JPH03104895A - Electroplating method - Google Patents
Electroplating methodInfo
- Publication number
- JPH03104895A JPH03104895A JP24150589A JP24150589A JPH03104895A JP H03104895 A JPH03104895 A JP H03104895A JP 24150589 A JP24150589 A JP 24150589A JP 24150589 A JP24150589 A JP 24150589A JP H03104895 A JPH03104895 A JP H03104895A
- Authority
- JP
- Japan
- Prior art keywords
- electric field
- thin film
- plating
- film
- electroplating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000009713 electroplating Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 39
- 230000005684 electric field Effects 0.000 claims abstract description 28
- 239000010409 thin film Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 21
- 239000010408 film Substances 0.000 abstract description 42
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、アルミニウムのような金属の薄膜上に、密着
性に優れためっき膜を形成するための電気めっき方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an electroplating method for forming a plating film with excellent adhesion on a thin film of metal such as aluminum.
（従来の技術）
アルミニウムは、イオン化傾向が卑であるため、通常の
大気中でも表面に容易に酸化膜が形成される。(Prior Art) Since aluminum has a low ionization tendency, an oxide film is easily formed on the surface even in normal atmosphere.
そのため、アルミニウム上に金属を電気めっきする場合
には、めっき工程に入る前に酸化膜を除去し表面を活性
にする必要がある。そして、このような表面の活性化方
法としては、従来から、めっき膜を形成しようとするア
ルミニウムの薄膜に、第４図に示すように、電気めっき
の際と逆方向の電界を一定時間連続的に印加し、表面の
酸化膜を電解エッチングする方法が採られていた。Therefore, when electroplating metal on aluminum, it is necessary to remove the oxide film and activate the surface before starting the plating process. Conventionally, as a method for activating such a surface, an electric field in the opposite direction to that during electroplating is continuously applied to the aluminum thin film on which the plating film is to be formed for a certain period of time, as shown in Figure 4. A method was adopted in which the oxide film on the surface was electrolytically etched.
（発明が解決しようとする課題）
しかしながら、上述したような従来の活性化方法におい
ては、粘着テープを用いた剥離試験に充分に耐えること
ができるような、密着性に優れためっき膜が得られるこ
ともあるが、極めて再現性に乏しく、印加される電流の
波形と印加時間、めっき液の温度と攪拌の度合、電極の
形状と電極間距離などの条件を同じくして活性化および
電気めっきを行っても、時として活性化が不充分で着膜
されなかったり、あるいはエッチング過剰で下地層が露
出してしまうことがあり、結果のばらつきが大きいとい
う問題があった。(Problem to be Solved by the Invention) However, in the conventional activation method as described above, a plating film with excellent adhesion that can sufficiently withstand a peel test using an adhesive tape cannot be obtained. However, the reproducibility is extremely poor, and activation and electroplating cannot be performed under the same conditions such as the applied current waveform and application time, the temperature of the plating solution and the degree of stirring, the shape of the electrodes and the distance between the electrodes. Even when etching is performed, the activation is sometimes insufficient and no film is deposited, or the underlying layer is exposed due to excessive etching, resulting in large variations in the results.
このようにめっき膜の密着性等に再現性が見られない原
因としては、めっき膜を析出させようとするアルミニウ
ム薄膜の表面酸化状態にばらつきが存在することが考え
られる。The reason for the lack of reproducibility in the adhesion of the plating film is thought to be that there are variations in the surface oxidation state of the aluminum thin film on which the plating film is to be deposited.
したがって、密着性に優れためつき膜を再現性良く形成
するには、それぞれのアルミニウム薄膜に固有の酸化状
態を知り、それに適合した活性化を実施する必要がある
が、このような方法は未だ開発されていないのが現状で
ある。Therefore, in order to form a prickly film with excellent adhesion and good reproducibility, it is necessary to know the unique oxidation state of each aluminum thin film and perform activation appropriate to that state, but such a method has not yet been developed. The current situation is that this has not been done.
本発明は、これらの問題を解決するためになされたもの
で、金属薄膜上に密着性に優れためっき膜を再現性良く
形成することができる電気めっき方法を提供することを
目的とする。The present invention was made to solve these problems, and an object of the present invention is to provide an electroplating method that can form a plating film with excellent adhesion on a metal thin film with good reproducibility.
