JP2014156629A - Etchant for copper or copper alloy, and method for etching copper or copper alloy using the same - Google Patents
Etchant for copper or copper alloy, and method for etching copper or copper alloy using the same Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 129
- 239000010949 copper Substances 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000004715 keto acids Chemical class 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 15
- -1 halogen ion Chemical class 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 238000007788 roughening Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 74
- 238000012360 testing method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000005498 polishing Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000007747 plating Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid 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
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- CGPVLUCOFNAVGV-UHFFFAOYSA-N copper;pentahydrate Chemical compound O.O.O.O.O.[Cu] CGPVLUCOFNAVGV-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Weting (AREA)
Abstract
Description
本発明は、銅または銅合金の表面をナノメートルのオーダーでエッチングすることのできるエッチング液およびそれを用いた銅または銅合金のエッチング方法に関する。 The present invention relates to an etching solution capable of etching the surface of copper or a copper alloy in the order of nanometers and a method for etching copper or a copper alloy using the same.
プリント基板を製造する際には、銅張積層板の不要部分の銅を薬品で溶解除去し、回路を形成する工程（エッチング工程）を行っている。また、このエッチング工程に先立ち、感光性樹脂（ドライフィルムレジスト：ＤＦＲ）を銅表面に張り付け、露光、現像し、銅表面にＤＦＲによる回路のマスクを形成している。このＤＦＲと銅表面とが強固に密着していないと、エッチング工程時にＤＦＲが銅表面から浮き、回路が断線し、所望の回路が得られず不良となる。そのため、ＤＦＲと銅表面とを密着させる方法として、古くはバフ研磨、ブラシ研磨、スクラブ研磨あるいはベルトサンダー研磨のような機械的研磨によって銅表面を粗化する方法が採用されていた。 When manufacturing a printed circuit board, an unnecessary portion of copper in the copper-clad laminate is dissolved and removed with a chemical to form a circuit (etching step). Prior to this etching step, a photosensitive resin (dry film resist: DFR) is attached to the copper surface, exposed and developed, and a DFR circuit mask is formed on the copper surface. If the DFR and the copper surface are not firmly adhered, the DFR floats from the copper surface during the etching process, the circuit is disconnected, and a desired circuit cannot be obtained, resulting in a failure. Therefore, as a method for bringing the DFR and the copper surface into close contact with each other, a method of roughening the copper surface by mechanical polishing such as buff polishing, brush polishing, scrub polishing or belt sander polishing has been used in the past.
しかしながら、プリント基板の高密度化、細線化、薄化が進み、特にフレキシブル回路基板に代表されるような薄物には、研磨機の構造上あるいは機械的な力を加えることによる基板の伸びによる寸法精度の低下が問題となり、機械的な研磨では対応できなくなった。そこで、機械的な研磨から薬品を使用した化学的研磨へと研磨方法が移行してきた。 However, printed circuit boards are becoming denser, thinner, and thinner, especially for thin objects such as flexible circuit boards, due to the structure of the polishing machine or the dimensions of the substrate due to mechanical force. Decrease in accuracy became a problem, and mechanical polishing could not cope. Therefore, the polishing method has shifted from mechanical polishing to chemical polishing using chemicals.
これまで化学的研磨の方法としては、例えば、特許文献１〜７に開示されているような酸と過酸化水素を含み、更に必要によりアゾール類等を含み、過酸化水素が数ｇ〜数百ｇ／Ｌ程度であるエッチング液が提案されている。そしてこれらのエッチング液はマイクロメートルオーダーでのエッチングを目的としている。 Conventional chemical polishing methods include, for example, acids and hydrogen peroxide as disclosed in Patent Documents 1 to 7, and further, if necessary, azoles and the like. An etching solution of about g / L has been proposed. These etchants are intended for etching in the micrometer order.
また、近年のセミアディティブ工法に代表されるＤＦＲをめっきレジストとして使用する場合、下地の銅シード層は１μｍ以下と非常に薄いため、同箇所に上記エッチング液を用いてナノメートルオーダーのエッチングをしようとすると、エッチング速度が速いため制御がし難く、また、仮にナノメートルオーダーのエッチングができたとしても粗化も不十分であるため実用できない。そのため、現状はエッチングの代わりに酸脱脂が用いられることが殆どであり、ＤＦＲの高密着が期待できない。 In addition, when using DFR, which is typified by the recent semi-additive method, as a plating resist, the underlying copper seed layer is very thin, 1 μm or less, so use the above etching solution at the same location to perform nanometer-order etching. Then, since the etching rate is high, it is difficult to control, and even if etching on the nanometer order is possible, roughening is insufficient and thus cannot be practically used. Therefore, at present, acid degreasing is mostly used instead of etching, and high adhesion of DFR cannot be expected.
