JP5425440B2 - Whisker suppression method in copper plating - Google Patents
Whisker suppression method in copper plating Download PDFInfo
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Description
本発明は、銅めっきにおけるウィスカーの抑制方法に関するものである。 The present invention relates to a method for suppressing whiskers in copper plating.
例えば、携帯電話やパソコンなどの電子部品として使用されるプリント配線基板は、酸性銅（硫酸銅）めっき処理によってその表面に銅箔が形成される。近時、めっき浴用添加剤の性能（耐ピット性、低電流部への付きまわり性など）が向上するに連れ、問題となってきているのが、銅めっきがヒゲ状に成長するいわゆる「ウィスカー」である。ウィスカーの大きさは、直径数μｍ〜数百μｍ、長さ数μｍ〜数ｍｍ程度であるが、通常の「ザラ」とは異なり、核の発見が困難か、または見つからないのが普通である。 For example, a printed wiring board used as an electronic component such as a mobile phone or a personal computer has a copper foil formed on the surface thereof by an acidic copper (copper sulfate) plating process. Recently, as the performance of plating bath additives (pit resistance, throwing power to low current parts, etc.) has improved, the problem is the so-called “whisker” where copper plating grows in a beard shape. Is. Whisker size is about several μm to several hundred μm in diameter and several μm to several mm in length, but unlike ordinary “Zara”, it is usually difficult to find the nucleus or not to be found. .
ウィスカー発生の確定的原因は未解明であるが、以下のような事柄がその原因の一部ではないかと考えられている。
(1) 近年、プリント配線基板の高密度化に伴って配線板の薄膜化が進んでいる。そのため、基板表面の機械研磨処理が省略されることもある。基板表面が酸化皮膜などで汚れていた場合、機械研磨処理が省かれると、添加剤の吸着ムラを生じてしまう可能性がある。添加剤の吸着ムラが生じた場合、析出電位が異なり、析出速度が異常に速くなってしまう箇所にヒゲ状のウィスカーが発生する。
(2) 酸性銅めっき浴中に、含りん銅とは異なる銅金属やイオンが混入され、それが核となってヒゲ状のウィスカーとなる。
Although the definitive cause of whisker occurrence is unclear, the following matters are thought to be part of the cause.
(1) In recent years, with the increase in the density of printed wiring boards, the thickness of wiring boards has been reduced. Therefore, the mechanical polishing process on the substrate surface may be omitted. When the substrate surface is soiled with an oxide film or the like, if the mechanical polishing treatment is omitted, there is a possibility that uneven adsorption of the additive occurs. When uneven adsorption of the additive occurs, the deposition potential is different, and whisker-like whiskers are generated at locations where the deposition rate becomes abnormally high.
(2) In the acidic copper plating bath, copper metal or ions different from phosphorous copper are mixed, and this becomes the core and becomes whisker-like whiskers.
上記ウィスカーの発生を抑制するには、
(a) 作業電流密度を下げ、めっきの析出速度を均一にする。
(b) 酸性銅めっき浴中への添加剤の添加量を多くし、吸着されにくい基板表面にも添加剤を吸着させるようにする。
(c) レべリング作用の高い添加剤を使用する。
(d) 不溶解性アノードを使用する。
(e) ＯＮ−ＯＦＦ電源を用いたり、印加する直流電源の極性を正負反転させながらめっきを行なう（特許文献１参照）。
などの方法で或る程度は可能である。しかしながら、どれも完全ではない。例えば、（ａ）の方法では生産能力が低下してしまう懸念があり、（ｂ）の方法では銅めっき皮膜の物性が低下してしまう懸念がある。また、（ｃ）の方法ではピットが発生しやすいなど、プリント配線基板の性能が低下してしまうおそれがある。
To suppress the occurrence of the above whiskers,
(a) Reduce the working current density and make the deposition rate uniform.
(b) The amount of additive added to the acidic copper plating bath is increased so that the additive is adsorbed on the substrate surface which is difficult to be adsorbed.
