JPS59116363A - Palladium activating liquid - Google Patents
Palladium activating liquidInfo
- Publication number
- JPS59116363A JPS59116363A JP22603782A JP22603782A JPS59116363A JP S59116363 A JPS59116363 A JP S59116363A JP 22603782 A JP22603782 A JP 22603782A JP 22603782 A JP22603782 A JP 22603782A JP S59116363 A JPS59116363 A JP S59116363A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- complexing agent
- plating
- activation
- wiring
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1813—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by radiant energy
- C23C18/1817—Heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、タングステンやモリブデンなどのＶＩａ族高
融点金属をメタライズ配線した湿式セラミック基板にお
いて、上記配線のみを活性化し、配線上のみに化学めっ
きできるようにするためのパラジウム活性化液に関する
。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention provides a method of activating only the wiring and chemical plating only on the wiring in a wet ceramic substrate on which metalized wiring is made of Group VIa high melting point metal such as tungsten or molybdenum. This invention relates to a palladium activating solution.
セラミック基板には、乾式基板と湿式基板とがある。そ
の内転式基板は、セラミック基板の上に貴金属を含むイ
ンクで印刷配線し、約１０００”Ｃ以下の温度で焼成す
るものである。Ceramic substrates include dry substrates and wet substrates. The adductor type board is a ceramic board with wiring printed on it using an ink containing a noble metal, and then fired at a temperature of about 1000''C or less.
この乾式基板は、配線が貴金属で形成されているので、
配線としての導体抵抗が小さく、又配線の腐蝕もなく、
（にはん／ど付性もｐく、特別な活性化処理を行なわな
くても、配線上のみに化学めっきが可能であり、いくつ
かの利点を有する。This dry board has wiring made of precious metal, so
The conductor resistance as wiring is low, and there is no corrosion of the wiring.
(It also has excellent soldering/dappling properties, and can be chemically plated only on wiring without special activation treatment, and has several advantages.
その反面、貴金属を用いるので高価であること、及び製
法上多層配線が困稚であるという欠点がある。On the other hand, it has disadvantages in that it is expensive because it uses precious metals, and that multilayer wiring is difficult to manufacture.
この乾式基板に代るものとして、湿式基板が考えられて
いる。即ち湿式基板は、粘土状の薄板にタングステンや
モリブデンなどの高融点金属を含むインクで印刷配線し
、この粘土状薄板を積み重ねて約１５００’Ｃの温度で
焼成するものである。A wet type substrate is being considered as an alternative to this dry type substrate. That is, the wet type substrate is made by printing wiring on clay-like thin plates with ink containing a high-melting point metal such as tungsten or molybdenum, stacking the clay-like thin plates and baking them at a temperature of about 1500'C.
このようにすることによって複雑な配線を多層構造に成
形することができる利点がある。This has the advantage that complex wiring can be formed into a multilayer structure.
しかしながら、配線導体が、高融点金属であるだめに、
導体抵抗が大きいこと、及び、■ｃやＬＳＩの半導体を
製造する際に配線同志を直接はんだ付けできないとと又
ワイヤボンデングができないなどの欠点がある。However, since the wiring conductor is a high melting point metal,
There are drawbacks such as high conductor resistance, and (1) the inability to directly solder wires to each other when manufacturing semiconductors such as C and LSI, and the inability to perform wire bonding.
この欠点を補うだめに、湿式基板では、高融点金属表面
を化学めっき処理することによって改質し、配線の導体
抵抗を小さくすると共にはんだ付け、ワイヤボンデング
を可能にしている。In order to compensate for this drawback, wet substrates are modified by chemically plating the high-melting point metal surface to reduce the conductor resistance of the wiring and to enable soldering and wire bonding.
しかしながら高融点金宅は、化学的に不活性であるので
、化学めっき処理をするには、一旦配線部分を活性化し
た後、化学めっきする必要゛がある。However, since high-melting point metal is chemically inert, it is necessary to activate the wiring portion before chemical plating.
上記活性化するだめの液として本出願人によってすでに
提案されている（特公昭５５−４３２７５号、特開昭５
．−９３１２９号）パラジウムが使用される。The above-mentioned activating liquid has already been proposed by the present applicant (Japanese Patent Publication No. 55-43275,
．． -93129) Palladium is used.
