JPH0456779A - Method for measuring passivation of electroless copper plating - Google Patents
Method for measuring passivation of electroless copper platingInfo
- Publication number
- JPH0456779A JPH0456779A JP16727190A JP16727190A JPH0456779A JP H0456779 A JPH0456779 A JP H0456779A JP 16727190 A JP16727190 A JP 16727190A JP 16727190 A JP16727190 A JP 16727190A JP H0456779 A JPH0456779 A JP H0456779A
- Authority
- JP
- Japan
- Prior art keywords
- potential
- plating
- copper
- electrode
- passivation
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 239000010949 copper Substances 0.000 title claims abstract description 48
- 238000002161 passivation Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- VWEWCZSUWOEEFM-WDSKDSINSA-N Ala-Gly-Ala-Gly Chemical compound C[C@H](N)C(=O)NCC(=O)N[C@@H](C)C(=O)NCC(O)=O VWEWCZSUWOEEFM-WDSKDSINSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は無電解銅めっきに関する。[Detailed description of the invention] [Industrial application field] The present invention relates to electroless copper plating.
従来、無電解銅めっきにおいて被めっき物が不動態化す
るのを検出する方式として、めっき液中に置かれた銅電
極の電位を測定する方式がある。Conventionally, as a method for detecting passivation of a plated object in electroless copper plating, there is a method of measuring the potential of a copper electrode placed in a plating solution.
この方式は銅電極への電位印加や電圧印加は行われず、
めっき液中の自然電位を測定するため、通常は一７００
ｍＶｖｓ、Ａ１Ａｇ’ｃｊ！ｊｉｉＪ後のめっき電位を
示す、不動態化が発生した場合は一３００ｍＶｖｓ、Ａ
ｇＡｇｃ１前後の不動態化電位を示す、従って、従来の
方式は原理上めっき電位から不動態化電位に変化するタ
イプの不動態化を検出するためのものである。従って、
すでにめっき液中にあってめっき電位になっている被め
っき物に対しては有効性がある。This method does not apply potential or voltage to the copper electrode,
To measure the natural potential in the plating solution, it is usually -700
mVvs, A1Ag'cj! plating potential after jiiJ, -300 mV vs. A if passivation occurs.
It shows the passivation potential around gAgc1, so the conventional method is for detecting the type of passivation that changes from plating potential to passivation potential in principle. Therefore,
It is effective for objects to be plated that are already in the plating solution and at the plating potential.
しかし、被めっき物がめつき液に入れられた直後は表面
の酸化皮膜のためにめっき電位よりもプラス側の電位に
なっている。この被めっき物の電位がマイナス側に変化
して、めっき電位となりめっきが析出するか、それとも
不動態化電位となりめっきが停止してしまうかが問題で
あり、従来の方法では測定することができなかった。However, immediately after the object to be plated is placed in the plating solution, the potential is more positive than the plating potential due to the oxide film on the surface. The problem is whether the potential of the object to be plated changes to the negative side and becomes a plating potential, causing plating to deposit, or whether it becomes a passivation potential and stops plating, which cannot be measured using conventional methods. There wasn't.
その原因は、銅電極が連続してめっき液中にあり、めっ
き電位で還元状態にあるのに対して、めっき液に入れら
れる被めっき物が銅の酸化状態になっているという違い
にある。この両者の条件の差のために、従来の不動態化
の測１方法ではめっき電位であると測定されているのに
被めっき物では不動態化が発生するという不具合が時々
発生した。The reason for this is that the copper electrode is continuously in the plating solution and is in a reduced state at the plating potential, whereas the object to be plated, which is placed in the plating solution, is in an oxidized copper state. Due to this difference in the conditions between the two, a problem sometimes occurred in which the conventional passivation measurement method measured the plating potential but resulted in passivation of the object to be plated.
本発明においては、従来の方法に加えて、ｗ４′ｒ！Ｌ
極の電位を予め不動態化電位に設定し、被めっき物がめ
つき液に入った時の状態に近づける方法を用いた。その
ため、銅電極、対極、および参照電極から成る測定部、
銅電極に不動態化電位を印加するための装置であるポテ
ンシオスタフト、および銅電極の電位を測定する電位計
から成る測定装置を作成した。この装置によって一度不
動態化電位とした銅電極の電位をめっき液中で測定した
。In the present invention, in addition to the conventional method, w4'r! L
A method was used in which the potential of the electrode was set in advance to a passivation potential to approximate the state when the object to be plated entered the plating solution. Therefore, the measurement part consists of a copper electrode, a counter electrode, and a reference electrode,
We created a measuring device consisting of a potentiostaft, which is a device for applying a passivation potential to a copper electrode, and an electrometer to measure the potential of the copper electrode. Using this device, the potential of the copper electrode, which was once set to passivation potential, was measured in the plating solution.
本方式の装置の測定部を無電解銅めっき液′に入れる０
次いでポテンシオスタフトを用いて銅電極の電位を銅の
不動態化電位になるように電位印加を行う０次に電位印
加を停止するとともに銅電極の電位の測定を開始する。Place the measuring part of the device of this method into the electroless copper plating solution.
