去されることなく、基板からバリアめっき層のみが除去されることを意味する。すなわち、バリアめっき層を選択的に除去するための溶解液（エッチング剤）としては、金属めっき層の構成金属が溶解されにくく、専らバリアめっき層の構成金属を溶解させる性質のものが利用される。このようなエッチング剤としては、例えば、過硫酸アンモニウムや、過硫酸ナトリウムを用いることができる。 Moreover, selectively removing the barrier plating layer means that only the barrier plating layer is removed from the substrate without removing other metal plating layers existing on the substrate. That is, as a solution (etching agent) for selectively removing the barrier plating layer, a solution that hardly dissolves the constituent metal of the metal plating layer and exclusively dissolves the constituent metal of the barrier plating layer is used. . As such an etchant, for example, ammonium persulfate or sodium persulfate can be used.
このようなことから、本発明に係る電鋳品における（金属めっき層、バリアめっき層、およびエッチング剤）の組み合わせとしては、特に限定されるものではないが、例えば、（ニッケル−コバルト合金、銅、過硫酸アンモニウム）の組み合わせを用いることができる。なお、この他にも（ニッケル−コバルト合金、チタン、チタンエッチング液）という組み合わせも可能である。 For this reason, the combination of (metal plating layer, barrier plating layer, and etching agent) in the electroformed product according to the present invention is not particularly limited. For example, (nickel-cobalt alloy, copper) , Ammonium persulfate) combinations can be used. In addition, a combination of (nickel-cobalt alloy, titanium, titanium etching solution) is also possible.
電鋳のプロセスにおいて鋳型として機能するレジストを構成する材料は、公知のものであれば特に限定されるものではないが、加工の容易性および入手のし易さから、熱硬化性樹脂や光硬化性樹脂を用いることが好ましく、例えば、光硬化性樹脂であるドライフィルムレジスト（ＤＦＲ）を用いることができる。該レジストは、基板上にラミネート（被膜）された後に、例えば、所定パターンを有するフォトマスクを用いて露光・現像等の処理を行うことによりその一部が除去され、所望の形状を有する本発明に係るレジスト（第１および第２のレジスト）として用いられる。 The material constituting the resist functioning as a mold in the electroforming process is not particularly limited as long as it is a known material. However, from the viewpoint of ease of processing and availability, a thermosetting resin or photocuring is possible. For example, a dry film resist (DFR) which is a photocurable resin can be used. After the resist is laminated (coated) on the substrate, a part of the resist is removed by, for example, exposure / development using a photomask having a predetermined pattern, and the resist has a desired shape. Used as a resist (first and second resists).
以下、本発明に係る電鋳品の製造方法を、図１の本発明に係る電鋳品の製造方法をフローとして示す説明図に従って説明する。なお、以下ではレジストとして、光硬化性樹脂であるドライフィルムレジスト（ＤＦＲ）を例として挙げるが、レジストはこれに限定されるものではない。 Hereinafter, the method for manufacturing an electroformed product according to the present invention will be described with reference to an explanatory diagram showing the method for manufacturing the electroformed product according to the present invention in FIG. 1 as a flow. In the following, a dry film resist (DFR), which is a photocurable resin, is taken as an example of the resist, but the resist is not limited to this.
（１）第１のレジストの形成
先ず、基板１（例えば、ステンレス鋼（ＳＵＳ））を、アルカリ脱脂、ＲＣＡ洗浄、およびクリーナー処理を用いて洗浄する（図１（ａ））。該基板１の表面に対して、第１のレジスト２１を構成するドライフィルムレジスト（ＤＦＲ）を、所望の厚さに一様にラミネート（被膜）する（図１（ｂ））。
基板１上のドライフィルムレジスト（ＤＦＲ）に対して所定パターンを有するフォトマスク１００を用いて露光を行う（図１（ｃ））。さらに、現像を行う。これらの処理によって、ドライフィルムレジスト（ＤＦＲ）から、レジスト内の一部が除去され、該除去された部分（第１のレジストに覆われていない部分２１ａ・２１ｂ・２１ｃ）を含む形状を有する第１のレジスト２１が得られる（図１（ｄ））。
(1) Formation of first resist First, the substrate 1 (for example, stainless steel (SUS)) is cleaned using alkali degreasing, RCA cleaning, and cleaner treatment (FIG. 1A). A dry film resist (DFR) constituting the first resist 21 is uniformly laminated (coated) to a desired thickness on the surface of the substrate 1 (FIG. 1B).
The dry film resist (DFR) on the substrate 1 is exposed using a photomask 100 having a predetermined pattern (FIG. 1C). Further, development is performed. By these processes, a part of the resist is removed from the dry film resist (DFR), and the removed part (parts 21a, 21b, 21c not covered with the first resist) has a shape including the shape. 1 resist 21 is obtained (FIG. 1D).