(c) Use additives with a high leveling effect.
(d) Use an insoluble anode.
(e) Plating is performed using an ON-OFF power source or reversing the polarity of a DC power source to be applied (see Patent Document 1).
It is possible to some extent by such a method. However, none are perfect. For example, there is a concern that the production capacity is lowered in the method (a), and there is a concern that the physical properties of the copper plating film are lowered in the method (b). Further, in the method (c), there is a possibility that the performance of the printed wiring board is deteriorated, for example, pits are easily generated.
本発明は、上記問題を解決することを課題とするもので、銅めっき処理に際して、特許文献１に開示されている電源電圧反転法を採用した上で、さらにこれを改良したものである。なお、ここに云う「電源電圧反転法」とは、カソード（負極）とアノード（正極）間に印加する直流電源電圧の極性を正負反転可能とし、プリント配線基板などの被めっき物をカソードとする通常の正電解と、被めっき物をアノードとする逆電解とを交互に切り替えながら銅めっき処理を行なう方法を指すものである。 An object of the present invention is to solve the above-mentioned problems. The copper plating process adopts the power supply voltage inversion method disclosed in Patent Document 1 and further improves it. The "power supply voltage reversal method" here refers to the polarity of the DC power supply voltage applied between the cathode (negative electrode) and the anode (positive electrode) can be reversed, and the object to be plated such as a printed wiring board is used as the cathode. This refers to a method of performing copper plating while alternately switching between normal positive electrolysis and reverse electrolysis using an object to be plated as an anode.
上記電源電圧反転法を採用すると、正電解時に基板表面に突出して生成される銅めっき皮膜は、逆電解時に優先的に溶解される。これを繰り返すことにより、ウィスカーの発生を抑制することが可能となる。しかしながら、電解条件によっては、ウィスカーの発生を完全に抑制できない場合もある。 When the above power supply voltage reversal method is employed, the copper plating film that protrudes from the substrate surface during forward electrolysis is preferentially dissolved during reverse electrolysis. By repeating this, generation of whiskers can be suppressed. However, depending on the electrolysis conditions, the generation of whiskers may not be completely suppressed.
そこで、本発明は、印加する直流電源、電極間距離、被めっき物の揺動条件などを最適な値に規定することにより、ウィスカーの発生を確実に抑制できるとともに、銅めっき面の光沢外観も良好なウィスカー抑制方法を開発したものである。 Therefore, the present invention can suppress the generation of whiskers by setting the DC power supply to be applied, the distance between the electrodes, the rocking condition of the object to be plated, etc. to the optimum values, and also the gloss appearance of the copper plating surface. A good whisker suppression method has been developed.
本発明のウィスカー抑制方法は、上記電源電圧反転法を用いた銅めっき処理に際して、電解条件として下記の〔条件１〕〜〔条件５〕を採用し、これらの条件を有機的に組み合わせたものである。 The whisker suppression method of the present invention employs the following [Condition 1] to [Condition 5] as electrolytic conditions in copper plating using the power supply voltage reversal method, and organically combines these conditions. is there.
すなわち、請求項１に係る発明は〔条件１〕＋〔条件２〕＋〔条件３〕、請求項２に係る発明は〔条件１〕＋〔条件２〕＋〔条件４〕、請求項３に係る発明は〔条件１〕＋〔条件２〕＋〔条件５〕を組み合わせたことをそれぞれ特徴とするものである。 That is, the invention is [Requirement 1] + [Requirement 2] + [Condition 3] according to 請 Motomeko 1, the invention according to claim 2 [Requirement 1] + [Requirement 2] + [Condition 4], claim 3 The inventions according to the above are characterized by combining [Condition 1] + [Condition 2] + [Condition 5].