さてこのパラジウムは、弱酸性アルカリ性溶液中におい
て以下の反応が行なわ刊２、酸化物或は水酸化物を生成
する。Now, this palladium undergoes the following reaction in a weakly acidic alkaline solution to produce an oxide or hydroxide.
Ｐｄ” ＋ Ｈ２０＝ Ｐｄ０−＋ ２Ｈ＋・・・・・
・・・・・・・・・・・・・・・・・・（１）ＰｄＺ＋
として存在できる濃度（ｍｏ Ｌ／Ｌ） ＝ １０ ”
３５”￥’−・・（１’）これを更に詳しく説明すると
、上式より、水溶液のｐＨが１５のとき、Ｐｄ２＋濃度
は、４．５Ｘ１Ｑ２＋１ｍｏ Ｌ ／Ｌとなる。一方、
エチレンジアミン四酢酸を用いて、、ｐＨ：１３の水溶
液中で、全量の（１０−３ｍｏｔ／ｌ） Ｐｄ２＋を、
４．５ Ｘ １０−２９ｍｏ Ｌ／ｌとなるまで錯化す
るだめには、以下の通りとなる。Pd" + H20= Pd0-+ 2H+...
・・・・・・・・・・・・・・・・・・(1) PdZ+
Concentration that can exist as (mo L/L) = 10"
35"￥'-...(1') To explain this in more detail, from the above equation, when the pH of the aqueous solution is 15, the Pd2+ concentration is 4.5X1Q2+1mo L /L. On the other hand,
A total amount of (10-3 mot/l) Pd2+ was prepared using ethylenediaminetetraacetic acid in an aqueous solution at pH: 13.
The procedure for complexing to 4.5 x 10-29 mo L/l is as follows.
即ち
ＥＤＴＡ’−＋Ｐｄ”−Ｐｄ−ＥＤＴＡ ＜生成定数、
１０１８．５） ・、、、、・＜シ）（ＥＤＴＡ’−
はエチレンジアミン四酢酸イオンを示す）の反応式から
水溶液中のＰｄ２＋の濃度は、次式で表わされる。That is, EDTA'-+Pd"-Pd-EDTA<generation constant,
1018.5) ・、、、・<shi)(EDTA'-
represents ethylenediaminetetraacetic acid ion), the concentration of Pd2+ in the aqueous solution is expressed by the following formula.
上式（２）においてＰｄ −ＥＤ’ｌ”Ａ濃度は、はぼ
１ｏ−３ｍａｔ／Ｌに近似できルノテ、Ｐｄ” ｍ 度
７５ｆ ４．５ Ｘ Ｉ Ｆ”ｍｏｌ／ｌとなるために
は、ＥＤＴＡ ’−濃度として７×１０ ’ ｍｏ ｔ
／ｌが必要ｆ６る。In the above formula (2), the Pd-ED'l"A concentration can be approximated to approximately 1o-3mat/L, and in order to become Pd"m degree 75f 4.5 X I F"mol/l, EDTA '-7 x 10' as concentration
/l is required f6.
そこでエチレンジアミン四酢酸（或はそのアルカリ金属
塩）の水溶液に対するＰｄ２＋の溶解度は１ｍｏｔ／を
以下であるから、パラジウム活性化液の中には、錯化し
たパラジウム（Ｐｄ −ＥＤＴＡ）と、遊離したパラジ
ウム（Ｐｄ２＋）以外にパラジウム酸化物（Ｐｄ０）を
含むことになる。Therefore, since the solubility of Pd2+ in an aqueous solution of ethylenediaminetetraacetic acid (or its alkali metal salt) is less than 1 mot/, the palladium activation solution contains complexed palladium (Pd-EDTA) and free palladium. It contains palladium oxide (Pd0) in addition to (Pd2+).
この活性化液を用いて、高融点金４によって配線したセ
ラミック基板を活性化したところ次のような問題が生じ
た。When this activation liquid was used to activate a ceramic substrate wired with high melting point gold 4, the following problem occurred.
即ち、活性化液中に存在する酸化パラジウム粒子が高融
点金属の配線以外のセラミック基板上に付着し、このよ
うにして付着した酸化パラジウム粒子がめつき核となっ
て、セラミック基板上にもめつきされ（以下この現象を
異常析出という）だ。That is, the palladium oxide particles present in the activating solution adhere to the ceramic substrate other than the high-melting point metal wiring, and the palladium oxide particles thus attached become plating nuclei and are also plated onto the ceramic substrate. (Hereinafter, this phenomenon will be referred to as abnormal precipitation).