（２）第１の金属めっき層の形成
該基板１をめっき液（例えば、ニッケルおよびコバルトを含有するめっき液）に浸漬させる。該基板を陰極として電流を通流させ、基板上の第１のレジストに覆われていない部分２１ａ・２１ｂ・２１ｃ（前記除去された部分）に対して、第１の金属めっき層３１（例えば、ニッケル−コバルト合金）を堆積させる電鋳（光沢電鋳）を行う（図１（ｅ））。光沢電鋳は、光沢のある電鋳品や硬度の高い電鋳品を得るのに有効である。
なお、該第１の金属めっき層３１を堆積させる方法は、電気めっきの他に、化学蒸着（ＣＶＤ）、物理蒸着（ＰＶＤ）、急速熱処理（ＲＴＰ）、リソグラフ等の薄膜分野における公知の成膜方法を用いることも可能である。
(2) Formation of first metal plating layer The substrate 1 is immersed in a plating solution (for example, a plating solution containing nickel and cobalt). Current is passed using the substrate as a cathode, and the first metal plating layer 31 (for example, the portion removed from the portions 21a, 21b, and 21c that are not covered with the first resist on the substrate) (for example, Electroforming (gloss electroforming) for depositing nickel-cobalt alloy) is performed (FIG. 1 (e)). Gloss electroforming is effective in obtaining glossy electroformed products and electroformed products having high hardness.
The first metal plating layer 31 is deposited by a known film formation method in the field of thin films such as chemical vapor deposition (CVD), physical vapor deposition (PVD), rapid thermal processing (RTP), and lithograph in addition to electroplating. It is also possible to use a method.
（３）バリアめっき層の形成
該堆積された第１の金属めっき層３１の表面に、バリアめっき層４をめっきするために、先ず、該基板１を、バリアめっき層４の構成金属（例えば、銅）を含むめっき液に浸漬させる。該基板１を陰極として該めっき液中に電流を通流させ、基板１上に露出している前記第１の金属めっき層３１に対して、めっきを行い、バリアめっき層４を堆積させる。このめっきによって、バリアめっき層４が第１の金属めっき層３１の表面を被覆し、該基板１の表面には、第１のレジスト２１およびバリアめっき層４により覆われた状態となる（図１（ｆ））。
(3) Formation of Barrier Plating Layer In order to plate the barrier plating layer 4 on the surface of the deposited first metal plating layer 31, first, the substrate 1 is made of a constituent metal of the barrier plating layer 4 (for example, Soaking in a plating solution containing copper. Current is passed through the plating solution using the substrate 1 as a cathode, the first metal plating layer 31 exposed on the substrate 1 is plated, and a barrier plating layer 4 is deposited. By this plating, the barrier plating layer 4 covers the surface of the first metal plating layer 31, and the surface of the substrate 1 is covered with the first resist 21 and the barrier plating layer 4 (FIG. 1). (F)).
（４）第２のレジストの形成
該基板１上に対して、上記第１のレジスト２１と同様に、さらに第２のレジスト２２をマスクとして、ラミネートする（図１（ｇ））。そして、該ラミネートされた第２のレジスト２２は、上記第１のレジスト２１と同様に、所定パターンを有するフォトマスク２００を用いて露光する（図１（ｈ））。さらに、現像を行う。結果として、その一部に除去された部分（第２のレジストに覆われていない部分２２ａ・２２ｂ）を含む形状を有する（図１（ｉ））。
(4) Formation of Second Resist Similarly to the first resist 21, the second resist 22 is laminated on the substrate 1 as a mask (FIG. 1 (g)). Then, similarly to the first resist 21, the laminated second resist 22 is exposed using a photomask 200 having a predetermined pattern (FIG. 1 (h)). Further, development is performed. As a result, it has a shape including a part removed (parts 22a and 22b not covered with the second resist) (FIG. 1 (i)).
（５）バリアめっき層のエッチング
次に、該第２のレジストに覆われていない部分２２ａ・２２ｂに露出したバリアめっき層４を、選択的に除去する。バリアめっき層４を選択的に除去する方法としては、例えば、上記のバリアめっき層４を含む基板１に対して、バリアめっき層４の構成金属を選択的にエッチング可能な溶液（例えば、過硫酸アンモニウム、過硫酸ナトリウム）に浸漬するかまたは当該溶液をスプレーで吹き付けることによって、バリアめっき層４の構成金属（例えば、銅）のみを該溶液中に溶解させることにより行うことができる（図１（ｊ））。
(5) Etching of barrier plating layer Next, the barrier plating layer 4 exposed in the portions 22a and 22b not covered with the second resist is selectively removed. As a method for selectively removing the barrier plating layer 4, for example, a solution (for example, ammonium persulfate) capable of selectively etching the constituent metal of the barrier plating layer 4 with respect to the substrate 1 including the barrier plating layer 4 described above. , Or by spraying the solution with a spray to dissolve only the constituent metal (for example, copper) of the barrier plating layer 4 in the solution (FIG. 1 (j )).