［発明の構或］
（課題を解決するための手段）
本発明の電気めっき方法は、金属薄膜上に金属を電気め
っきする方法において、非水溶液系または水溶液系のめ
っき浴中に前記金属薄膜を浸漬し、その表面上にアノー
ド用金属に対して生じた正電圧を消滅させるまで、電圧
を測定しつつ逆方向の電界をパルス的に印加する活性化
工程と、前記活性化工程が終了した後直ちに前記めっき
浴中で開始する電気めっき工程とを有することを特徴と
している。[Structure of the Invention] (Means for Solving the Problem) The electroplating method of the present invention is a method for electroplating a metal on a metal thin film, in which the metal thin film is placed in a non-aqueous or aqueous plating bath. An activation step in which an electric field in the opposite direction is applied in a pulsed manner while measuring the voltage until the positive voltage generated on the surface of the anode metal is extinguished; and after the activation step is completed. The electroplating process immediately starts in the plating bath.
本発明における活性化工程の詳細を以下に説明する。The details of the activation step in the present invention will be explained below.
すなわち、その上にめっき膜を析出形成させようとする
アルミニウム等の金属薄膜を、有機溶媒系のような非水
溶液系または水溶液系のめっき液（めっき浴）中に浸漬
すると、電界を印加せずとも金属薄膜上に、アルミニウ
ム等のアノード用金屈に対して常に正電圧が生じる。そ
してこの正電圧は、金属薄膜表面の酸化状態に対応して
異なった値を示すため、薄膜表面に形或された酸化膜の
存在に起因するものと考えられる。In other words, when a thin metal film such as aluminum on which a plating film is to be deposited is immersed in a non-aqueous or aqueous plating solution (plating bath) such as an organic solvent, no electric field is applied. In both cases, a positive voltage is always generated on the metal thin film with respect to the anode metal such as aluminum. Since this positive voltage shows different values depending on the oxidation state of the surface of the metal thin film, it is considered to be due to the presence of an oxide film formed on the surface of the thin film.
一般に、表面酸化膜は逆電界（めっきの際と逆方向の電
界）を印加することによってエッチングされていくが、
それに伴って上記正電圧値も減衰していくことが予想さ
れる。Generally, a surface oxide film is etched by applying a reverse electric field (an electric field in the opposite direction to that during plating).
It is expected that the positive voltage value will also attenuate accordingly.
そのため、本発明においては、例えば第１図（ａ）、（
ｂ）にそれぞれ示すような電流および電圧波形を設定し
、この波形に対応する逆電界をパルス的に印加した（Ｏ
Ｎ−Ｔ ＩＭＥ）後、無電界状態に戻す（ＯＦＦ−ＴＩ
ＭＥ）というサイクルを繰返すとともに、ＯＦＦ−ＴＩ
ＭＥ時に前記正電圧値を測定する。Therefore, in the present invention, for example, FIG.
The current and voltage waveforms shown in b) were set, and a reverse electric field corresponding to these waveforms was applied in a pulsed manner (O
N-T IME), then return to no electric field state (OFF-TI
ME) and repeat the cycle OFF-TI.
The positive voltage value is measured during ME.
そして、この正電圧の値が０になったとき、表面の酸化
膜が完全に除去され活性化が完了したものと判断する。When the value of this positive voltage becomes 0, it is determined that the oxide film on the surface has been completely removed and activation has been completed.
なお、このようなパルス電流波形としては、ＯＮ−ＴＩ
ＭＥが０．５ 〜２０ｍ ｓｅｃでＯ Ｆ Ｆ − Ｔ
Ｉ ＭＥが５０〜１０００ｍ ｓｅｃであり、かつＯ
Ｎ−Ｔｌ〜・ＩＥ時の電流密度が２〜２ＯＡ ／ ｄ
ｒｒｒである波形を使用することが望ましい。In addition, as such a pulse current waveform, ON-TI
OFF-T when ME is 0.5 to 20 msec
IME is 50 to 1000 msec, and O
N-Tl~・current density during IE is 2~2OA/d
It is desirable to use a waveform that is rrr.
すなわち、ＯＮ−Ｔ ＩＭＥが０．５ｍｓｅｃより短い
と、電解エッチング作用が不充分で酸化膜が完全には除
去されず、反対にこれが２０ｍ ｓｅｃより長い場合に
は、エッチング過剰が生じ好ましくない。That is, if the ON-T IME is shorter than 0.5 msec, the electrolytic etching effect is insufficient and the oxide film is not completely removed, whereas if it is longer than 20 msec, excessive etching occurs, which is not preferable.