また、より近年では銅シード層と結合している絶縁樹脂層は銅回路の表皮抵抗の懸念から、表面粗さ（Ｒａ）も３００ｎｍ以下であることが要求され、それに伴い絶縁樹脂表層の粗化に関しても低減対策が要求されている。更に、絶縁樹脂層の平滑化に伴い、シード層も平滑に仕上るため、ＤＦＲとのアンカー効果も低下してしまい、密着性の確保がより一層困難となってきている。 Further, in recent years, the insulating resin layer bonded to the copper seed layer is required to have a surface roughness (Ra) of 300 nm or less due to concern about the skin resistance of the copper circuit. There is also a demand for reduction measures. Further, as the insulating resin layer is smoothed, the seed layer is also finished smoothly, so that the anchor effect with the DFR is also lowered, and it is becoming more difficult to ensure adhesion.
従って、本発明の課題は、ナノメートルオーダーでのエッチングにより、銅や銅合金を微細に粗化させ、ＤＦＲ、絶縁樹脂等を強固に密着できる表面に仕上げることのできる技術を提供することである。 Accordingly, an object of the present invention is to provide a technique capable of finely roughing copper or a copper alloy by etching on the order of nanometers and finishing it to a surface capable of firmly adhering DFR, insulating resin, and the like. .
本発明者らは、上記課題を解決するために鋭意研究した結果、意外にも過酸化水素および無機オキソ酸を含有するエッチング液において、過酸化水素の含有量を従来と比較してごく少量の範囲にすることにより、上記課題を解決できることを見出した。 As a result of diligent research to solve the above problems, the present inventors have unexpectedly found that in an etching solution containing hydrogen peroxide and an inorganic oxo acid, the content of hydrogen peroxide is very small compared to the conventional one. It has been found that the above-mentioned problems can be solved by making the range.
すなわち、本発明は過酸化水素および無機オキソ酸を含有し、過酸化水素の含有量が０.１〜１ｇ／Ｌであることを特徴とする銅または銅合金用エッチング液である。 That is, the present invention is an etching solution for copper or copper alloy, which contains hydrogen peroxide and an inorganic oxo acid, and the content of hydrogen peroxide is 0.1 to 1 g / L.
また、本発明は銅または銅合金を上記銅または銅合金用エッチング液で処理することを特徴とする銅または銅合金のエッチング方法である。 The present invention is also a copper or copper alloy etching method characterized by treating copper or a copper alloy with the above-mentioned etching solution for copper or copper alloy.
本発明によれば、銅または銅合金を制御よくナノメートルオーダーで微細に粗化できるため、ＤＦＲ、絶縁樹脂等を強固に密着できる表面に仕上げることができる。 According to the present invention, since copper or a copper alloy can be finely roughened in a nanometer order with good control, it is possible to finish the surface on which DFR, insulating resin, and the like can be firmly adhered.
また、本発明に用いられるエッチング液は、従来のエッチング液における過酸化水素および無機オキソ酸の使用濃度に比べ、２０分の１以下の濃度で使用することができるため、廃液する際の中和廃液の負荷低減も図れ、環境配慮にも優れたエッチング液である。 Further, the etching solution used in the present invention can be used at a concentration of 1/20 or less compared to the concentration of hydrogen peroxide and inorganic oxo acid used in the conventional etching solution. It is an etching solution that can reduce the load of waste liquid and is excellent in environmental considerations.
本発明の銅または銅合金用エッチング液（以下、「本発明のエッチング液」という）は、過酸化水素および無機オキソ酸を含有し、過酸化水素の含有量が０.１〜１ｇ／Ｌ、好ましくは０.１２〜０.９ｇ／Ｌ、より好ましくは０.１５〜０.８ｇ／Ｌのものである。 The etching solution for copper or copper alloy of the present invention (hereinafter referred to as “etching solution of the present invention”) contains hydrogen peroxide and an inorganic oxo acid, and the hydrogen peroxide content is 0.1 to 1 g / L, Preferably it is from 0.12 to 0.9 g / L, more preferably from 0.15 to 0.8 g / L.
また、本発明のエッチング液に含有される無機オキソ酸の種類は、特に限定されず、例えば、硝酸、硫酸、リン酸等が挙げられる。これらの無機オキソ酸は１種または２種以上を用いることができる。本発明のエッチング液における無機オキソ酸の含有量も特に限定されないが、例えば、０.１〜５００ｇ／Ｌであり、好ましくは０.３〜２００ｇ／Ｌである。より具体的に無機オキソ酸として硫酸を用いる場合には、例えば、０.１〜２００ｇ／Ｌが好ましく、０.３〜１００ｇ／Ｌがより好ましく、０．４〜５０ｇ／Ｌが特に好ましい。なお、廃水処理を懸念する場合、硫酸の量は０.４〜５ｇ／Ｌが適切である。 Moreover, the kind of inorganic oxo acid contained in the etching liquid of this invention is not specifically limited, For example, nitric acid, a sulfuric acid, phosphoric acid etc. are mentioned. These inorganic oxo acids can be used alone or in combination of two or more. The content of the inorganic oxo acid in the etching solution of the present invention is not particularly limited, but is, for example, 0.1 to 500 g / L, preferably 0.3 to 200 g / L. More specifically, when sulfuric acid is used as the inorganic oxo acid, for example, 0.1 to 200 g / L is preferable, 0.3 to 100 g / L is more preferable, and 0.4 to 50 g / L is particularly preferable. In addition, when worried about wastewater treatment, the amount of sulfuric acid is appropriately 0.4 to 5 g / L.