（６）第２の金属めっき層の形成
バリアめっき層４を選択的に除去した後に基板１上に露出した第１の金属めっき層３１に対して、さらに第２の金属めっき層３２を堆積させる。第２の金属めっき層３２は、通常は、第１の金属めっき層３１と同じ金属を用いるが、第１の金属めっき層３１と異なる金属を用いることも可能である。
上記の第１の金属めっき層３１を基板１上に堆積させた場合と同様にして、該基板１をめっき液（例えば、ニッケルおよびコバルトを含有するめっき液）に浸漬させる。該基板１を陰極として電流を通流させ、基板１上の該第２のレジストに覆われていない部分２２ａ・２２ｂ（前記除去された部分）に対して、第２の金属めっき層３２（例えば、ニッケル−コバルト合金）を電鋳（光沢電鋳）により堆積させる（図１（ｋ））。
(6) Formation of second metal plating layer A second metal plating layer 32 is further deposited on the first metal plating layer 31 exposed on the substrate 1 after the barrier plating layer 4 is selectively removed. . The second metal plating layer 32 normally uses the same metal as the first metal plating layer 31, but a metal different from the first metal plating layer 31 can also be used.
Similarly to the case where the first metal plating layer 31 is deposited on the substrate 1, the substrate 1 is immersed in a plating solution (for example, a plating solution containing nickel and cobalt). Current is passed using the substrate 1 as a cathode, and a second metal plating layer 32 (for example, the portions 22a and 22b (the removed portions) not covered with the second resist on the substrate 1) , Nickel-cobalt alloy) is deposited by electroforming (gloss electroforming) (FIG. 1 (k)).
（７）レジストおよびバリアめっき層の除去
第１のレジスト２１および第２のレジスト２２を化学的操作および／または物理的操作（機械的操作）により除去（剥離）する（図１（ｌ））。さらに、バリアめっき層４を、上記と同様にしてエッチングにより除去する（図１（ｍ））。
(7) Removal of resist and barrier plating layer The first resist 21 and the second resist 22 are removed (peeled) by a chemical operation and / or a physical operation (mechanical operation) (FIG. 1 (l)). Further, the barrier plating layer 4 is removed by etching in the same manner as described above (FIG. 1 (m)).
以上により、多層の金属めっき層から成る本発明に係る多層構造の電鋳品が得られる（図１（ｍ））。本発明に係る多層構造の電鋳品は、基板１が含まれるものおよび基板１が含まれないものも、用途に応じて作成することが可能である。すなわち、本発明に係る電鋳品は、基板１の剥離の有無によって、第１の金属めっき層３１および第２の金属めっき層３２のみから成るものとすることもでき、また、第１の金属めっき層３１および第２の金属めっき層３２に基板１が付属して成るものとすることもできる。本発明に係る電鋳品は、例えば、第１の金属めっき層３１および第２の金属めっき層３２のみから成るものとしては、図２に示すような不規則な凹凸形状を高い強度のもとで形成することが可能である。 As described above, an electroformed product having a multilayer structure according to the present invention comprising a multilayer metal plating layer is obtained (FIG. 1 (m)). The multi-layered electroformed product according to the present invention can be produced depending on the application, including those including the substrate 1 and those not including the substrate 1. That is, the electroformed product according to the present invention can be composed of only the first metal plating layer 31 and the second metal plating layer 32 depending on whether the substrate 1 is peeled off, or the first metal. The substrate 1 may be attached to the plating layer 31 and the second metal plating layer 32. For example, the electroformed product according to the present invention is formed of only the first metal plating layer 31 and the second metal plating layer 32, and has an irregular uneven shape as shown in FIG. It is possible to form with.