〔条件１〕印加する直流電源
カソード、アノード間に印加する直流電源の条件は、次の通りとする。
(i)正電解時
電流値＝０．５〜２０Ａ／ｄｍ２（好ましくは１〜５Ａ／ｄｍ２）
通電時間＝０．１〜１０００ｍｓ（好ましくは１０〜１００ｍｓ）
(ii)逆電解時
電流値＝０．５〜６０Ａ／ｄｍ２（好ましくは１〜１５Ａ／ｄｍ２）
通電時間＝０．０１〜１００ｍｓ（好ましくは０．１〜１００ｍｓ）
(iii)電流比
正電解の電流値：逆電解の電流値＝１：１〜１：３
なお、電流比が１：１、すなわち１を超えるとウィスカーが発生し、電流比が１：３、すなわち１／３≒０．３３３未満になると光沢外観が得られなくなる。
(iv)通電時間比
正電解の通電時間：逆電解の通電時間＝２０：１〜１００：１
なお、通電時間比が２０：１、すなわち２０／１＝２０未満になると光沢外観が得られなくなり、通電時間比が１００：１、すなわち１００／１＝１００を超えるとウィスカーが発生する。
[Condition 1] DC power supply to be applied The conditions of the DC power supply applied between the cathode and the anode are as follows.
(i) Current value during positive electrolysis = 0.5 to 20 A / dm 2 (preferably 1 to 5 A / dm 2 )
Energizing time = 0.1 to 1000 ms (preferably 10 to 100 ms)
(ii) Reverse electrolysis current value = 0.5 to 60 A / dm 2 (preferably 1 to 15 A / dm 2 )
Energizing time = 0.01 to 100 ms (preferably 0.1 to 100 ms)
(iii) Current ratio Current value of positive electrolysis: Current value of reverse electrolysis = 1: 1 to 1: 3
When the current ratio is 1: 1, that is, exceeds 1, whiskers are generated. When the current ratio is 1: 3, that is, less than 1 / 3≈0.333, a glossy appearance cannot be obtained.
(iv) Energizing time ratio Energizing time for positive electrolysis: Energizing time for reverse electrolysis = 20: 1 to 100: 1
When the energization time ratio is 20: 1, that is, less than 20/1 = 20, a glossy appearance cannot be obtained, and when the energization time ratio exceeds 100: 1, that is, 100/1 = 100, whiskers are generated.
〔条件２〕電極間距離
電極間距離（アノードとカソード間の距離）の条件は、次の通りとする。
電極間距離＝３〜３００ｍｍ（好ましくは２０〜１００ｍｍ）
なお、電極間距離が３ｍｍ未満では、現実的に装置の施工が困難である。３００ｍｍを超えるとウィスカーが発生する。
[Condition 2] Distance between electrodes The condition of the distance between electrodes (the distance between the anode and the cathode) is as follows.
Distance between electrodes = 3 to 300 mm (preferably 20 to 100 mm)
In addition, if the distance between electrodes is less than 3 mm, it is actually difficult to construct the apparatus. When it exceeds 300 mm, whiskers are generated.
〔条件３〕被めっき物のＸ軸揺動
被めっき物のＸ軸揺動条件は、次の通りとする。なお、「Ｘ軸揺動」とは、被めっき物（例えば、プリント配線基板）がアノードに向かって近づいたり遠ざかったりする向きの往復運動をいう。
揺動ストローク＝±５〜５０ｍｍ（好ましくは±１０〜３０ｍｍ）
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ（好ましくは１〜５ｃｍ／ｓｅｃ）
[Condition 3] X-axis swing of the object to be plated The X-axis swing conditions of the object to be plated are as follows. The “X-axis swing” refers to a reciprocating motion in a direction in which an object to be plated (for example, a printed wiring board) approaches or moves away from the anode.
Swing stroke = ± 5-50mm (preferably ± 10-30mm)
Swing speed = 0.1-10 cm / sec (preferably 1-5 cm / sec)
〔条件４〕被めっき物のＹ軸揺動
被めっき物のＹ軸揺動条件は、次の通りとする。なお、「Ｙ軸揺動」とは、被めっき物（例えば、プリント配線基板）とアノードとを結ぶ軸線（Ｘ軸）に対して直交する向きの往復運動をいう。
揺動ストローク＝±５〜５０ｍｍ（好ましくは±１０〜３０ｍｍ）
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ（好ましくは１〜５ｃｍ／ｓｅｃ）
[Condition 4] Y-axis swing of the object to be plated The Y-axis swing condition of the object to be plated is as follows. The “Y-axis swing” refers to a reciprocating motion in a direction orthogonal to an axis line (X axis) connecting an object to be plated (for example, a printed wiring board) and an anode.