Next, a potential is applied using a potentiostat so that the potential of the copper electrode becomes a copper passivation potential.The potential application is stopped at the 0th order, and measurement of the potential of the copper electrode is started.
銅電極は初め電位印加によって不動態化電位であるが、
電位印加の停止とともにめっき液の作用を受は変化する
。めっき液が正常であれば銅電極の電位はめっき電位と
なり銅めっきが析出する。一方、めっき液が異常であれ
ば銅電極の電位はめっき電位とはならず、不動態化電位
のままで銅めっきは析出しない。本方式ではめっき電位
の上限を適当に、例えば−６０ＱｍＶｖｓ、ＡｇＡｇｃ
ｌに設定し、電位印加を停止してからめっき電位の上限
になるまでの時間を測定することによって不動態化の測
定ができる。The copper electrode is initially at a passivation potential by applying a potential;
The effect of the plating solution changes as the potential application stops. If the plating solution is normal, the potential of the copper electrode becomes the plating potential, and copper plating is deposited. On the other hand, if the plating solution is abnormal, the potential of the copper electrode will not reach the plating potential, but will remain at the passivation potential and no copper plating will be deposited. In this method, the upper limit of the plating potential is set appropriately, for example, -60QmVvs, AgAgc
Passivation can be measured by setting the plating potential to 1 and measuring the time from stopping the potential application to reaching the upper limit of the plating potential.
実施例では、以下の測定装置を使用した。 In the examples, the following measuring device was used.
銅電極として直径１．０ｍｓ、長さ３．０ａｍの銅線を
使用し、対極として１．０＋ｓＸ１．ｏ口ｘＱ、ｌ ｃ
ｍの白金板を使用し、参照電極として東亜電波工業製の
銀塩化銀電極ＭＳ−３０５ＤＳを使用した。電位印加用
および電位測定用として北斗電工製ボテンシオスタッ）
ＨＡ３０１を使用した。無電解銅めっき液は表１のめっ
き液を使用した。A copper wire with a diameter of 1.0 ms and a length of 3.0 am was used as a copper electrode, and a copper wire with a diameter of 1.0 ms and a length of 1.0 s×1. o mouth x Q, l c
A silver silver chloride electrode MS-305DS manufactured by Toa Denpa Kogyo Co., Ltd. was used as a reference electrode. Botensiostat made by Hokuto Denko for potential application and potential measurement)
HA301 was used. The electroless copper plating solution shown in Table 1 was used.
一方、比較例として実施例と同一の銅電極と参照電極お
よびポテンシオスタフトから成る装置を使用した。On the other hand, as a comparative example, an apparatus consisting of the same copper electrode, reference electrode, and potentiosteft as in the example was used.
以上の装置およびめっき液において、実施例と比較例を
検討した。実施例では銅電極に一３００ｍＶｖｓ、Ａｇ
Ａｇｃｊ！を３０秒間印加し、その後電位印加を停止し
て２分間電位を測定した。Examples and comparative examples were investigated using the above-mentioned apparatus and plating solution. In the example, -300 mV vs. Ag was applied to the copper electrode.
Agcj! was applied for 30 seconds, and then the potential application was stopped and the potential was measured for 2 minutes.
方、比較例では電位印加を行わず、実施例と同一めっき
液を同時に測定した。測定例１では、実施例における銅
電位が約１０秒で約−７００ｍＶｖＫノ
ｓ、ＡｇＡｇｃｆとなりめっき電位となったが、測定例
２では２分後でも約−３５０ｍＶｖｓ、ＡｇＡｇ ｃ
１でめっき電位にはならなかった。一方、比較例では測
定例１． ２ともめっき電位約−７００ｍＶｖｓ、Ａｇ
Ａｇｃ＃を示しており差を示していない。すなわち、比
較例では不動態化しないように見えるめっき液の場合に
も実施例を適用することによって不動態化する場合があ
ることを測定できる。On the other hand, in a comparative example, the same plating solution as in the example was measured at the same time without applying a potential. In measurement example 1, the copper potential in the example became about -700 mVvKs, AgAgcf, in about 10 seconds, reaching the plating potential, but in measurement example 2, even after 2 minutes, it became about -350 mVvs, AgAg c
1 did not reach the plating potential. On the other hand, in the comparative example, measurement example 1. Both plating potentials are approximately -700mV vs, Ag
Agc# is shown and no difference is shown. That is, even in the case of a plating solution that does not appear to be passivated in the comparative example, it can be determined that the plating solution may be passivated by applying the example.
さらに、この実施例と比較例を表１のめっき液において
５日間連続して測定した。不動態化の定義は実施例では
電位印加停止後１分以内に銅電位が一６００ｍＶｖｓ、
ＡｇＡｇｃｌ以下にならない場合とし、比較例では銅電
位が一６００ｍＶｖｓ、ＡｇＡｇｃ１以上になった場合
とした０表２に各側における不動態化発生回数を示す、
実施例は比較例の約１０倍不動態化を検出しており、不
動態化検出能力が高いことを示す。Furthermore, this Example and Comparative Example were continuously measured for 5 days using the plating solution shown in Table 1. In the example, the definition of passivation is that within 1 minute after stopping the potential application, the copper potential is 1600 mV vs.