また、ＯＦＦ−Ｔ ＩＭＥが５０ｍ ｓｅｃより短いと
、このときに正電圧をａＦＪ定することが難しく、反対
にＯＦＦ−ＴＩＭＥをｉｏ００ｍ ｓｅｃ以上としても
、特にメリットがないばかりでなく、かえって活性化に
要する時間が長くなってしまうため好ましくない。Furthermore, if the OFF-TIME is shorter than 50 m sec, it is difficult to determine the positive voltage aFJ at this time, and conversely, even if the OFF-TIME is set to io00 m sec or more, not only is there no particular advantage, but it may actually lead to less activation. This is not preferable because it takes a long time.
さらに、ＯＮ−ＴＩＭＥ時の電流密度が２Ａ／ｄｉｒｒ
未満の場合には、電解エッチング効果が充分に得られず
、反対に２０Ａ ／ ｄ ｒ＃を越えた場合には、エッ
チング過剰になるおそれがあり好ましくない。Furthermore, the current density during ON-TIME is 2A/dirr.
If it is less than 20 A/d r#, sufficient electrolytic etching effect cannot be obtained, and if it exceeds 20 A/d r#, excessive etching may occur, which is not preferable.
こうして活性化が終了した後、直ちに同じめっき浴中で
電気めっきを開始する。Immediately after activation is completed, electroplating is started in the same plating bath.
めっき条件としては、室温（２０〜２５℃）でめっきを
行う場合には電流密度を０．３〜１．５Ａ ／ ｄ ｒ
ｆの範囲にするものとし、かつ直流あるいはパルスによ
って電界めっきを行う。The plating conditions include a current density of 0.3 to 1.5 A/dr when plating is performed at room temperature (20 to 25°C).
f range, and electroplating is performed using direct current or pulses.
このようにして金属薄膜表面の活性化および電気めっき
を行うことによって、密着性に優れためっき膜が極めて
再現性良く得られる。By activating the surface of the metal thin film and electroplating in this manner, a plated film with excellent adhesion can be obtained with extremely good reproducibility.
（作 用）
本発明の電気めっき方法においては、有機溶媒系または
水溶液系のめっき浴中に浸漬された金属薄膜に、逆方向
の電界がパルス的に印加されることによって表面の活性
化が行われるが、このような逆電界印加のサイクルが繰
返されるにしたがって、ＯＦＦ−ＴＩＭＥ時の金属薄膜
表面の正電圧値は減衰していく。(Function) In the electroplating method of the present invention, the surface is activated by applying a pulsed electric field in the opposite direction to the metal thin film immersed in an organic solvent-based or aqueous plating bath. However, as this cycle of applying a reverse electric field is repeated, the positive voltage value on the surface of the metal thin film during OFF-TIME attenuates.
金属薄膜表面の酸化膜は、同じ金属のめつき洛中におい
て電気的二重層となるものであるから、これに起因して
発生する正電圧値が逆電界の印加によって減衰していく
ことは、酸化膜のエッチングされていくことに対応する
。The oxide film on the surface of a metal thin film forms an electrical double layer when the same metal is plated, so the fact that the positive voltage value generated due to this attenuates due to the application of a reverse electric field is due to oxidation. This corresponds to the fact that the film is being etched.
したがって、この正電圧の値が０になった時点をもって
、表面の酸化膜が完全に除去され活性化が完了したもの
と判断し、直ちにめっき工程を開始することによって、
金属薄膜上に密着性に優れためっき膜が形成され、また
その再現性も極めて良好となる。Therefore, when the value of this positive voltage becomes 0, it is determined that the oxide film on the surface has been completely removed and activation has been completed, and by immediately starting the plating process,
A plating film with excellent adhesion is formed on the metal thin film, and its reproducibility is also extremely good.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
実施例１
アルミナ／ Ｔａ−９１０２膜／アルミニウム膜（厚さ
８μａ＋）からなる面積５８ｃ−のサーマルプリントヘ
ッド（Ｔ Ｐ Ｈ）用基板を、予め窒素雰囲気に保持さ
れた塩化アルミニウムとブチルビリジニウムクロリドと
からなる溶融塩めっき浴に浸漬し、以下．に示すような
逆パルス電界を印加することによって、アルミニウム膜
表面を活性化した。Example 1 A substrate for a thermal print head (TPH) with an area of 58 cm and made of alumina/Ta-9102 film/aluminum film (thickness 8 μa+) was heated with aluminum chloride and butylpyridinium chloride kept in a nitrogen atmosphere in advance. Immerse it in a molten salt plating bath consisting of: The surface of the aluminum film was activated by applying a reverse pulsed electric field as shown in FIG.