Swing stroke = ± 5-50mm (preferably ± 10-30mm)
Swing speed = 0.1-10 cm / sec (preferably 1-5 cm / sec)
〔条件５〕被めっき物のＸ−Ｙ軸揺動
被めっき物のＸ−Ｙ軸揺動条件は、次の通りとする。なお、「Ｘ−Ｙ軸揺動」とは、上記Ｘ軸揺動とＹ軸揺動を同時に行なう往復運動をいう。
Ｘ軸揺動：上記Ｘ軸揺動条件に同じ
Ｙ軸揺動：上記Ｙ軸揺動条件に同じ
[Condition 5] X-Y axis swing of the object to be plated The XY axis swing conditions of the object to be plated are as follows. “X-Y axis swing” refers to a reciprocating motion in which the X-axis swing and the Y-axis swing are simultaneously performed.
X axis swing: Same as above X axis swing condition Y axis swing: Same as above Y axis swing condition
なお、被めっき物をめっき浴の入り口から出口に向かって連続搬送しながら銅めっきを行なう場合には、被めっき物の搬送速度は０．０１〜１０ｃｍ／ｓｅｃ、好ましくは１〜５ｃｍ／ｓｅｃとするのがよい。 In addition, when performing copper plating while continuously conveying the object to be plated from the entrance to the outlet of the plating bath, the conveyance speed of the object to be plated is 0.01 to 10 cm / sec, preferably 1 to 5 cm / sec. It is good to do.
本発明によれば、電源電圧反転法を用いた銅めっき処理に際して、印加する直流電源、電極間距離、被めっき物の揺動条件などを最適な値に規定したので、ウィスカーの発生を確実に抑制できるとともに、銅めっき面の光沢外観も良好なウィスカー抑制方法を提供することができる。 According to the present invention, in the copper plating process using the power supply voltage reversal method, the DC power to be applied, the distance between the electrodes, the rocking condition of the object to be plated, etc. are regulated to the optimum values, so that the generation of whiskers is ensured. It is possible to provide a method for suppressing whisker that can be suppressed and also has a good gloss appearance on the copper-plated surface.
［第１の実施の形態］
柱状の無酸素銅を硫酸銅めっき浴１Ｌ当たり２ｄｍ２の負荷で２４時間漬け込んだ。そのめっき液に添加剤を添加し、被めっき物に電気めっき処理を行なった。電気めっき後、被めっき物を取り出し、表面に発生したウィスカーの個数を実態顕微鏡にて数えた。その結果を表１に示す。なお、比較のため、従来方法の結果も示す。
[First Embodiment]
Columnar oxygen-free copper was immersed in a load of 2 dm 2 per liter of copper sulfate plating bath for 24 hours. Additives were added to the plating solution, and electroplating was performed on the object to be plated. After the electroplating, the object to be plated was taken out, and the number of whiskers generated on the surface was counted with an actual microscope. The results are shown in Table 1. For comparison, the result of the conventional method is also shown.
硫酸銅めっき浴の基本組成は、硫酸銅５水和物＝７５ｇ／Ｌ、硫酸＝１８０ｇ／Ｌ、塩素＝６０ｍｇ／Ｌである。また、正電解電流値＝５Ａ／ｄｍ２ 、めっき処理時間＝２０分、浴温＝２５℃、めっき浴の攪拌はエアー攪拌である。添加剤は、ＣＵ−ＢＲＩＴＥ ２１（荏原ユージライト（株）製）を使用した。 The basic composition of the copper sulfate plating bath is copper sulfate pentahydrate = 75 g / L, sulfuric acid = 180 g / L, and chlorine = 60 mg / L. Further, the positive electrolysis current value = 5 A / dm 2 , the plating treatment time = 20 minutes, the bath temperature = 25 ° C., and the stirring of the plating bath is air stirring. As an additive, CU-BRITE 21 (manufactured by Sugawara Eugleite Co., Ltd.) was used.