なお、本発明のエッチング液における過酸化水素と無機オキソ酸の比率は特に限定されないが、例えば、過酸化水素と、無機オキソ酸として硫酸を用いる場合の比率は、ｇ／Ｌ単位で、１：１.５、好ましくは１：２、より好ましくは１：２.５以上である。 The ratio of hydrogen peroxide to inorganic oxo acid in the etching solution of the present invention is not particularly limited. For example, the ratio when hydrogen peroxide and sulfuric acid are used as the inorganic oxo acid is 1: g / L. The ratio is 1.5, preferably 1: 2, more preferably 1: 2.5 or more.
更に、本発明のエッチング液には、更に、Ｃｕ２＋等の銅イオンを含有させてもよい。本発明エッチング液における銅イオンの含有量は、特に限定されないが、例えば、０.１〜８０ｇ／Ｌが好ましく、０.５〜５０ｇ／Ｌがより好ましく、１〜４０ｇ／Ｌが特に好ましい。なお、銅イオン源としては、特に限定されないが、例えば、硫酸銅・５水和物等の水溶性の銅塩や、金属銅等が挙げられる。 Furthermore, the etching solution of the present invention may further contain copper ions such as Cu 2+ . Although content of the copper ion in this invention etching liquid is not specifically limited, For example, 0.1-80 g / L is preferable, 0.5-50 g / L is more preferable, 1-40 g / L is especially preferable. In addition, although it does not specifically limit as a copper ion source, For example, water-soluble copper salts, such as copper sulfate and pentahydrate, metallic copper, etc. are mentioned.
また更に、本発明のエッチング液には、更に、ハロゲンイオンを含有させてもよい。本発明エッチング液におけるハロゲンイオンの含有量は、特に限定されないが、例えば、０.００００１〜０.０５ｇ／Ｌであり、好ましくは０.００００１〜０.０２ｇ／Ｌである。より具体的にハロゲンイオンとして塩素イオンを用いる場合には、例えば、０.０５〜１０ｍｇ／Ｌが好ましく、０.１〜５ｍｇ／Ｌがより好ましく、０.５〜３ｍｇ／Ｌが特に好ましい。なお、ハロゲンイオン源としては、特に限定されないが、例えば、塩化ナトリウム、塩酸、塩化第二銅等が挙げられる。 Furthermore, the etching solution of the present invention may further contain halogen ions. The content of halogen ions in the etching solution of the present invention is not particularly limited, but is, for example, 0.0001 to 0.05 g / L, preferably 0.0001 to 0.02 g / L. More specifically, when chlorine ions are used as the halogen ions, for example, 0.05 to 10 mg / L is preferable, 0.1 to 5 mg / L is more preferable, and 0.5 to 3 mg / L is particularly preferable. In addition, although it does not specifically limit as a halogen ion source, For example, sodium chloride, hydrochloric acid, cupric chloride, etc. are mentioned.
なお、本発明のエッチング液のｐＨは、特に限定されないが、例えば、４以下、好ましくは０.５〜２である。なお、廃水処理を懸念する場合には、ｐＨは１.３〜２.３が好ましい。 The pH of the etching solution of the present invention is not particularly limited, but is, for example, 4 or less, preferably 0.5-2. In addition, when worried about wastewater treatment, the pH is preferably 1.3 to 2.3.
本発明のエッチング液は、必須成分である過酸化水素および無機オキソ酸と、必要により銅イオン源、ハロゲンイオン源を、水に溶解させることによって調製することができる。この時、過酸化水素は分解しやすい性質から、別途公知である過酸化水素の安定剤となる物質、例えば、プロパノール等のアルコール類やエチレングリコール等のグリコールエーテル類等を含有させてもよい The etching solution of the present invention can be prepared by dissolving hydrogen peroxide and inorganic oxo acid, which are essential components, and, if necessary, a copper ion source and a halogen ion source in water. At this time, because hydrogen peroxide is easily decomposed, a known hydrogen peroxide stabilizer, for example, alcohols such as propanol or glycol ethers such as ethylene glycol may be included.