この異常析出の厚さが１μｍ以内のとき１＃ｉ：、肉眼
では、観察されないが、並行して配線された導体間の絶
縁抵抗の低下として現われる。When the thickness of this abnormal precipitation is 1 μm or less, 1#i: Although it is not observed with the naked eye, it appears as a decrease in insulation resistance between conductors wired in parallel.
又異常析出の厚さが５μｍを越えると、セラミ・ツク基
板全体が灰色となって肉眼によって観察することができ
、導体間の抵抗が極めて小さくなる。If the thickness of the abnormal precipitation exceeds 5 μm, the entire ceramic substrate becomes gray and can be observed with the naked eye, and the resistance between the conductors becomes extremely small.
この異常析出を防止する目的で、活性化液中の酸化物を
除去するだめに細孔度０．６μｍのフィルターによって
活性化液を濾過しても、フィルターを通過したパラジウ
ム酸化物が活性化液中に存在することになり、上述の異
常析出現象を皆無にすることができなかった。In order to prevent this abnormal precipitation, even if the activation liquid is filtered through a filter with a pore size of 0.6 μm in order to remove the oxides in the activation liquid, the palladium oxide that has passed through the filter will remain in the activation liquid. Therefore, it was not possible to completely eliminate the above-mentioned abnormal precipitation phenomenon.
その結果、高密度に配線された基板を高絶縁性を維持し
て製作することができず、湿式基板の基本的な問題とな
っている。又配線が高密度化への傾向にあり、且−多層
配線への傾向にある中で、異常析出が起らない活性化液
の開発が急がれているのが現状である。As a result, it is impossible to manufacture a board with high density wiring while maintaining high insulation properties, which is a fundamental problem with wet-type boards. In addition, with the trend toward higher wiring density and multilayer wiring, there is an urgent need to develop an activating solution that does not cause abnormal precipitation.
本発明は、上記従来の欠点乃至は、事情を鑑みなされた
ものであって、セラミック基板のＶＩＡ族金属配線のみ
にパラジウムを付着させ、後工程の化学めっきでの異常
析出を皆無にすることができるパラジウム活性化液を提
供せんとするものである。The present invention has been made in view of the above-mentioned conventional drawbacks and circumstances, and it is possible to attach palladium only to the VIA group metal wiring of a ceramic substrate, thereby completely eliminating abnormal precipitation in the subsequent chemical plating process. The purpose is to provide a palladium activation solution that can be used.
即ち本発明は、水溶性パラジウム塩と、ｐＨ調幣剤を含
肩するパラジウム液に、パラジウムの。That is, the present invention includes a palladium solution containing a water-soluble palladium salt and a pH adjusting agent.
錯化剤としてポリエチレンイミンを添加することによっ
て、異常析出が起らないことを実験によって確認し、更
に、このパラジウム活性化液において、膣液のｐＨ、パ
ラジウム含有量、及び錯化剤とパラジウムのモル濃度比
を変化させ、その最適値を実験によって確認し、異常析
出が起らないパラジウム活性化液にしたことを特徴とす
るものである。It was confirmed through experiments that abnormal precipitation does not occur by adding polyethyleneimine as a complexing agent, and furthermore, in this palladium activation solution, the pH of vaginal fluid, the palladium content, and the relationship between the complexing agent and palladium were determined. The palladium activation solution is characterized by varying the molar concentration ratio and confirming its optimum value through experiments to create a palladium activation solution that does not cause abnormal precipitation.
以下本発明の一実施例について説明する。発。 An embodiment of the present invention will be described below. From.
間者らは、一般的な化合物について、最初に試みた。They first tried common compounds.
即ち一般的な化合物の水溶７ｊ、１１に対する溶解度・
ば、約１ ｍｏｔ／ｌであるが、屯金属の錯化剤は、一
般的に毒性が強く、且つ廃液処理が難しいことを考え、
約０．２ ｍａｔ／Ｌ 、程度の濃度にしてｐｄ２＋濃
度を４．５ Ｘ １ｏ−２９ｍｏｔ／ｚにするための錯
化剤とパラジウムとの生成定数を式（２）を参考にして
求めたところ、パラジウムと錯化剤がモル比で１＝１で
結合するものは、１０２６．１：２で結合するもので１
０２７．１：４で結合するもので１０２８となり、この
必要値を満足するものは、アンモニア（ＮＨ３で１ｏ２
９，６）のみであることが確認された。That is, the solubility of general compounds in water 7j, 11.