なお、この第１の実施の形態を始めとして、以下に述べる各実施の形態では、被めっき物として、スルーホールなどが開けられていない銅張積層板（ＣＥＭ−３、銅表面の機械研磨なし）を使用した。 In addition, in each embodiment described below including this first embodiment, a copper-clad laminate (CEM-3, without mechanical polishing of the copper surface) in which a through hole or the like is not opened as an object to be plated )It was used.
（本発明方法１）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝２０：１
電極間距離＝１００ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：０．５Ｌ槽（幅１２０ｍｍ×縦６５ｍｍ×高さ１２０ｍｍ）
被めっき面積：０．５ｄｍ２
(Method 1 of the present invention)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 20: 1
Distance between electrodes = 100mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X-axis oscillation (oscillation stroke = ± 10mm, oscillation speed = 0.05cm / sec)
Plating tank: 0.5L tank (width 120mm x height 65mm x height 120mm)
Plating area: 0.5 dm 2
（従来方法１）
電解方法：直流電解法（電源極性の反転なし）
正電解電流値＝５Ａ／ｄｍ２
電極間距離＝３５０ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度：０．０５ｃｍ／ｓｅｃ）
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional method 1)
Electrolysis method: DC electrolysis method (no reversal of power supply polarity)
Positive electrolysis current value = 5 A / dm 2
Distance between electrodes = 350mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X-axis oscillation (oscillation stroke = ± 10mm, oscillation speed: 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
（従来方法２）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝２０：１
電極間距離＝３５０ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional method 2)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 20: 1
Distance between electrodes = 350mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X-axis oscillation (oscillation stroke = ± 10mm, oscillation speed = 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
［第２の実施の形態］
試験方法は、第１の実施の形態と同様である。添加剤として、ＣＵ−ＢＲＩＴＥ ３１（荏原ユージライト（株）製）を使用した。その結果を表２に示す。なお、比較のため、従来方法の結果も示す。
[Second Embodiment]
The test method is the same as in the first embodiment. As an additive, CU-BRITE 31 (manufactured by Sugawara Eugleite Co., Ltd.) was used. The results are shown in Table 2. For comparison, the result of the conventional method is also shown.
（本発明方法２）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝２０：１
電極間距離＝１００ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Method 2 of the present invention)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 20: 1
Distance between electrodes = 100mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed = 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
（従来方法３）
電解方法：直流電解法（電源極性の反転なし）
正電解電流値＝５Ａ／ｄｍ２
電極間距離＝１００ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度：０．０５ｃｍ／ｓｅｃ）
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional method 3)
Electrolysis method: DC electrolysis method (no reversal of power supply polarity)
Positive electrolysis current value = 5 A / dm 2
Distance between electrodes = 100mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed: 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
（従来例４）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝２０：１
電極間距離＝３５０ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional example 4)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 20: 1
Distance between electrodes = 350mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed = 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
［第３の実施の形態］
試験方法は、第２の実施の形態と同様である。アノードとして板状の不溶解性ＩｒＯ２／Ｔｉを使用した。その結果を表３に示す。なお、比較のため、従来方法の結果も示す。
[Third Embodiment]
The test method is the same as in the second embodiment. Plate-shaped insoluble IrO 2 / Ti was used as the anode. The results are shown in Table 3. For comparison, the result of the conventional method is also shown.