なお、本発明のエッチング液の好ましい態様としては、以下の（１）〜（３）が挙げられる。
（１）過酸化水素および無機オキソ酸を含有し、過酸化水素の含有量が０.１〜１ｇ／Ｌであるエッチング液
（２）過酸化水素および無機オキソ酸のみを含有し、過酸化水素の含有量が０.１〜１ｇ／Ｌであるエッチング液
（３）過酸化水素および無機オキソ酸と、銅イオンおよび／または塩素イオンのみを含有し、過酸化水素の含有量が０.１〜１ｇ／Ｌであるエッチング液
In addition, as a preferable aspect of the etching liquid of this invention, the following (1)-(3) is mentioned.
(1) Etching solution containing hydrogen peroxide and inorganic oxo acid with a hydrogen peroxide content of 0.1 to 1 g / L. (2) Containing only hydrogen peroxide and inorganic oxo acid. (3) Hydrogen peroxide and inorganic oxo acid, and only copper ions and / or chlorine ions, and hydrogen peroxide content of 0.1 to 1 g / L Etching solution that is 1 g / L
斯くして得られる本発明のエッチング液で、銅または銅合金を銅溶解量から算出したエッチング量としてナノメーターのオーダー、好ましくは１〜５００ｎｍ、より好ましくは１０〜３００ｎｍでエッチングすることができる。このエッチングにより表面粗さ（Ｒａ）３００ｎｍ以下の要求を満たすことができる。 With the etching solution of the present invention thus obtained, the etching amount of copper or copper alloy calculated from the amount of dissolved copper can be etched in the order of nanometers, preferably 1 to 500 nm, more preferably 10 to 300 nm. This etching can satisfy the requirement of surface roughness (Ra) of 300 nm or less.
本発明のエッチング液で処理される銅または銅合金としては、純銅、黄銅、青銅、白銅、ベリリウム銅等が挙げられ、また、具体的な形態としては、エッチング対象となる被処理物の表面に銅または銅合金を有するものであれば特に限定されず、例えば、銅張積層板の電解銅（銅合金）箔または圧延銅（銅合金）箔、銅張積層板上の電解銅（銅合金）めっき、樹脂上に形成された無電解銅（銅合金）等が挙げられる。 Examples of the copper or copper alloy to be treated with the etching solution of the present invention include pure copper, brass, bronze, white copper, beryllium copper and the like, and as a specific form, on the surface of the object to be etched. No particular limitation as long as it has copper or copper alloy, for example, electrolytic copper (copper alloy) foil or rolled copper (copper alloy) foil of copper-clad laminate, electrolytic copper (copper alloy) on copper-clad laminate Examples thereof include electroless copper (copper alloy) formed on plating and resin.
本発明のエッチング液で銅または銅合金を処理するには、従来公知のエッチング液を用いた処理方法が利用でき、例えば、エッチング液を入れた処理槽内に、表面に銅または銅合金を有する被処理物を浸漬する方法、エッチング液を被処理物にスプレーする方法等が挙げられる。これらの方法の中でもスプレーする方法が均一に粗化できることから好ましい。また、浸漬する方法においては、被処理物の表面にエッチング液との液流を当てるようにすることが好ましい。 In order to treat copper or a copper alloy with the etching solution of the present invention, a conventionally known processing method using an etching solution can be used. For example, a copper or copper alloy is provided on the surface in a treatment tank containing the etching solution. Examples include a method of immersing the object to be processed, a method of spraying an etching solution on the object to be processed, and the like. Among these methods, the spraying method is preferable because it can be uniformly roughened. In the dipping method, it is preferable that a liquid flow with an etching solution is applied to the surface of the object to be processed.
また、上記処理における処理温度は、特に限定されないが、例えば、エッチング液の液温は１０〜５０℃、好ましくは２０〜４０℃である。また、処理時間は、使用するエッチング液の組成、液温、エッチング対象物の銅層の状態（厚さや表面状態）、目的とするエッチング量等により適宜決定されるので特に限定されないが、例えば、３〜３００秒、好ましくは１０〜１２０秒である。 Moreover, the process temperature in the said process is although it does not specifically limit, For example, the liquid temperature of etching liquid is 10-50 degreeC, Preferably it is 20-40 degreeC. Further, the treatment time is not particularly limited because it is appropriately determined depending on the composition of the etching solution to be used, the liquid temperature, the state of the copper layer of the etching target (thickness and surface state), the target etching amount, etc. It is 3 to 300 seconds, preferably 10 to 120 seconds.
上記のようにして本発明のエッチング液で銅または銅合金にエッチングを行った後は、銅または銅合金を十分に洗浄し、乾燥させ、次の工程に用いればよい。次の工程としては、特に限定されないが、例えば、ＤＦＲ、ソルダーレジスト、層間絶縁樹脂、カバーレイ等の塗布・接着工程が挙げられる。 After etching copper or a copper alloy with the etching solution of the present invention as described above, the copper or copper alloy may be sufficiently washed, dried, and used in the next step. Although it does not specifically limit as a next process, For example, application | coating and adhesion processes, such as DFR, a soldering resist, interlayer insulation resin, a coverlay, are mentioned.