For example, it is about 1 mot/l, but considering that tun metal complexing agents are generally highly toxic and difficult to treat waste liquid,
The production constant of the complexing agent and palladium to make the pd2+ concentration 4.5 x 1o-29 mot/z at a concentration of about 0.2 mat/L was determined using equation (2) as a reference. , one in which palladium and complexing agent are combined in a molar ratio of 1=1 is 1026.1:2 and 1
027.1:4 is 1028, and the one that satisfies this required value is ammonia (1o2 with NH3).
9,6) was confirmed.
しかしながら、アンモニアは、アルカリ性情゛液中では
揮発するので、／＆度変化が急速であり、目つ分析が困
難であるため液管理が困難であること、及び臭気が強い
ことと毒性が強いことから、実用化することが不可能で
ある。However, since ammonia volatilizes in alkaline fluids, its temperature changes rapidly, making it difficult to conduct clear analysis, making it difficult to manage the solution, as well as having a strong odor and toxicity. Therefore, it is impossible to put it into practical use.
そこで発明者らは、なおもアンモニア以外の錯化剤を見
出すべく鋭意実験研究した結果、アルカリ性溶液中で、
ある種の錯化剤は、金属イオン−錯化剤−水酸イオンか
ら成る錯体を生成・することを見出し、これに適合する
化合物として、ポリエチレンイミン化合物を選び一実験
したところ著しるしい効果を持つことを確認した。Therefore, the inventors conducted intensive experimental research to find a complexing agent other than ammonia, and found that in an alkaline solution,
It was discovered that a certain type of complexing agent forms a complex consisting of a metal ion, a complexing agent, and a hydroxide ion.A polyethyleneimine compound was selected as a compound compatible with this, and an experiment showed that it had a remarkable effect. I confirmed that I have it.
この化合物は、東京化成工業（株）などの薬品メーカで
売られている公知の化合物である。基本分子構造は、
ＮＨ２（ＣＨ２ＣＨ２ＮＨ）ｍＨ・・・・・・・・・・
・・・（３）（この式でｍは重合度である。）
で示され、平均分子量は、５００〜１０００００である
。This compound is a known compound sold by drug manufacturers such as Tokyo Chemical Industry Co., Ltd. The basic molecular structure is NH2(CH2CH2NH)mH・・・・・・・・・
...(3) (In this formula, m is the degree of polymerization.) The average molecular weight is 500 to 100,000.
この化合物とパラジウムとの生成定数は、確認していな
いが、金属イオンがパラジウムであることから、上記と
同じような錯体が生成さ−れ、この生成定数がパラジウ
ム酸化物を生成することのない大きな値になっているも
のと考える。The formation constant between this compound and palladium has not been confirmed, but since the metal ion is palladium, a complex similar to the above is formed, and this formation constant does not lead to the formation of palladium oxide. I think it is a large value.
先ず第１図に評価用のサンプルを示す。図において、こ
のサンプルは、セラミック基板２上にタングステンメタ
ラ・イズを２５ｍｍ Ｘ ２．５ｍｍの正方形１ （以
下ランドという）にして、１６５個に分は形成させたも
のである。この基板にＮｉめつきを行ない、その析出程
度を見ることによって、ノくラジウム活性化液の性能を
評価した。First, Fig. 1 shows a sample for evaluation. In the figure, this sample has 165 tungsten metallized squares 1 (hereinafter referred to as lands) of 25 mm x 2.5 mm formed on a ceramic substrate 2. The performance of the radium activation solution was evaluated by plating Ni on this substrate and observing the degree of Ni plating.
即ち各ランド以外のセラミック基板上にＮｉめつきが析
出しだ場合は異常析出とし、又各ランド全部がＮｉめっ
きされない場合は、析出むらが生じたものとして評価し
た。That is, when Ni plating was deposited on the ceramic substrate other than each land, it was evaluated as abnormal deposition, and when all of the lands were not plated with Ni, it was evaluated that uneven precipitation had occurred.