すなわち電流波形に関しては、ＯＮ−ＴＩＭＥの電流密
度をＩＯＡ／ｄｒｒｒ，電圧波形に関してはＯＮ−Ｔ
ＩＭＥ（７）電圧を２０ｖ１かっＯＦＦ−ＴＩＭＥを
１００ｍ ｓｅｃとするとともに、ＯＮ−ＴＩＭＥをｌ
ｍｓｅｃ ， ２ｍｓｅｃ ， ４ｍｓｅｃとそれ
ぞれ変えた逆パルス電界をそれぞれ印加し、アノード用
アルミニウム板（ ９９．９９重量％）に対するアルミ
ニウム膜表面の正電圧の値を測定した。In other words, for the current waveform, the ON-TIME current density is IOA/drrr, and for the voltage waveform, ON-T
IME (7) voltage 20v1 OFF-TIME
100m sec and ON-TIME l
A reverse pulse electric field of 3 msec, 2 msec, and 4 msec was applied, and the value of the positive voltage on the surface of the aluminum film with respect to the anode aluminum plate (99.99% by weight) was measured.
そして、この正電圧値が０になるまでの時間を、いろい
ろな初期値を有するアルミニウム膜に対してそれぞれ／
Ｉｐ１定した
この測定結果を第２図のグラフに示す。The time it takes for this positive voltage value to reach 0 is then calculated as / for aluminum films with various initial values.
The results of this measurement, in which Ip1 was determined, are shown in the graph of FIG.
次いで、基板のアルミニウム膜表面の正電圧値が０にな
った時点で、逆パルス電界の印加を停止し、直ちに基板
を陰極とし上記アノード用アルミニウム板を陽極とし、
電流密度がＬＡ／ｄｒｒｒになるように直流電圧を印加
することによって電気めっきを行った。Next, when the positive voltage value on the surface of the aluminum film of the substrate becomes 0, the application of the reverse pulse electric field is stopped, and the substrate is immediately used as a cathode, and the aluminum plate for anode is used as an anode,
Electroplating was performed by applying a DC voltage so that the current density was LA/drrr.
こうして厚さ ｌ−１０μｍの密着性の良いアルミニウ
ム膜が形成された。In this way, a highly adhesive aluminum film with a thickness of 1-10 μm was formed.
また比較のために、アルミニウム膜表面の正電圧値（Ｖ
）が０になる前に活性化を終了し、直ちに同様な条件で
めっきを行った。For comparison, the positive voltage value (V
Activation was completed before ) reached 0, and plating was immediately performed under the same conditions.
その結果、■≧０．１０の場合にはめっき膜が着膜せず
、０．ｌＯ≧Ｖ≧０．Ｏｌの場合には、着膜するが、粘
着テープによる剥離試験に耐えられるような密着性の良
いめっき膜は得られなかった。As a result, when ■≧0.10, no plating film was deposited, and when 0.10. lO≧V≧0. In the case of Ol, a film was formed, but a plating film with good adhesion that could withstand a peel test using an adhesive tape could not be obtained.
実施例２
ＴＰＨ用の共通電極用導電膜を形成する部分を除き、実
施例１で使用したＴＰＨ用基板上に厚さ数ｌＯμ鑓のレ
ジストコートを施したものを基板として使用し、その上
に実施例１と同様にしてアルミニウムめっきを行った。Example 2 The TPH substrate used in Example 1 was coated with a resist coating several 10 μm in thickness, except for the part where the conductive film for the common electrode for TPH was formed, and then Aluminum plating was performed in the same manner as in Example 1.
その結果、実施例１と同様に密着性に優れたアルミニウ
ム膜が極めて再現性良く得られた。As a result, as in Example 1, an aluminum film with excellent adhesion was obtained with extremely good reproducibility.
実施例３
アルミナ／ Ｔａ−Ｓｉ０２ ｐＡ／クロムおよび銅薄
膜（厚さ合計０．５μ偏）からなるＴＰＨ用基板を、予
め脱脂洗浄処理を行うことなく酸性銅めっき液（ｒＡ酸
銅１００ｇ ／ １２ トＩＡ酸１００ｇ ／ ｉ、残
部水。）中に浸漬し、両極性のパルス電流を允生じ得る
電源を用い、実施例１と同様にして銅７８膜表面の活性
化を行った。Example 3 A TPH substrate consisting of alumina/Ta-Si02pA/chromium and copper thin film (total thickness 0.5μ) was coated with an acidic copper plating solution (rA acid copper 100g/12t) without prior degreasing and cleaning treatment. The surface of the Copper 78 film was activated in the same manner as in Example 1 using a power source capable of generating bipolar pulse currents.