なお、上記多層構造の電鋳品は、積層される金属めっき層が２層のものについて記載したが、本発明に係る上記処理を繰り返し適用すること、すなわち、本発明に係る電鋳品は、第３のレジストおよび第３の金属めっき層、第４のレジストおよび第４の金属めっき層、あるいはそれ以上の多層のレジストおよび金属めっき層を繰り返し用いることによって、３層、４層、あるいはそれ以上の多層となる金属めっき層から成る電鋳品を得ることができ、さらにアスペクト比が高い多段電鋳品としての利用も可能である。 In addition, although the multi-layered electroformed product has been described as having two metal plating layers to be laminated, applying the above treatment according to the present invention repeatedly, that is, the electroformed product according to the present invention is By repeatedly using a third resist and a third metal plating layer, a fourth resist and a fourth metal plating layer, or more multilayer resists and metal plating layers, three layers, four layers or more It is possible to obtain an electroformed product composed of a multi-layered metal plating layer, and it is also possible to use it as a multistage electroformed product having a high aspect ratio.
このようにして得られる本発明に係る電鋳品は、製造過程にめっきしたバリアめっき層が残存していないという特徴を有する。このように、製造過程に使用した不純物が含有していないことから、本発明に係る電鋳品は、電鋳品本来の構成材料である金属めっき層のみから多層構造が形成され、所望の強度および特性を発揮する。すなわち、本発明に係る電鋳品は、製造過程に使用した不純物が残存するという従来の多層構造の電鋳品では得られない効果を奏する。その優れた効果の１つとして密着性の高さがあり、本発明に係る電鋳品は、従来の電鋳品と比べて高い密着性が示されている（後述の実施例２参照）。 The electroformed product according to the present invention thus obtained has a feature that no barrier plating layer plated in the manufacturing process remains. Thus, since the impurities used in the manufacturing process do not contain, the electroformed product according to the present invention has a multilayer structure formed only from the metal plating layer that is the original constituent material of the electroformed product, and has a desired strength. And exhibit properties. In other words, the electroformed product according to the present invention has an effect that cannot be obtained with a conventional multi-layered electroformed product in which impurities used in the manufacturing process remain. One of the excellent effects is high adhesiveness, and the electroformed product according to the present invention shows high adhesiveness compared to the conventional electroformed product (see Example 2 described later).
本発明に係る電鋳品は、ダイヤフラム、プローブ、リードフレーム、フィルター、メタルマスク、金属メッシュ等として広範な分野にわたり利用することができる。 The electroformed product according to the present invention can be used in a wide range of fields as a diaphragm, a probe, a lead frame, a filter, a metal mask, a metal mesh, and the like.
以下に実施例を示すが、この実施例は本発明に係る電鋳品を単に例示するためのものであり、本発明を限定するものではない。
◇第１の金属めっき層について（※従来品も同じ）
めっき液：ニッケル−コバルトめっき液、厚み：４μｍ
◇第２の金属めっき層について（※従来品も同じ）
めっき液：ニッケル−コバルトめっき液、厚み：７μｍ
◇バリアめっき層について（本発明）
めっき液：硫酸銅めっき液、厚み：１〜２μｍ
◇ストライクめっき層について（従来）
めっき液：ニッケルめっき液、厚み：０．０５〜１μｍ
Although an Example is shown below, this Example is only for exemplifying the electroformed product according to the present invention, and does not limit the present invention.
◇ About the first metal plating layer (* same for conventional products)
Plating solution: Nickel-cobalt plating solution, thickness: 4 μm
◇ About the second metal plating layer (* same for conventional products)
Plating solution: Nickel-cobalt plating solution, thickness: 7 μm
◇ Barrier plating layer (present invention)
Plating solution: copper sulfate plating solution, thickness: 1-2 μm
◇ Strike plating layer (conventional)
Plating solution: Nickel plating solution, thickness: 0.05-1 μm
（実施例１）
先ず、基板となるステンレス鋼（ＳＵＳ）（厚み：３００μｍ）を、アルカリ脱脂、ＲＣＡ洗浄、クリーナー処理を用いて洗浄した。該基板の表面に対して、ドライフィルムレジスト（ＤＦＲ）を、１０ミクロンオーダーで一様に塗布し、基板上にラミネート（被膜）した。ドライフィルムレジスト（ＤＦＲ）に対して露光および現像を行い、レジストパターンを形成した。
Example 1
First, stainless steel (SUS) (thickness: 300 μm) serving as a substrate was cleaned using alkali degreasing, RCA cleaning, and cleaner treatment. A dry film resist (DFR) was uniformly applied to the surface of the substrate on the order of 10 microns and laminated (coated) on the substrate. The dry film resist (DFR) was exposed and developed to form a resist pattern.
該基板を、ニッケルおよびコバルトを含有するめっき液に浸漬させ、該基板を陰極として電流を通流させ、基板上の該レジストに覆われていない部分（前記除去された部分）に対して、ニッケル−コバルト合金を堆積させる電鋳（光沢電鋳）を行った。得られた基板をめっき液から取り出して乾燥させた。 The substrate is immersed in a plating solution containing nickel and cobalt, and a current is passed through the substrate as a cathode. The portion of the substrate that is not covered with the resist (the removed portion) is exposed to nickel. -Electroforming (gloss electroforming) to deposit a cobalt alloy was performed. The obtained substrate was taken out from the plating solution and dried.