（本発明方法３）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝１０Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：２
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝８０：１
電極間距離＝５０ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Method 3 of the present invention)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 10 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 2
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 80: 1
Distance between electrodes = 50mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed = 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
（従来方法５）
電解方法：直流電解法（電源極性の反転なし）
正電解電流値＝５Ａ／ｄｍ２
電極間距離＝５０ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度：０．０５ｃｍ／ｓｅｃ）
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Conventional method 5)
Electrolysis method: DC electrolysis method (no reversal of power supply polarity)
Positive electrolysis current value = 5 A / dm 2
Distance between electrodes = 50mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed: 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
（従来方法６）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝１０Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：２
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝８０：１
電極間距離＝３５０ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±２０ｍｍ、揺動速度＝０．０５ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Conventional method 6)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 10 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 2
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 80: 1
Distance between electrodes = 350mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 20mm, oscillation speed = 0.05cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
［第４の実施の形態］
試験方法は、第１の実施の形態と同様である。その結果を表４に示す。なお、比較のため、従来方法の結果も示す。
[Fourth Embodiment]
The test method is the same as in the first embodiment. The results are shown in Table 4. For comparison, the result of the conventional method is also shown.
（本発明方法４）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝７．５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１．５
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝４０：１
電極間距離＝３００ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ＋Ｙ軸揺動（Ｘ，Ｙともに、揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Method 4 of the present invention)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 7.5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1.5
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 40: 1
Distance between electrodes = 300mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X + Y axis oscillation (both X and Y, oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
（従来方法７）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝７．５Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１．５
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝４０：１
電極間距離＝３５０ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ＋Ｙ軸揺動（Ｘ，Ｙともに、揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional method 7)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 7.5 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1.5
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 40: 1
Distance between electrodes = 350mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X + Y axis oscillation (both X and Y, oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 0.5 dm 2
（従来方法８）
電解方法：ＯＮ−ＯＦＦ電解法（ON時間(ms)：OFF時間(ms)＝１０：１）
正電解電流値＝５Ａ／ｄｍ２
電極間距離＝１００ｍｍ
アノード：板状含りん銅（０．５ｄｍ２）
揺動：Ｘ＋Ｙ軸揺動（Ｘ，Ｙともに、揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：０．５Ｌ槽（幅１２０ｍｍ×縦６５ｍｍ×高さ１２０ｍｍ）
被めっき面積：０．５ｄｍ２
(Conventional method 8)
Electrolysis method: ON-OFF electrolysis method (ON time (ms): OFF time (ms) = 10: 1)
Positive electrolysis current value = 5 A / dm 2
Distance between electrodes = 100mm
Anode: Plate-shaped phosphorous copper (0.5 dm 2 )
Oscillation: X + Y axis oscillation (both X and Y, oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 0.5L tank (width 120mm x height 65mm x height 120mm)
Plating area: 0.5 dm 2
［第５の実施の形態］
試験方法は、第３の実施の形態と同様である。その結果を表５に示す。なお、比較のため、従来方法の結果も示す。
[Fifth Embodiment]
The test method is the same as in the third embodiment. The results are shown in Table 5. For comparison, the result of the conventional method is also shown.