Table 2 shows the number of passivation occurrences on each side.
The example detects about 10 times more passivation than the comparative example, indicating that the passivation detection ability is high.
本発明により無電解銅めっきの不動態化を従来の約１０
倍の精度で検出でき、めっき浴成分や調整やエアレーシ
ョンの調整などの対策をより早く行える。その結果、不
動態化によるめっき厚手などの不良を低減するのに有効
である。According to the present invention, the passivation of electroless copper plating can be improved by approximately 10% compared to the conventional method.
Detection can be performed with twice the accuracy, allowing countermeasures such as adjusting plating bath components and aeration to be taken more quickly. As a result, it is effective in reducing defects such as thick plating due to passivation.
Claims (1)
電極からなる測定部と銅電極に電位を印加する装置と銅
電極の電位を測定する装置を用い、めっき液中において
銅電極に銅の不動態化電位を印加した後電位の印加を停
止し、銅電極の電位を測定し無電解銅めっきのめっき電
位になるまでの時間を測定する方式の不動態化の測定方
法。1. In electroless copper plating, a measurement unit consisting of a copper electrode, a counter electrode, and a reference electrode, a device that applies a potential to the copper electrode, and a device that measures the potential of the copper electrode are used to passivate copper to the copper electrode in the plating solution. A method for measuring passivation that involves applying a potential, then stopping the application of the potential, measuring the potential of the copper electrode, and measuring the time until it reaches the plating potential of electroless copper plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16727190A JPH0456779A (en) | 1990-06-26 | 1990-06-26 | Method for measuring passivation of electroless copper plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16727190A JPH0456779A (en) | 1990-06-26 | 1990-06-26 | Method for measuring passivation of electroless copper plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0456779A true JPH0456779A (en) | 1992-02-24 |
Family
ID=15846650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16727190A Pending JPH0456779A (en) | 1990-06-26 | 1990-06-26 | Method for measuring passivation of electroless copper plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0456779A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020054417A (en) * | 2000-12-28 | 2002-07-08 | 이구택 | Electricity chemical method for analyzing Fe content of galvannealed steel sheets |
| DE19957067B4 (en) * | 1999-11-26 | 2004-02-12 | Technische Universität Dresden | Method and arrangement for monitoring the electroless metal deposition |
-
1990
- 1990-06-26 JP JP16727190A patent/JPH0456779A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19957067B4 (en) * | 1999-11-26 | 2004-02-12 | Technische Universität Dresden | Method and arrangement for monitoring the electroless metal deposition |
| KR20020054417A (en) * | 2000-12-28 | 2002-07-08 | 이구택 | Electricity chemical method for analyzing Fe content of galvannealed steel sheets |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2935947B2 (en) | Method for selectively monitoring trace components in plating baths | |
| JPH0456779A (en) | Method for measuring passivation of electroless copper plating | |
| US9593931B2 (en) | Palladium coating thickness measurement | |
| KR970013166A (en) | Method of evaluating surface state of metal and method of manufacturing semiconductor device | |
| JPH0627075A (en) | Pinhole evaluation method for inorganic material coatings based on iron-based materials | |
| BR9606317A (en) | Method for measuring an electrochemical activity | |
| Pratt et al. | High-accuracy differential-pulse anodic stripping voltammetry with indium as an internal standard | |
| JPH1114582A (en) | Diagnosis method for corrosion resistance of structural materials | |
| JPS58141531A (en) | Semiconductor element metal thin film etching apparatus | |
| Do Duc et al. | Electrochemical behavior of Sn8Hg (gamma-2) and dental amalgam in a phosphate buffer solution | |
| JPS5421797A (en) | Coating film deterioration detecting method | |
| JP2776145B2 (en) | Measuring device for coating weight of plated steel sheet | |
| SU608088A1 (en) | Method of determining the mode of mass transfer melt in liquid-metal | |
| JPH0798296A (en) | Measuring method for concentration of additive in electroless copper plating liquid | |
| US5955150A (en) | Method for testing materials for use in electroless plating | |
| JPS63202081A (en) | Amorphous magnetic material by plating method | |
| SU1032328A1 (en) | Method of producing pickups for cyclic deformation checking | |
| JPS56160608A (en) | Method of measuring surface area of object to be plated | |
| JPH0379794A (en) | Method for controlling plating solution | |
| KR0128237Y1 (en) | Ion injection amount inspection device | |
| CN114892250A (en) | Method for rapidly detecting long-term electroplating applicability of alkaline copper plating solution on neodymium iron boron surface | |
| JPS5422760A (en) | Evaluating method for si crystal | |
| JPS57158364A (en) | Measuring method for electroless plating reaction | |
| JP2633490B2 (en) | Manufacturing method of printed wiring board | |
| JPS5492065A (en) | Measuring method for manufacturing process evaluation of semiconductor device |