該基板を銅が含まれるめっき液に浸漬させた。該基板を陰極として電流を通流させ、基板に対して、銅を堆積させるめっきを行った。該基板上に、さらにレジストをマスクとしてラミネートし、露光および現像を行った。 The substrate was immersed in a plating solution containing copper. The substrate was used as a cathode, and an electric current was passed therethrough, and plating for depositing copper was performed on the substrate. On the substrate, a resist was further laminated as a mask, and exposure and development were performed.
該基板に対して、過硫酸アンモニウムに浸漬し、めっきされた銅を溶解させた。該基板に対して、上記と同様に、該基板を、ニッケルおよびコバルトを含有するめっき液に浸漬させる。該基板を陰極として電流を通流させ、基板上の該レジストに覆われていない部分（前記除去された部分）に対して、ニッケル−コバルト合金を堆積させる電鋳（光沢電鋳）を行った。 The substrate was immersed in ammonium persulfate to dissolve the plated copper. Similar to the above, the substrate is immersed in a plating solution containing nickel and cobalt. Electroplating (gloss electroforming) was performed by depositing a nickel-cobalt alloy on the portion of the substrate that was not covered with the resist (the removed portion), with the substrate serving as a cathode. .
第１および第２のレジストを化学的操作および／または物理的操作（機械的操作）により剥離した。この時点（上述した図１（ｌ）に相当する）での電鋳体のＳＥＭ画像を、図３（ａ）〜（ｃ）に示す。図３（ａ）は、電鋳体を水平面から傾き４０°の位置から写したものである。図３（ｂ）及び（ｃ）は、電鋳体を真上から写したものである。このＳＥＭ画像に写された電鋳体は、図３（ｄ）の断面模式図に示すように、ステンレス鋼（基板１）と、このステンレス鋼上のニッケル−コバルト合金（第１の金属めっき層３１）と、このニッケル−コバルト合金上にさらに積層されたニッケル−コバルト合金（第２の金属めっき層３２）及び銅（バリアめっき層４）から構成され、上述した図１（ｌ）のうち、中央部分周辺の箇所（すなわち、図１（ｊ）でのレジスト（第２のレジスト２２）に覆われていない部分２２ｂに対して、ニッケル−コバルト合金（第２の金属めっき層３２）が形成された箇所）に相当する。 The first and second resists were stripped by chemical operation and / or physical operation (mechanical operation). The SEM images of the electroformed body at this point (corresponding to FIG. 1 (l) described above) are shown in FIGS. FIG. 3A shows the electroformed body taken from a position at an inclination of 40 ° from the horizontal plane. FIGS. 3B and 3C show the electroformed body taken from directly above. As shown in the schematic cross-sectional view of FIG. 3D, the electroformed body imaged in this SEM image is made of stainless steel (substrate 1) and a nickel-cobalt alloy (first metal plating layer on the stainless steel). 31) and a nickel-cobalt alloy (second metal plating layer 32) and copper (barrier plating layer 4) further laminated on the nickel-cobalt alloy, and among the above-described FIG. 1 (l), A nickel-cobalt alloy (second metal plating layer 32) is formed on the portion 22b around the center portion (that is, the portion 22b not covered with the resist (second resist 22) in FIG. 1 (j)). Equivalent to
なお、得られたＳＥＭ画像では、上層のニッケル−コバルト合金（第２の金属めっき層３２）の下部周辺の一部が、わずかに張り出した形状（図３（ｄ）に示す張り出し部３２ａ）を有していたが、これは、図１（ｉ）のレジスト（第２のレジスト２２）に覆われていない部分２２ｂに露出した銅（バリアめっき層４）に対するエッチングを行った際に、このレジスト（第２のレジスト２２）に覆われていない部分２２ｂに隣接する銅（バリアめっき層４）（すなわち、図１（ｉ）の中央部分周辺のレジスト（第２のレジスト２２）の直下にある銅（バリアめっき層４））の一部がわずかに除去され、この除去された箇所にニッケル−コバルト合金（第２の金属めっき層３２）が堆積されることで形成されたものである。図３（ａ）〜（ｃ）に示されるＳＥＭ画像から、基板上に、ニッケル−コバルト合金層と銅層が各々明確な別領域として滑らかに堆積されたことが確認された。 In the obtained SEM image, a part of the lower periphery of the upper nickel-cobalt alloy (second metal plating layer 32) slightly protrudes (a protruding portion 32a shown in FIG. 3D). However, this is because the resist (copper plating layer 4) exposed in the portion 22b not covered with the resist (second resist 22) in FIG. Copper (barrier plating layer 4) adjacent to the portion 22b not covered with the (second resist 22) (that is, the copper immediately below the resist (second resist 22) around the central portion of FIG. 1 (i)) A part of (barrier plating layer 4)) is slightly removed, and a nickel-cobalt alloy (second metal plating layer 32) is deposited on the removed portion. From the SEM images shown in FIGS. 3A to 3C, it was confirmed that the nickel-cobalt alloy layer and the copper layer were each smoothly deposited as distinct regions on the substrate.