次に、セラミック基板サンプルをめっきする１寸での工
程と処理条件について第２図を基に説明する。図におい
て、セラミック基板サンプルを、工程ＩにてＮａ ＯＨ
１００ｙ ／７ 、液温６０°Ｃの溶液中に１０分間浸
清して脱脂し、その後水道水にて２分間、純水にて０．
５分間水洗し［程■）、次いで液温６０゛Ｃの活性化液
に８分浸漬して活性化しく工程ｍ）、水道水にて５分間
、純水にて０５分間水洗した（工程Ｉｖ）。次いで工程
Ｖにて液温９０゛ｃのカニゼン梨シューマロ８０に１０
分間浸漬してＮｉメッキを行い、水道水にて１０分間純
水にて０５分間水洗しく工程ｖｒ）、最終的にドライヤ
にて乾燥した（工程■）。実験槽は、ビー力１ｔに各工
程（水洗工程と乾燥工程以外の工程）に要する液を入れ
、ウォータバスにて所定の温度に設定した。Next, a one-dimensional process and processing conditions for plating a ceramic substrate sample will be explained based on FIG. 2. In the figure, the ceramic substrate sample was treated with NaOH in step I.
100y/7, degreased by immersion in a solution with a liquid temperature of 60°C for 10 minutes, then immersed in tap water for 2 minutes, and purified water for 0.2 minutes.
Washed with water for 5 minutes [Step 2], then immersed in an activation solution at a liquid temperature of 60°C for 8 minutes to activate (Step M), washed with tap water for 5 minutes and purified water for 05 minutes (Step Iv). ). Next, in step V, add 80 to 10 ounces of Kanizen Pear Shumallow at a liquid temperature of 90°C.
Ni plating was performed by dipping for 10 minutes, followed by washing with tap water for 10 minutes and pure water for 05 minutes (step vr), and finally drying with a dryer (step 2). In the experimental tank, liquids required for each process (processes other than the washing process and the drying process) were placed in a 1 ton beaker, and the temperature was set to a predetermined temperature using a water bath.
（イ）パラジウム活性化液の組成について、水溶性パラ
ジウム塩とｐＩ（調整剤を含有するパラジウム活性化液
にパラジウムの錯化剤としてポリエチレンイミンを添加
した。この時のポリエチレンイミンの平均分子量は、５
００〜１０００００であり、水溶性パラジウム塩の濃度
（ｍｏｔ／ｌ）とＡｐＨ値を変化させ、Ｎｉめつきをし
たところ、一部分の水溶性パラジウム塩の濃度とｐＨ値
を除いて、すべてのランド上のみにＮｉが析出し、パラ
ジウム塩の錯化剤として、適していることが確認されだ
。(a) Regarding the composition of the palladium activation liquid, polyethyleneimine was added as a palladium complexing agent to the palladium activation liquid containing a water-soluble palladium salt and a pI (adjusting agent).The average molecular weight of the polyethyleneimine at this time was: 5
00 to 100,000, and when the concentration (mot/l) of the water-soluble palladium salt and the ApH value were changed and Ni plating was performed, all of the land surfaces except for the concentration and pH value of the water-soluble palladium salt in a part of the land were changed. Ni was precipitated only on the surface of the catalyst, confirming its suitability as a complexing agent for palladium salts.
（ロ）パラジウム塩の１度について、
活性化液１を当りのパラジウム塩の濃度は、１０’より
小さくなるとパラジウムの析出量が少なくなり、ランド
の活性化が充分でな（Ｎｉめつきの析出がしにくくなっ
た。又１０−３以上では、パラジウムが完全に溶解せず
、セラミック基板に付着して異常析出が発生し、パラジ
ウム塩の濃度は、１０’〜１０−３が適していることが
確認された。(b) If the concentration of palladium salt per 1 degree of palladium salt is less than 10', the amount of palladium precipitated will decrease, and the activation of the land will be insufficient (the precipitation of Ni plating will be reduced). Furthermore, if the concentration is higher than 10-3, palladium will not be completely dissolved and will adhere to the ceramic substrate and cause abnormal precipitation, so it is recommended that the concentration of palladium salt is between 10' and 10-3. confirmed.
（ハ）錯化剤／パラジウムのモル？／％度比について１
、この濃度比が１０−２以下になると、酸化パラジウム
或は、水酸化パラジウムが発生し異常析出が発生した。(c) Complexing agent/mole of palladium? /%About the ratio1
When this concentration ratio became 10-2 or less, palladium oxide or palladium hydroxide was generated and abnormal precipitation occurred.