（本発明方法５）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝６Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１．２
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝４０：１
電極間距離＝３００ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Method 5 of the present invention)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 6 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1.2
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 40: 1
Distance between electrodes = 300mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
（従来方法９）
電解方法：電源電圧反転法
正電解電流値＝５Ａ／ｄｍ２
逆電解電流値＝６Ａ／ｄｍ２
電流比＝正電解の電流値：逆電解の電流値＝１：１．２
通電時間比＝正電解時間（ｍｓ）：逆電解時間（ｍｓ）＝４０：１
電極間距離＝３５０ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Conventional method 9)
Electrolysis method: power supply voltage reversal method Positive electrolysis current value = 5 A / dm 2
Reverse electrolysis current value = 6 A / dm 2
Current ratio = current value of forward electrolysis: current value of reverse electrolysis = 1: 1.2
Energization time ratio = forward electrolysis time (ms): reverse electrolysis time (ms) = 40: 1
Distance between electrodes = 350mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
（従来方法１０）
電解方法：ＯＮ−ＯＦＦ電解法（ＯＮ時間(ms)：ＯＦＦ時間(ms)＝１０：１）
正電解電流値＝５Ａ／ｄｍ２
電極間距離＝１００ｍｍ
アノード：不溶解性ＩｒＯ２／Ｔｉ（６．２５ｄｍ２）
揺動：Ｙ軸揺動（揺動ストローク＝±１０ｍｍ、揺動速度＝２ｃｍ／ｓｅｃ)
めっき槽：８０Ｌ槽（幅５００ｍｍ×縦５００ｍｍ×高さ５００ｍｍ）
被めっき面積：６．２５ｄｍ２
(Conventional method 10)
Electrolysis method: ON-OFF electrolysis method (ON time (ms): OFF time (ms) = 10: 1)
Positive electrolysis current value = 5 A / dm 2
Distance between electrodes = 100mm
Anode: Insoluble IrO 2 / Ti (6.25 dm 2 )
Oscillation: Y-axis oscillation (oscillation stroke = ± 10mm, oscillation speed = 2cm / sec)
Plating tank: 80L tank (width 500mm x length 500mm x height 500mm)
Plating area: 6.25 dm 2
上記各試験結果から明らかなように、本発明方法によるときは、ウィスカーの発生を確実に抑制できることが確認された。同時に、銅めっき表面の光沢も十分で外観も良好なことも確認された。 As is clear from the above test results, it was confirmed that whisker generation can be reliably suppressed when the method of the present invention is used. At the same time, it was also confirmed that the gloss of the copper plating surface was sufficient and the appearance was good.
上記実施の形態では、被めっき物としてプリント配線基板（ＦＰＣ基板を含む）を用いた場合について例示したが、本発明方法を適用可能な被めっき物はプリント配線基板に限られるものではない。例えば、銅,ニッケル,クロムなどを含む金属を液相または気相めっきにて被覆したポリイミドなどの樹脂フィルムに銅めっきを施す場合などにも適用できるものである。 In the said embodiment, although illustrated about the case where a printed wiring board (a FPC board is included) was used as a to-be-plated object, the to-be-plated object which can apply the method of this invention is not restricted to a printed wiring board. For example, the present invention can be applied to a case where copper plating is applied to a resin film such as polyimide coated with a metal containing copper, nickel, chromium or the like by liquid phase or vapor phase plating.
Claims (3)
〔条件１〕印加する直流電源
(i)正電解時
電流値＝０．５〜２０Ａ／ｄｍ２
通電時間＝０．１〜１０００ｍｓ
(ii)逆電解時
電流値＝０．５〜６０Ａ／ｄｍ２
通電時間＝０．０１〜１００ｍｓ
(iii)電流比
正電解の電流値：逆電解の電流値＝１：１〜１：３
(iv)通電時間比
正電解の通電時間：逆電解の通電時間＝２０：１〜１００：１
〔条件２〕電極間距離＝３〜３００ｍｍ
〔条件３〕被めっき物のＸ軸揺動
揺動ストローク＝±５〜５０ｍｍ
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ The polarity of the DC power supply voltage applied between the cathode and anode can be reversed, and copper plating is performed while alternately switching between normal positive electrolysis using the object to be plated as the cathode and reverse electrolysis using the object as the anode as the anode. In the plating method to be performed, the following [Condition 1] + [Condition 2] + [Condition 3] are adopted as electrolytic conditions for copper plating.