さらに、上記と同様に銅をエッチングにより除去した。以上により、多層の金属めっき層から成る本発明に係る多層構造の電鋳品が得られた。得られた本発明に係る多層構造の電鋳品のＳＥＭ画像を図４（ａ）〜（ｃ）に示す。図４（ａ）は、電鋳体を水平面から傾き４０°の位置から写したものである。図４（ｂ）及び（ｃ）は、電鋳体を真上から写したものである。
このＳＥＭ画像に写された電鋳体は、図４（ｄ）の断面模式図に示すように、ステンレス鋼（基板１）と、このステンレス鋼（基板１）上の２層のニッケル−コバルト合金（第１の金属めっき層３１及び第２の金属めっき層３２）から構成され、上述した図１（ｍ）のうち、中央部分周辺の箇所（すなわち、図１（ｊ）でレジスト（第２のレジスト２２）に覆われていない部分２２ｂに対して、ニッケル−コバルト合金（第２の金属めっき層３２）が形成された箇所）に相当する。
図４（ａ）〜（ｃ）に示されるＳＥＭ画像から、本発明に係る多層構造の電鋳品は、上記図３（ａ）で示された基板上の銅層が全て除去され、結果として、銅を含まないコバルト−ニッケル合金から構成されることが確認された。このことから、従来のニッケルストライクめっきを用いた多層構造の電鋳品では、層間密着力を高めるために使用されたニッケルが、完成品である多層構造の電鋳品に残存していたが、本発明に係る多層構造の電鋳品では、このニッケルのような中間材料の残存が無いことから、従来の電鋳品とは異なるものであることが確認された。
Further, copper was removed by etching in the same manner as described above. As described above, an electroformed product having a multilayer structure according to the present invention composed of multiple metal plating layers was obtained. SEM images of the obtained multilayered electroformed product according to the present invention are shown in FIGS. FIG. 4A shows the electroformed body copied from a position at an inclination of 40 ° from the horizontal plane. 4 (b) and 4 (c) show the electroformed body taken from directly above.
As shown in the schematic cross-sectional view of FIG. 4D, the electroformed body imaged in this SEM image is stainless steel (substrate 1) and two layers of nickel-cobalt alloy on the stainless steel (substrate 1). (The first metal plating layer 31 and the second metal plating layer 32), and in FIG. 1 (m) described above, the resist (second The portion 22b not covered with the resist 22) corresponds to a nickel-cobalt alloy (a portion where the second metal plating layer 32) is formed).
From the SEM images shown in FIGS. 4 (a) to 4 (c), in the electroformed product having a multilayer structure according to the present invention, the copper layer on the substrate shown in FIG. It was confirmed to be composed of a cobalt-nickel alloy containing no copper. From this, in the conventional multi-layered electroformed product using nickel strike plating, the nickel used to increase the interlayer adhesion remained in the multi-layered electroformed product, which is the finished product, It was confirmed that the electroformed product having a multilayer structure according to the present invention is different from the conventional electroformed product because there is no residual intermediate material such as nickel.
（実施例２）
上記で得られた本発明に係る多層構造の電鋳品に対して剥離試験を行った。
実施した剥離試験の内容は、得られた電鋳品をテープで上下に挟んで貼りつけて１８０°折曲げて剥離するかどうかを確認した。この場合に、積層された１層目と２層目の金属めっき層同士が剥がれてしまう場合には密着性が弱いということが示される。
比較例として、本発明の金属めっき層（銅めっき）に替えて、従来のニッケルストライクめっきを用いて得られた電鋳品に対しても、該剥離試験を行った。本発明に係る電鋳品、および従来の電鋳品のいずれのサンプルに対しても該剥離試験を１０回実施した。
(Example 2)
A peel test was performed on the electroformed product having a multilayer structure according to the present invention obtained above.
The content of the peel test carried out was confirmed as to whether or not the obtained electroformed product was sandwiched between tapes and attached, bent 180 ° and peeled off. In this case, when the laminated first and second metal plating layers are peeled off, it indicates that the adhesion is weak.