又この濃度比が１００以上では、パラジウムの析出が少
なくなり、Ｎｉめつきの析出むらが生じた。このことが
ら錯化剤とパラジウムのモル濃度比は、１０−２〜１０
０が適していることが確認された。Moreover, when this concentration ratio was 100 or more, precipitation of palladium decreased and uneven precipitation of Ni plating occurred. Based on this, the molar concentration ratio of the complexing agent and palladium is 10-2 to 10
It was confirmed that 0 is suitable.
（ニ）活性化液のｐＨＫついて、
活性化液のｐｌＦ（値が９では、Ｎｉめつきの析出むら
を生じ、１０〜１４．５の値のとき正常にＮｉめつきが
析出することが確認された。又１）Ｈ値１５では、活性
化液が黒化して使用不能になった。(d) Regarding the pHK of the activation solution, it was confirmed that the plF of the activation solution (when the value is 9, uneven precipitation of Ni plating occurs, and when the value is between 10 and 14.5, Ni plating is deposited normally. 1) At an H value of 15, the activation liquid turned black and became unusable.
（ホ）パラジウム塩について、
パラジウム塩として、硝酸バラ゛ジウム、硫酸パラジウ
ムを使用してもよい結果が得られたことが確認できた。(e) Regarding palladium salts, it was confirmed that good results were obtained when using palladium nitrate and palladium sulfate as palladium salts.
次に実施例について説明する。第１表において、パラジ
ウム活性化液の組成として水溶性パラジウム塩とｐＨ調
整材を含有するパラジウム活性化液に、パラジウムの錯
化剤として、ポリエチレンイミンを添加したものを用い
、パラジウム塩のｔａ ＋ｖ−％ ｐ、Ｈ，錯化剤と
パラジウムのモル濃度比、ポリエチレンイミン錯化剤の
平均分子量、をそれぞれ変化させて実験した０なお表中
の析出状態欄の記号においてＸ印は、Ｎｉめっきが異常
析出した場合の状態を、○印は、正常な析出。Next, an example will be described. In Table 1, the composition of the palladium activation solution is a palladium activation solution containing a water-soluble palladium salt and a pH adjusting agent, with polyethyleneimine added as a palladium complexing agent, and the palladium salt is ta +v. -% p, H, the molar concentration ratio of the complexing agent and palladium, and the average molecular weight of the polyethyleneimine complexing agent were varied. The state when abnormal precipitation occurs is marked ○, which indicates normal precipitation.
を又○印は、析出むらをそれぞれ示す。Also, the ○ marks indicate uneven precipitation.
第１表において、実施１）ｌ１１〜５は、パラジウム塩
の濃度を変えた場合のＮｉめっきの析出に与える影響を
検討したものであシ、塩化パラジウム濃度として１０−
６〜１０−３ｍｏｔ／ｌの範囲が良いことが判った。即
ちパラジウム濃度がこの範囲より小さい値になると、パ
ラジウムの析出量が少なく、Ｎ１めつきが析出し碓くな
った。文通に上記範囲より大きな値になると、塩化パラ
ジウム（粉末）が完全に溶解しなくなり、塩化パラジウ
ムが、セラミック基板のパターン外に付着し、Ｎｉめり
きによる異常析出を生じた。実施例６〜７は、パラジウ
ム塩として、硝酸パラジウム、硫酸パラジウムも使用で
きることを示す。実施例８〜１３は、錯化剤に用いたポ
リエチレンイミンの分子量の影響を示す。分子量５００
〜１０００００の範囲でも使用できることが判る。In Table 1, Examples 1) l11 to 5 were conducted to examine the effect of varying the concentration of palladium salt on the precipitation of Ni plating.
It was found that a range of 6 to 10-3 mot/l is good. That is, when the palladium concentration became a value smaller than this range, the amount of palladium precipitated was small, and the N1 plating was precipitated and became unsuitable. When the value was larger than the above range, palladium chloride (powder) was not completely dissolved, and palladium chloride adhered to the outside of the pattern on the ceramic substrate, causing abnormal precipitation due to Ni plating. Examples 6-7 show that palladium nitrate and palladium sulfate can also be used as palladium salts. Examples 8-13 demonstrate the effect of the molecular weight of the polyethyleneimine used as the complexing agent. Molecular weight 500
It can be seen that a range of 100,000 to 100,000 can also be used.