すなわちＯＮ−ＴＩＭＥをｌｍｓｅｃＳＯＦＦ 一ＴＩ
ＭＥを１００ｍ ｓｅｃとし、ＩＯＡ ／ ｄ ｒｒｒ
の電流密度で逆パルス電界を繰返して印加した。In other words, ON-TIME and lmsec SOFF - TI
ME is 100m sec, IOA/d rrr
A reverse pulsed electric field was repeatedly applied at a current density of .
そしてこのとき、基板の銅薄膜表面の正電位を電源メー
タを用いて監視し、正電圧が発生しなくなった特点から
約１０ｓｃｃ後に活性化を終了し、次いで５Ａ ／ ｄ
ｒｒｌ’の電流密度となるように直流を印加し、銅の
電気めっきを行った。At this time, the positive potential of the copper thin film surface of the substrate was monitored using a power meter, and activation was completed approximately 10 sc after the point where no positive voltage was generated, and then 5 A/d.
Direct current was applied so that the current density was rrl', and copper electroplating was performed.
こうして厚さ ５μ国の密着性の良い銅めっき膜が形威
された。In this way, a copper plating film with a thickness of 5 μm and excellent adhesion was created.
また同様にして活性化が終了した基板に対し、第３図に
示すように、活性化の際に印加した波形を残したパルス
電界を印加してめっきを行ったところ、下地の銅薄膜の
損傷がより少なくつき回りの良いめっき膜が形成された
。In addition, when plating was performed on a substrate that had been activated in the same way by applying a pulsed electric field that retained the waveform applied during activation, as shown in Figure 3, the underlying copper thin film was damaged. A plating film with good coverage was formed.
［発明の効果］
以上説明したように本発明の方法によれば、アルミニウ
ム薄膜のような金属薄膜の表面を効率的に活性化し、そ
の上に密着性に優れためっき膜を確実にかつ再現性良く
形成することができる。[Effects of the Invention] As explained above, according to the method of the present invention, the surface of a metal thin film such as an aluminum thin film can be efficiently activated, and a plating film with excellent adhesion can be formed thereon reliably and reproducibly. Can be formed well.
第１図（ａ）、（ｂ）は本発明の方法の活性化工程にお
いて印加される逆パルス電界の電流波形および電圧波形
の一例をそれぞれ示す図、第２図は本発明の実施例で測
定したアルミニウム膜表面の正電圧の初期値とこの値が
０になるまでの時間との関係を示したグラフ、第３図は
他の実施例のめっき工程で使用したパルス電界の電流波
形を示す図、第４図は従来の電気めっき方法において印
加される電流波形を示す図である。Figures 1 (a) and (b) are diagrams showing an example of the current and voltage waveforms of the reverse pulsed electric field applied in the activation step of the method of the present invention, respectively, and Figure 2 is a diagram showing examples of the current and voltage waveforms of the reverse pulsed electric field applied in the activation step of the method of the present invention, and Figure 2 is a diagram showing examples of the waveforms of the reverse pulsed electric field applied in the activation step of the method of the present invention. Figure 3 is a graph showing the relationship between the initial value of the positive voltage on the surface of the aluminum film and the time until this value becomes 0. Figure 3 is a diagram showing the current waveform of the pulsed electric field used in the plating process of another example. , FIG. 4 is a diagram showing a current waveform applied in a conventional electroplating method.
Claims (2)
、 非水溶液系または水溶液系のめっき浴中に前記金属薄膜
を浸漬し、その表面上にアノード用金属に対して生じた
正電圧を消滅させるまで、電圧を測定しつつ逆方向の電
界をパルス的に印加する活性化工程と、 前記活性化工程が終了した後直ちに前記めっき浴中で開
始する電気めっき工程と を有することを特徴とする電気めっき方法。(1) In a method of electroplating a metal on a metal thin film, the metal thin film is immersed in a non-aqueous or aqueous plating bath, and the positive voltage generated on its surface with respect to the anode metal is extinguished. an activation step of applying an electric field in the opposite direction in a pulsed manner while measuring a voltage up to the point where the plating step is completed, and an electroplating step that starts in the plating bath immediately after the activation step is completed. Plating method.