As a comparative example, the peel test was performed on an electroformed product obtained by using conventional nickel strike plating instead of the metal plating layer (copper plating) of the present invention. The peel test was carried out 10 times for both the electroformed product according to the present invention and the conventional electroformed product.
（剥離試験の結果）
＜剥離が起こらなかった割合＞
従来の電鋳品（ニッケルストライクめっき使用）：５０％
本発明に係る電鋳品（銅めっき使用）：１００％
(Result of peel test)
<Rate where peeling did not occur>
Conventional electroformed product (using nickel strike plating): 50%
Electroformed product according to the present invention (using copper plating): 100%
上記の剥離試験の結果により、従来の電鋳品では５０％の電鋳品が１層目と２層目が剥離したが、本発明に係る電鋳品では剥離が起こらなかったということが確認された。
なお、本発明に係る電鋳品を第１の金属めっき層３１側に折り曲げて第１の金属めっき層３１および第２の金属めっき層３２相互間の一端に剥離応力を加えた場合の電子顕微鏡に基づく説明図を図５に示す。図５に示すように、金属めっき層間の接合部の剥がれが無く、すなわち、第１の金属めっき層３１および第２の金属めっき層３２との接合部Ａでは剥離は発生しなかった。その代わりに、その接合部Ａ近傍の第１の金属めっき層３１において、第２の金属めっき層３２で覆われていない露出表面部の箇所Ｂが引きちぎられるような剥離が認められた。このことから、第１の金属めっき層３１および第２の金属めっき層３２相互間は、強固に密着していることが確認された。
このように、本発明の電鋳品は、従来の電鋳品と比較して剥離しにくいことが示された。
As a result of the above peeling test, it was confirmed that 50% of the electroformed product was peeled off in the first layer and the second layer in the conventional electroformed product, but no peeling occurred in the electroformed product according to the present invention. It was done.
An electron microscope when the electroformed product according to the present invention is bent toward the first metal plating layer 31 and peeling stress is applied to one end between the first metal plating layer 31 and the second metal plating layer 32. FIG. 5 shows an explanatory diagram based on the above. As shown in FIG. 5, there was no peeling at the joint between the metal plating layers, that is, no peeling occurred at the joint A with the first metal plating layer 31 and the second metal plating layer 32. Instead, in the first metal plating layer 31 in the vicinity of the joint A, peeling was observed such that the portion B of the exposed surface portion that was not covered with the second metal plating layer 32 was torn off. From this, it was confirmed that the first metal plating layer 31 and the second metal plating layer 32 are firmly adhered to each other.
Thus, it was shown that the electroformed product of the present invention is less likely to be peeled off than the conventional electroformed product.
１ 基板
２１ 第１のレジスト
２１ａ、２１ｂ、２１ｃ 第１のレジストに覆われていない部分
２２ 第２のレジスト
２２ａ、２２ｂ 第２のレジストに覆われていない部分
３１ 第１の金属めっき層
３２ 第２の金属めっき層
３２ａ 張り出し部
４ バリアめっき層
１００、２００ フォトマスク
DESCRIPTION OF SYMBOLS 1 Board | substrate 21 1st resist 21a, 21b, 21c The part 22 which is not covered with the 1st resist 2nd resist 22a, 22b The part which is not covered with the 2nd resist 31 1st metal plating layer 32 2nd Metal plating layer 32a Overhang portion 4 Barrier plating layer 100, 200 Photomask
Claims (4)
第１の金属めっき層の上に、該金属めっき層と異種の金属から成るバリアめっき層をめっきする工程、および前記バリアめっき層を選択的に除去する工程を含むことを特徴とする電鋳品の製造方法。 A first metal plating layer is deposited on a portion of the substrate not covered with the first resist, a second resist is coated thereon, and a second resist is covered on the portion not covered with the second resist. In a method of depositing a metal plating layer and peeling off the first and second resists to produce an electroformed product,
An electroformed product comprising: a step of plating a barrier plating layer made of a metal different from the metal plating layer on the first metal plating layer; and a step of selectively removing the barrier plating layer Manufacturing method.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0645232A (en) * | 1992-04-24 | 1994-02-18 | Wisconsin Alumni Res Found | Formation of fine structure, by multiple- level deep-x-ray lithography, provided with sacrificial layer |
| JPH08334903A (en) * | 1995-06-05 | 1996-12-17 | Think Lab Kk | Screen plate and its production |
| US5685491A (en) * | 1995-01-11 | 1997-11-11 | Amtx, Inc. | Electroformed multilayer spray director and a process for the preparation thereof |