実施例１４〜１８は、錯化剤／Ｐｄ濃度のモル比を変え
、Ｎｉめつきの析出状態に与える影響を検討。In Examples 14 to 18, the molar ratio of complexing agent/Pd concentration was changed to examine the effect on the precipitation state of Ni plating.
したものである。このモル比の値が小さいと、酸化パラ
ジウム或は、水酸化パラジウムの発生が起り、異常析出
が発生した。文通に大きいと、パラジウムの析出が少な
くなり、Ｎｉめりきの析出むらが生じた。その範囲は、
下限がＯｏｌ、上限が１００であることが判った。This is what I did. When the value of this molar ratio was small, palladium oxide or palladium hydroxide was generated, resulting in abnormal precipitation. When the size of the correspondence was large, the precipitation of palladium decreased and uneven precipitation of Ni plating occurred. The range is
It was found that the lower limit is Ool and the upper limit is 100.
実施例１９〜２１は、パラジウム活性化液のｐＨの影響
を示す。ｐＨ９では、Ｎｉめりきの析出がし難くなり、
ｐ）（１０〜１４．５の時、Ｎｉめつきの析出が正常で
あることが判った。又ｐＩ（１５の場合は、パラジウム
活性化液が黒化して使用不能となった。Examples 19-21 show the effect of pH of palladium activation solution. At pH 9, Ni plating becomes difficult to precipitate,
When pI was 10 to 14.5, the precipitation of Ni plating was found to be normal. When pI was 15, the palladium activation solution turned black and became unusable.
第２表は、パラジウム塩の濃度を５Ｘ１０ 、錯化剤
／Ｐｄ濃度のモル比１０１１（１４にし、錯化剤として
エチレンジアミン四酢酸ナトリウムとグリシンを使用し
て検討したところ、Ｎｉめつきが異常析出し、ここでも
錯化剤としてポリエチレンイミンが、最適であることが
、確認された。Table 2 shows that when the concentration of palladium salt was 5X10, the molar ratio of complexing agent/Pd concentration was 1011 (14), and sodium ethylenediaminetetraacetate and glycine were used as complexing agents, abnormal Ni plating was observed. However, it was confirmed that polyethyleneimine is the most suitable complexing agent here as well.
この異常析出の原因は、ポリエチレンイミンの生成定数
に対して、エチレンジアミン四酢酸す） ＩＪウム及び
グリシンの生成定数が可成り小さいことが考えられ、酸
化パラジウム或は水酸化パラジウムが生成し、異常析出
するものと考える０
なお第１表の実施例ＮＯ３のパラジウム活性化液の組成
によれば、タングステン表面を活性化液１４当、１００
ｄ靜／を処理してもニッケルメッキ１寸正常に析出し、
活性化液の安定性が確認できた。又モリブデン配線をし
またセラミック基板も、上記と全く同じ処理効果が得ら
れ、Ｖｌａ族高融点金属に対し、安定した活性化液であ
ることが確認できた。The cause of this abnormal precipitation is thought to be that the production constants of ethylenediaminetetraacetic acid and glycine are considerably smaller than the production constant of polyethyleneimine, and palladium oxide or palladium hydroxide is produced, resulting in the abnormal precipitation. According to the composition of the palladium activating solution in Example No. 3 in Table 1, the tungsten surface was coated with 14 parts of the activating solution and 100 parts of the activating solution.
Even after treatment, 1 inch of nickel plating was deposited normally,
The stability of the activation solution was confirmed. Furthermore, the same treatment effect as above was obtained on a ceramic substrate with molybdenum wiring, and it was confirmed that the activating solution was stable for Vla group high melting point metals.
以上詳述した通シ、本発明のパラジウム活性化液によれ
ば、パラジウム塩と、ｐＨ調整剤を含有するパラジウム
液に、パラジウムの錯化剤としてポリエチレンイミンを
添加した活性化液にしだので、■Ｉａ族高融点の金属に
よってセラミック基板上に配線された配線のみを活性化
することができ、その結果としてめっき工程において配
線部分のみにめっきして改質させ、めっきの異常析出や
析出むらをなくし、導体抵抗の小さい、はんだ付性のよ
い、ワイヤボンデングが可能な、活性化液を得ることが
できた。As detailed above, according to the palladium activation solution of the present invention, the activation solution is obtained by adding polyethyleneimine as a palladium complexing agent to a palladium solution containing a palladium salt and a pH adjuster. ■It is possible to activate only the wiring wired on the ceramic substrate using a Group Ia high melting point metal, and as a result, only the wiring portion is plated and modified in the plating process, and abnormal precipitation and uneven precipitation of the plating can be prevented. We were able to obtain an activation liquid that has low conductor resistance, good solderability, and is wire bondable.