なお、本発明のエッチング液で処理を行う好ましい態様としては、銅張積層板とＤＦＲを用いたプリント配線基板の製造工程における以下の処理（１）〜（３）が挙げられる。
（１）銅張積層板の電解銅（銅合金）箔または圧延銅（銅合金）箔への表面処理
（２）銅張積層板上の電解銅（銅合金）めっきへの表面処理
（３）樹脂上に形成された無電解銅（銅合金）めっきへの表面処理
In addition, as a preferable aspect which processes with the etching liquid of this invention, the following processes (1)-(3) in the manufacturing process of the printed wiring board using a copper clad laminated board and DFR are mentioned.
(1) Surface treatment of electrolytic copper (copper alloy) foil or rolled copper (copper alloy) foil of copper clad laminate (2) Surface treatment of electrolytic copper (copper alloy) plating on copper clad laminate (3) Surface treatment for electroless copper (copper alloy) plating formed on resin
以下、本発明を実施例を挙げて詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples at all.
実 施 例 １
エッチング液の調製：
硫酸０.７ｇ／Ｌ、過酸化水素０.３ｇ／Ｌ、過酸化水素の安定剤としてプロパノール０.５ｇ／Ｌを含む水溶液を調製し、これをエッチング液とした（ｐＨ：１.８）。
Example 1
Etching solution preparation:
An aqueous solution containing 0.7 g / L of sulfuric acid, 0.3 g / L of hydrogen peroxide, and 0.5 g / L of propanol as a hydrogen peroxide stabilizer was prepared and used as an etching solution (pH: 1.8).
実 施 例 ２
エッチング液の調製：
硫酸０.７ｇ／Ｌ、過酸化水素０.３ｇ／Ｌ、硫酸銅・５水和物２０ｇ／Ｌ（銅イオンとして５ｇ／Ｌ）、過酸化水素の安定剤としてプロパノール０.５ｇ／Ｌを含む水溶液を調製し、これをエッチング液とした（ｐＨ：２.２）。
Example 2
Etching solution preparation:
Contains 0.7 g / L of sulfuric acid, 0.3 g / L of hydrogen peroxide, 20 g / L of copper sulfate pentahydrate (5 g / L as copper ions), and 0.5 g / L of propanol as a hydrogen peroxide stabilizer. An aqueous solution was prepared and used as an etching solution (pH: 2.2).
実 施 例 ３
エッチング液の調製：
硫酸を０.４ｇ／Ｌ、過酸化水素を０.１５ｇ／Ｌに代えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：２.０）。
Example 3
Etching solution preparation:
An etching solution was prepared in the same manner as in Example 2 except that sulfuric acid was changed to 0.4 g / L and hydrogen peroxide was changed to 0.15 g / L (pH: 2.0).
実 施 例 ４
エッチング液の調製：
硫酸を２.５ｇ／Ｌ、過酸化水素を０.８ｇ／Ｌに代えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：１.７）。
Example 4
Etching solution preparation:
An etching solution was prepared in the same manner as in Example 2 except that sulfuric acid was changed to 2.5 g / L and hydrogen peroxide was changed to 0.8 g / L (pH: 1.7).
実 施 例 ５
エッチング液の調製：
硫酸を３.５ｇ／Ｌ、過酸化水素を１.０ｇ／Ｌに代えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：１.４）。
Example 5
Etching solution preparation:
An etching solution was prepared in the same manner as in Example 2 except that sulfuric acid was changed to 3.5 g / L and hydrogen peroxide was changed to 1.0 g / L (pH: 1.4).
実 施 例 ６
エッチング液の調製：
硫酸を０.７ｇ／Ｌ、過酸化水素を０.３ｇ／Ｌ、硫酸銅・５水和物を８０ｇ／Ｌ（銅イオンとして２０ｇ／Ｌ）に代えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：２.１）。
Example 6
Etching solution preparation:
Example 2 was repeated except that sulfuric acid was changed to 0.7 g / L, hydrogen peroxide was changed to 0.3 g / L, and copper sulfate pentahydrate was changed to 80 g / L (20 g / L as copper ions). Thus, an etching solution was prepared (pH: 2.1).
実 施 例 ７
エッチング液の調製：
更に、塩化ナトリウムを３.３ｍｇ／Ｌ（塩素イオンとして２ｍｇ／Ｌ）を加えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：２.２）。
Example 7
Etching solution preparation:
Further, an etching solution was prepared in the same manner as in Example 2 except that 3.3 mg / L of sodium chloride (2 mg / L as chloride ion) was added (pH: 2.2).