[Condition 1] DC power supply to be applied
(i) Current value during positive electrolysis = 0.5 to 20 A / dm2
Energizing time = 0.1 to 1000 ms
(ii) Current value during reverse electrolysis = 0.5 to 60 A / dm 2
Energizing time = 0.01-100ms
(iii) Current ratio Current value of positive electrolysis: Current value of reverse electrolysis = 1: 1 to 1: 3
(iv) Energizing time ratio Energizing time for positive electrolysis: Energizing time for reverse electrolysis = 20: 1 to 100: 1
[Condition 2] Distance between electrodes = 3 to 300 mm
[Condition 3] X-axis oscillation of the object to be plated Oscillation stroke = ± 5 to 50 mm
Oscillation speed = 0.1-10cm / sec
〔条件１〕印加する直流電源
(i)正電解時
電流値＝０．５〜２０Ａ／ｄｍ２
通電時間＝０．１〜１０００ｍｓ
(ii)逆電解時
電流値＝０．５〜６０Ａ／ｄｍ２
通電時間＝０．０１〜１００ｍｓ
(iii)電流比
正電解の電流値：逆電解の電流値＝１：１〜１：３
(iv)通電時間比
正電解の通電時間：逆電解の通電時間＝２０：１〜１００：１
〔条件２〕電極間距離＝３〜３００ｍｍ
〔条件４〕被めっき物のＹ軸揺動
揺動ストローク＝±５〜５０ｍｍ
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ The polarity of the DC power supply voltage applied between the cathode and anode can be reversed, and copper plating is performed while alternately switching between normal positive electrolysis using the object to be plated as the cathode and reverse electrolysis using the object as the anode as the anode. In the plating method to be performed, the following [Condition 1] + [Condition 2] + [Condition 4] are employed as electrolytic conditions for copper plating, and the method for suppressing whiskers in copper plating is characterized in that:
[Condition 1] DC power supply to be applied
(i) Current value during positive electrolysis = 0.5 to 20 A / dm2
Energizing time = 0.1 to 1000 ms
(ii) Current value during reverse electrolysis = 0.5 to 60 A / dm 2
Energizing time = 0.01-100ms
(iii) Current ratio Current value of positive electrolysis: Current value of reverse electrolysis = 1: 1 to 1: 3
(iv) Energizing time ratio Energizing time for positive electrolysis: Energizing time for reverse electrolysis = 20: 1 to 100: 1
[Condition 2] Distance between electrodes = 3 to 300 mm
[Condition 4] Y-axis swing of the object to be plated Swing stroke = ± 5-50mm
Oscillation speed = 0.1-10cm / sec
〔条件１〕印加する直流電源
(i)正電解時
電流値＝０．５〜２０Ａ／ｄｍ２
通電時間＝０．１〜１０００ｍｓ
(ii)逆電解時
電流値＝０．５〜６０Ａ／ｄｍ２
通電時間＝０．０１〜１００ｍｓ
(iii)電流比
正電解の電流値：逆電解の電流値＝１：１〜１：３
(iv)通電時間比
正電解の通電時間：逆電解の通電時間＝２０：１〜１００：１
〔条件２〕電極間距離＝３〜３００ｍｍ
〔条件５〕被めっき物のＸ−Ｙ軸揺動
Ｘ軸揺動：揺動ストローク＝±５〜５０ｍｍ
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ
Ｙ軸揺動：揺動ストローク＝±５〜５０ｍｍ
揺動速度＝０．１〜１０ｃｍ／ｓｅｃ The polarity of the DC power supply voltage applied between the cathode and anode can be reversed, and copper plating is performed while alternately switching between normal positive electrolysis using the object to be plated as the cathode and reverse electrolysis using the object as the anode as the anode. In the plating method to be performed, the following [Condition 1] + [Condition 2] + [Condition 5] are adopted as electrolytic conditions for copper plating.
[Condition 1] DC power supply to be applied
(i) Current value during positive electrolysis = 0.5 to 20 A / dm2
Energizing time = 0.1 to 1000 ms
(ii) Current value during reverse electrolysis = 0.5 to 60 A / dm 2
Energizing time = 0.01-100ms
(iii) Current ratio Current value of positive electrolysis: Current value of reverse electrolysis = 1: 1 to 1: 3
(iv) Energizing time ratio Energizing time for positive electrolysis: Energizing time for reverse electrolysis = 20: 1 to 100: 1
[Condition 2] Distance between electrodes = 3 to 300 mm
[Condition 5] X-Y axis swing of the object to be plated X-axis swing: Swing stroke = ± 5-50mm
Oscillation speed = 0.1-10cm / sec
Y-axis swing: Swing stroke = ± 5-50mm
Oscillation speed = 0.1-10cm / sec
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