性化工程において印加される電界パルスの波形が、電界
印加時間が０．５〜２０ｍｓｅｃ、無電界時間が５０〜
１０００ｍｓｅｃ、かつ電界印加時の電流密度が２〜２
０Ａ／ｄｍ＾２であることを特徴とする電気めっき方法
。(2) In the electroplating method according to claim 1, the waveform of the electric field pulse applied in the activation step is such that the electric field application time is 0.5 to 20 msec and the no electric field time is 50 to 20 msec.
1000 msec and current density when applying electric field is 2 to 2
An electroplating method characterized by 0A/dm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1241505A JP2723305B2 (en) | 1989-09-18 | 1989-09-18 | Electroplating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1241505A JP2723305B2 (en) | 1989-09-18 | 1989-09-18 | Electroplating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03104895A true JPH03104895A (en) | 1991-05-01 |
| JP2723305B2 JP2723305B2 (en) | 1998-03-09 |
Family
ID=17075328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1241505A Expired - Lifetime JP2723305B2 (en) | 1989-09-18 | 1989-09-18 | Electroplating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2723305B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209279A1 (en) * | 2016-06-03 | 2017-12-07 | 古河電気工業株式会社 | Surface treatment material, production method thereof, and component formed using surface treatment material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54109037A (en) * | 1978-01-27 | 1979-08-27 | Seiko Epson Corp | Noble metal plating method |
| JPS62297492A (en) * | 1986-06-16 | 1987-12-24 | Nagano Pref Gov | Method for plating aluminum by electrolytic activation |
-
1989
- 1989-09-18 JP JP1241505A patent/JP2723305B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54109037A (en) * | 1978-01-27 | 1979-08-27 | Seiko Epson Corp | Noble metal plating method |
| JPS62297492A (en) * | 1986-06-16 | 1987-12-24 | Nagano Pref Gov | Method for plating aluminum by electrolytic activation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209279A1 (en) * | 2016-06-03 | 2017-12-07 | 古河電気工業株式会社 | Surface treatment material, production method thereof, and component formed using surface treatment material |
| JP6279170B1 (en) * | 2016-06-03 | 2018-02-14 | 古河電気工業株式会社 | Surface treatment material, method for producing the same, and component formed using the surface treatment material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2723305B2 (en) | 1998-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3234110A (en) | Electrode and method of making same | |
| ATE54186T1 (en) | SELECTIVE ELECTROLYTIC STRIPPING OF METALLIC COATINGS FROM METALLIC BASE SUBSTRATES. | |
| JPH03104895A (en) | Electroplating method | |
| JP3506826B2 (en) | Aluminum material and manufacturing method thereof | |
| JPS59185799A (en) | Electrolytic coloring process for anode oxide coating | |
| JP2000355795A (en) | Surface treatment of aluminum and aluminum alloy | |
| JPS6257718B2 (en) | ||
| JPH01156496A (en) | Formation of corrosion-resistant coating film on stainless steel member | |
| EP0065421A1 (en) | Method of treating a surface of an aluminum to form a pattern thereon | |
| JPS61276996A (en) | Surface treatment of titanium or alloy thereof | |
| JP2008153556A (en) | Manufacturing method of heatsink substrate for electric circuit | |
| JPS6221079B2 (en) | ||
| JP3655932B2 (en) | Method for producing colored titanium material with excellent adhesion of oxide film | |
| JP2729835B2 (en) | Method for forming ceramic film on aluminum substrate surface | |
| JPS6326375A (en) | Method for starting electroless plating | |
| JP2763136B2 (en) | Method for forming etching nuclei on aluminum foil for electrolytic capacitor electrode | |
| JP2654991B2 (en) | Multicolor surface treatment method for aluminum material | |
| JPS6345398A (en) | Method for electrolytically coloring aluminum or aluminum alloy | |
| RU2109854C1 (en) | Method for treatment of articles surface made of aluminum or its alloys prior to application of coating of functional purpose | |
| JP3112381B2 (en) | Surface treatment method of mother plate for producing seed plate during copper electrorefining | |
| JP2000309882A (en) | Surface treating method for magnesium material | |
| JPH041079B2 (en) | ||
| JPS63271118A (en) | Encoder for which coherence luminous flux is utilized | |
| JPH01306594A (en) | Method for coating ferrite sintered body by electrodeposition | |
| JPH01205092A (en) | Electrolytic coloring method for aluminum or aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071128 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081128 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091128 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term |