実 施 例 ８
エッチング液の調製：
硫酸を９０ｇ／Ｌに代えたこと以外は、実施例２と同様にしてエッチング液を調製した（ｐＨ：０.３）。
Example 8
Etching solution preparation:
An etching solution was prepared in the same manner as in Example 2 except that sulfuric acid was changed to 90 g / L (pH: 0.3).
比 較 例 １
エッチング液の調製：
硫酸９０ｇ／Ｌ、過酸化水素２０ｇ／Ｌ、硫酸銅・５水和物２０ｇ／Ｌ、過酸化水素の安定剤としてプロパノール０.５ｇ／Ｌを含む水溶液を調製し、これをエッチング液とした（ｐＨ：０.３）。
Comparative Example 1
Etching solution preparation:
An aqueous solution containing 90 g / L of sulfuric acid, 20 g / L of hydrogen peroxide, 20 g / L of copper sulfate pentahydrate, and 0.5 g / L of propanol as a hydrogen peroxide stabilizer was prepared as an etching solution ( pH: 0.3).
比 較 例 ２
エッチング液の調製：
硫酸を４５ｇ／Ｌ、過酸化水素を１０ｇ／Ｌに代えたこと以外は、比較例１と同様にしてエッチング液を調製した（ｐＨ：０.５）。
Comparative Example 2
Etching solution preparation:
An etching solution was prepared in the same manner as in Comparative Example 1 except that sulfuric acid was changed to 45 g / L and hydrogen peroxide was changed to 10 g / L (pH: 0.5).
比 較 例 ３
エッチング液の調製：
硫酸を１ｇ／Ｌに代えたこと以外は、比較例１と同様にしてエッチング液を調製した（ｐＨ：１.７）。
Comparative Example 3
Etching solution preparation:
An etching solution was prepared in the same manner as in Comparative Example 1 except that the sulfuric acid was changed to 1 g / L (pH: 1.7).
試 験 例 １
エッチング試験：
各実施例および比較例で調製したエッチング液を各々２００ｍＬガラスビーカに入れ、液温を３０℃に保ち、その液中に市販の銅張積層板（日立化成工業社製、商品名：ＭＣＬ−Ｅ６７）の試験片（５ｃｍ×５ｃｍ）を浸漬し、エッチング量（銅溶解量から算出）が１００ｎｍ程度となるよう処理時間を調整して処理を行った。この処理後に得られた試験片は十分に水洗し、乾燥させた。これらの試験片について、その表面状態を走査電子顕微鏡写真（ＳＥＭ）観察（１万倍）を行い、以下の評価基準で表面仕上がり状態を判断した。また、表面処理後の銅張積層板の表面に粘着テープ（積水化学社製のポリエステルテープ、商品名：ＬＩＴＨＯＧＲＡＰＨＩＣ）を圧着後、テープを剥離し、銅張り積層板の銅表面に残存するテープ糊の転着状態を目視で調べ、以下の評価基準で評価を行った。これらの結果を処理時間とエッチング量と共に表１に示した。また、実施例１、２、７および比較例１のエッチング液を用いて銅張り積層板をエッチングした後の表状態のＳＥＭ像（１万倍）を図１〜４に示した。
Test example 1
Etching test:
Each of the etching solutions prepared in each Example and Comparative Example was put into a 200 mL glass beaker, the liquid temperature was kept at 30 ° C., and a commercially available copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E67). ) Test piece (5 cm × 5 cm), and the treatment time was adjusted so that the etching amount (calculated from the copper dissolution amount) was about 100 nm. The test piece obtained after this treatment was sufficiently washed with water and dried. About these test pieces, the surface state was observed by scanning electron micrograph (SEM) (10,000 times), and the surface finish state was judged according to the following evaluation criteria. In addition, adhesive tape (Polyester tape manufactured by Sekisui Chemical Co., Ltd., trade name: LITHOGRAPHIC) is pressure-bonded to the surface of the copper clad laminate after the surface treatment, the tape is peeled off, and the tape glue remaining on the copper surface of the copper clad laminate The transfer state was visually checked and evaluated according to the following evaluation criteria. These results are shown in Table 1 together with the processing time and the etching amount. Moreover, the SEM image (10,000 times) of the surface state after etching a copper clad laminated board using the etching liquid of Example 1, 2, 7 and the comparative example 1 was shown to FIGS.
＜仕上がり状態の評価基準＞
（評価） （内容）
○ ： 表面に微細な凹凸が形成されている。
× ： 表面に微細な凹凸が形成されていない。
<Evaluation criteria for finished condition>
(Evaluation) (Content)
○: Fine irregularities are formed on the surface.
X: No fine irregularities are formed on the surface.
＜密着性の評価基準＞
（評価） （内容）
○ ： テープ糊の転着が一部でもある。
× ： テープ糊の転着が全て欠損している。
<Adhesion evaluation criteria>
(Evaluation) (Content)
○: Transfer of tape glue is partly.
X: All transfer of tape glue is missing.