| JPH11176411A (en) * | 1997-12-11 | 1999-07-02 | Kyushu Hitachi Maxell Ltd | Safety valve device for battery and its manufacture |
| JPH11186262A (en) * | 1997-12-17 | 1999-07-09 | Sanyo Electric Co Ltd | Manufacture of semiconductor device |
| JP2001316862A (en) * | 2000-05-02 | 2001-11-16 | Citizen Watch Co Ltd | Three-dimensional electrocast product, manufacturing method, and three-dimensional electrocast sheet |
| JP2002187374A (en) * | 2000-12-20 | 2002-07-02 | Kyushu Hitachi Maxell Ltd | Electroformed metal mask and method for manufacturing the same |
| JP2003072021A (en) * | 2001-09-03 | 2003-03-12 | Process Lab Micron:Kk | Metal mask for printing |
| JP2005154879A (en) * | 2003-11-28 | 2005-06-16 | Canon Components Inc | Metal mask for vapor deposition, and method of producing vapor deposition pattern using the same |
| JP2005532015A (en) * | 2002-06-27 | 2005-10-20 | マイクロファブリカ インク | Miniature RF and microwave components and methods for manufacturing such components |
| JP2006063362A (en) * | 2004-08-25 | 2006-03-09 | Kyushu Hitachi Maxell Ltd | Method for producing electrode body |
| JP2006287034A (en) * | 2005-04-01 | 2006-10-19 | Shinko Electric Ind Co Ltd | Manufacturing method of wiring substrate utilizing electrolytic plating |
| US20070099417A1 (en) * | 2005-10-28 | 2007-05-03 | Applied Materials, Inc. | Adhesion and minimizing oxidation on electroless CO alloy films for integration with low K inter-metal dielectric and etch stop |
| JP2009152544A (en) * | 2007-10-09 | 2009-07-09 | Applied Materials Inc | Method of forming void in multilevel interconnection structure |
| JP2015066818A (en) * | 2013-09-30 | 2015-04-13 | 日立マクセル株式会社 | Metal mask manufacturing method |
-
2014
- 2014-02-14 JP JP2014026944A patent/JP6284144B2/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0645232A (en) * | 1992-04-24 | 1994-02-18 | Wisconsin Alumni Res Found | Formation of fine structure, by multiple- level deep-x-ray lithography, provided with sacrificial layer |
| US5685491A (en) * | 1995-01-11 | 1997-11-11 | Amtx, Inc. | Electroformed multilayer spray director and a process for the preparation thereof |
| JPH08334903A (en) * | 1995-06-05 | 1996-12-17 | Think Lab Kk | Screen plate and its production |
| JPH11176411A (en) * | 1997-12-11 | 1999-07-02 | Kyushu Hitachi Maxell Ltd | Safety valve device for battery and its manufacture |
| JPH11186262A (en) * | 1997-12-17 | 1999-07-09 | Sanyo Electric Co Ltd | Manufacture of semiconductor device |
| JP2001316862A (en) * | 2000-05-02 | 2001-11-16 | Citizen Watch Co Ltd | Three-dimensional electrocast product, manufacturing method, and three-dimensional electrocast sheet |
| JP2002187374A (en) * | 2000-12-20 | 2002-07-02 | Kyushu Hitachi Maxell Ltd | Electroformed metal mask and method for manufacturing the same |
| JP2003072021A (en) * | 2001-09-03 | 2003-03-12 | Process Lab Micron:Kk | Metal mask for printing |
| JP2005532015A (en) * | 2002-06-27 | 2005-10-20 | マイクロファブリカ インク | Miniature RF and microwave components and methods for manufacturing such components |
| JP2005154879A (en) * | 2003-11-28 | 2005-06-16 | Canon Components Inc | Metal mask for vapor deposition, and method of producing vapor deposition pattern using the same |
| JP2006063362A (en) * | 2004-08-25 | 2006-03-09 | Kyushu Hitachi Maxell Ltd | Method for producing electrode body |
| JP2006287034A (en) * | 2005-04-01 | 2006-10-19 | Shinko Electric Ind Co Ltd | Manufacturing method of wiring substrate utilizing electrolytic plating |
| US20070099417A1 (en) * | 2005-10-28 | 2007-05-03 | Applied Materials, Inc. | Adhesion and minimizing oxidation on electroless CO alloy films for integration with low K inter-metal dielectric and etch stop |
| JP2009152544A (en) * | 2007-10-09 | 2009-07-09 | Applied Materials Inc | Method of forming void in multilevel interconnection structure |
| JP2015066818A (en) * | 2013-09-30 | 2015-04-13 | 日立マクセル株式会社 | Metal mask manufacturing method |
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