実施例１〜８のエッチング液を用いた場合は、エッチングの速度がエッチング量の目標である１００ｎｍ程度とするのに都合がよく、更に微細な凹凸形状も形成されため仕上がり状態がよく、密着性もよかった。一方、比較例１〜３のエッチング液を用いた場合では、エッチングの速度が速く１００ｎｍ程度に合わせることが困難な上、微細な凹凸形状も形成されなかったため密着性もよくなかった。また、実施例２〜８のエッチング液により、エッチング液に銅イオンや塩素イオンが存在しても性能に影響がなく、更に粗化状態がよいことが分かった。 When the etching solutions of Examples 1 to 8 are used, it is convenient for the etching rate to be about 100 nm, which is the target of the etching amount, and a fine uneven shape is also formed so that the finished state is good and the adhesion is good. It was good too. On the other hand, when the etching solutions of Comparative Examples 1 to 3 were used, the etching rate was high and it was difficult to adjust to about 100 nm, and the fine uneven shape was not formed, so the adhesion was not good. In addition, it was found that the etching solutions of Examples 2 to 8 did not affect the performance even when copper ions or chlorine ions were present in the etching solution, and further improved the roughening state.
試 験 例 ２
エッチング試験：
試験片を、市販の銅張積層板（日立化成工業社製、商品名：ＭＣＬ−Ｅ６７）に、硫酸銅めっき液（株式会社ＪＣＵ製、商品名：キューブライトＶＦII）を用いて電気めっきを行い、銅皮膜を３μｍの厚さで施したものに代えたこと以外は、試験例１と同様にしてエッチング試験を行った。また、試験例１と同様にして仕上がり状態および密着性を判断した。これらの結果を処理時間とエッチング量と共に表２に示した。また、実施例１、２、７および比較例１のエッチング液を用いて銅張り積層板に銅皮膜を３μｍの厚さで施したものをエッチングした後の表状態のＳＥＭ像（１万倍）を図５〜８に示した。
Test example 2
Etching test:
The test piece was electroplated on a commercially available copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E67) using a copper sulfate plating solution (manufactured by JCU Corporation, trade name: Cubelite VFII). The etching test was performed in the same manner as in Test Example 1 except that the copper film was replaced with a film having a thickness of 3 μm. Further, the finished state and adhesion were determined in the same manner as in Test Example 1. These results are shown in Table 2 together with the processing time and etching amount. Moreover, the SEM image (10,000 times) of the surface state after etching what applied the copper membrane | film | coat to the thickness of 3 micrometers on the copper clad laminated board using the etching liquid of Example 1, 2, 7 and the comparative example 1 Are shown in FIGS.
実施例１〜８のエッチング液を用いた場合は、エッチングの速度がエッチング量の目標である１００ｎｍ程度とするのに都合がよく、更に微細な凹凸形状も形成されため仕上がり状態がよく、密着性もよかった。一方、比較例１〜３のエッチング液を用いた場合では、エッチングの速度が速く１００ｎｍ程度に合わせることが困難な上、微細な凹凸形状も形成されなかったため密着性もよくなかった。また、実施例２〜８のエッチング液により、エッチング液に銅イオンや塩素イオンが存在しても性能に影響がなく、更に粗化状態がよいことが分かった。 When the etching solutions of Examples 1 to 8 are used, it is convenient for the etching rate to be about 100 nm, which is the target of the etching amount, and a fine uneven shape is also formed so that the finished state is good and the adhesion is good. It was good too. On the other hand, when the etching solutions of Comparative Examples 1 to 3 were used, the etching rate was high and it was difficult to adjust to about 100 nm, and the fine uneven shape was not formed, so the adhesion was not good. In addition, it was found that the etching solutions of Examples 2 to 8 did not affect the performance even when copper ions or chlorine ions were present in the etching solution, and further improved the roughening state.
試 験 例 ３
ピール強度の測定：
積層用樹脂の密着性の確認として、試験例２の実施例５または比較例１で使用した、エッチング処理後の硫酸銅めっき（株式会社ＪＣＵ製、商品名：キューブライトＶＦＩＩ）基板表面に対して、市販のラミネートタイプ樹脂（味の素ファインテクノ製：ＡＢＦ−ＧＸ−９２）を真空ラミネート法の標準条件で積層した。積層後にピール強度を測定した（ＪＩＳ：Ｃ６４８１に準拠）。その結果を表３に示した。
Test example 3
Peel strength measurement:
As a confirmation of the adhesion of the resin for laminating, the copper sulfate plating after the etching treatment used in Example 5 of Comparative Example 2 or Comparative Example 1 (JCU Co., Ltd., trade name: Cubelite VFII) on the substrate surface A commercially available laminate type resin (manufactured by Ajinomoto Fine Techno: ABF-GX-92) was laminated under the standard conditions of the vacuum laminating method. The peel strength was measured after lamination (according to JIS: C6481). The results are shown in Table 3.
ピール強度測定の結果、実施例５のエッチング液を用いた場合は、比較例１の従来のエッチング液を用いた場合と比較して２倍ものピール強度が得られた。これは実施例５のエッチング液により銅めっき表面に微細な凹凸が形成され、それによるアンカー効果によって密着性が向上したと考えられる。 As a result of the peel strength measurement, when the etching solution of Example 5 was used, a peel strength twice as much as that obtained when the conventional etching solution of Comparative Example 1 was used was obtained. This is considered to be because fine unevenness was formed on the surface of the copper plating by the etching solution of Example 5, and the adhesion was improved by the anchor effect.
本発明のエッチング液は、銅または銅合金をナノメートルのオーダーでエッチングすることができるので、著しい薄化が進むプリント基板の製造プロセスにおける銅または銅合金表面の微細凹凸による高密着仕上げ処理としてきわめて有用な手段である。
以 上
The etching solution of the present invention can etch copper or a copper alloy on the order of nanometers. Therefore, the etching solution of the present invention is extremely suitable as a high adhesion finishing process due to fine irregularities on the surface of a copper or copper alloy in a process of manufacturing a printed board that is remarkably thin. It is a useful tool.
that's all
Claims (6)
A method for etching copper or copper alloy, comprising treating copper or copper alloy with the copper or copper alloy etching solution according to any one of claims 1 to 5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521501A (en) * | 2016-12-05 | 2017-03-22 | 河北工业大学 | Brass alloy with macro-hole, micron-hole and nano-hole hierarchical hole structure and application thereof |
| CN107620067A (en) * | 2017-09-18 | 2018-01-23 | 中国电子科技集团公司第五十五研究所 | A kind of engraving method of silver-copper brazing alloy |
| CN113314473A (en) * | 2021-05-26 | 2021-08-27 | 绍兴德汇半导体材料有限公司 | Ceramic substrate graphical structure and manufacturing method thereof |
| CN113481508A (en) * | 2021-05-26 | 2021-10-08 | 绍兴德汇半导体材料有限公司 | Etching solution and etching method for removing etching residues of ceramic substrate |
| CN113488446A (en) * | 2021-05-26 | 2021-10-08 | 绍兴德汇半导体材料有限公司 | Ceramic substrate graphical structure and manufacturing method thereof |
| CN115161641A (en) * | 2022-07-08 | 2022-10-11 | 苏州迈为科技股份有限公司 | Etching solution additive, etching solution, application of etching solution and etching process |
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| JP2002266088A (en) * | 2001-03-07 | 2002-09-18 | Yamatoya & Co Ltd | Soft etching agent for copper clad laminate |
| JP2005330572A (en) * | 2003-07-25 | 2005-12-02 | Mec Kk | Etchant, replenishment solution and method for producing copper wiring using the same |
| JP2011523790A (en) * | 2008-06-03 | 2011-08-18 | マクダーミッド インコーポレーテッド | Acid resistance promoting composition |
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| JP2001262374A (en) * | 2000-03-09 | 2001-09-26 | Lg Philips Lcd Co Ltd | Etching agent for copper, method for manufacturing substrate for electronic aperture using the same and electronic apparatus |
| JP2002266088A (en) * | 2001-03-07 | 2002-09-18 | Yamatoya & Co Ltd | Soft etching agent for copper clad laminate |
| JP2005330572A (en) * | 2003-07-25 | 2005-12-02 | Mec Kk | Etchant, replenishment solution and method for producing copper wiring using the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106521501A (en) * | 2016-12-05 | 2017-03-22 | 河北工业大学 | Brass alloy with macro-hole, micron-hole and nano-hole hierarchical hole structure and application thereof |
| CN107620067A (en) * | 2017-09-18 | 2018-01-23 | 中国电子科技集团公司第五十五研究所 | A kind of engraving method of silver-copper brazing alloy |
| CN107620067B (en) * | 2017-09-18 | 2019-11-12 | 中国电子科技集团公司第五十五研究所 | A kind of engraving method of silver-copper brazing alloy |
| CN113314473A (en) * | 2021-05-26 | 2021-08-27 | 绍兴德汇半导体材料有限公司 | Ceramic substrate graphical structure and manufacturing method thereof |
| CN113481508A (en) * | 2021-05-26 | 2021-10-08 | 绍兴德汇半导体材料有限公司 | Etching solution and etching method for removing etching residues of ceramic substrate |
| CN113488446A (en) * | 2021-05-26 | 2021-10-08 | 绍兴德汇半导体材料有限公司 | Ceramic substrate graphical structure and manufacturing method thereof |
| CN115161641A (en) * | 2022-07-08 | 2022-10-11 | 苏州迈为科技股份有限公司 | Etching solution additive, etching solution, application of etching solution and etching process |
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