又パラジウム塩の濃度、活性化液のｐＨ値、及びポリエ
チレンイミンとＰｄのモル比、を適当な範囲に調節する
ことにより、より安定したパラジウム活性化液にするこ
とができ、ますます高密度化する配線及び多層化への技
術指向の要求に対応することができるなど多大の効果を
奏する０In addition, by adjusting the concentration of palladium salt, the pH value of the activation solution, and the molar ratio of polyethyleneimine to Pd within appropriate ranges, it is possible to make the palladium activation solution more stable, resulting in even higher density. It has great effects, such as being able to respond to technology-oriented demands for wiring and multilayering.
第１図は、めっき特性の評価に用いたモデルセラミック
基板を、第２図はメノキ工程を示す図である。
１・・・・・セラミック基板のランド、２・・・・セラ
ミック基板。
第 ／閃
栴２図FIG. 1 shows a model ceramic substrate used for evaluating plating characteristics, and FIG. 2 shows an agate wood process. 1... Ceramic board land, 2... Ceramic board. No./Sensen 2
Claims (1)
化した後めっき処理して高融点金属を改質化させるだめ
の活性化液において、水溶性パラジウム塩とｐＨ調整剤
を含有せるパラジウム活性化液に、パラジウムの錯化剤
としてポリエチレンイミンを添加した仁とを特徴とする
パラジウム活性化液。 ２、特許請求の範囲第１項の水溶性パラジウム塩におい
て、塩化パラジウム、硝酸パラジウム、硫酸パラジウム
よりなる群中から選ばれた１種以上のパラジウム塩を含
むことを特徴とするパラジウム活性化液。 ３ 特許請求の範囲第１項のｐＨＭｔｍ整剤において、
アルカリ金属の水酸化物であることを特徴とするパラジ
ウム活性化液。 ４、 高融点金属を基板上に印刷配線し、該配線を活性
化した後、めっき処理して高融点金属を改質化させるだ
めの活性化液において、該活性化液のｐＨを１０〜１４
５、活性化液１リットル肖シのパラジウム量１０−６〜
１０−３ｍｏｔ、錯化剤ｌくラカムのモル濃度比１０−
２〜１００とし、該錯化剤としてポリエチレンイミンを
使用したことを特徴とするパラジウム活性化液０[Claims] 1. A water-soluble palladium salt and A palladium activation liquid comprising a palladium activation liquid containing a pH adjuster and polyethyleneimine added thereto as a complexing agent for palladium. 2. A palladium activation solution comprising one or more types of palladium salts selected from the group consisting of palladium chloride, palladium nitrate, and palladium sulfate in the water-soluble palladium salt according to claim 1. 3. In the pHMtm adjustment agent according to claim 1,
A palladium activation liquid characterized by being an alkali metal hydroxide. 4. After printing wiring of a high melting point metal on a substrate and activating the wiring, adjust the pH of the activation liquid to 10 to 14 in the activation solution used to modify the high melting point metal by plating.
5. Amount of palladium in 1 liter of activation solution: 10-6 ~
10-3mot, molar concentration ratio of complexing agent l to lacham 10-
2 to 100, and polyethyleneimine is used as the complexing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22603782A JPS59116363A (en) | 1982-12-24 | 1982-12-24 | Palladium activating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22603782A JPS59116363A (en) | 1982-12-24 | 1982-12-24 | Palladium activating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59116363A true JPS59116363A (en) | 1984-07-05 |
Family
ID=16838781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22603782A Pending JPS59116363A (en) | 1982-12-24 | 1982-12-24 | Palladium activating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59116363A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02178990A (en) * | 1988-11-02 | 1990-07-11 | Schering Ag | Substrate material conditioner for manufacturing printed circuit |
| JPH06279602A (en) * | 1993-03-26 | 1994-10-04 | Idemitsu Petrochem Co Ltd | Polyolefin resin molded product capable of being plated in electroless state |
| JP2005206905A (en) * | 2004-01-23 | 2005-08-04 | Ebara Corp | Substrate treatment method and device, and treatment liquid |
| WO2011118439A1 (en) * | 2010-03-23 | 2011-09-29 | Jx日鉱日石金属株式会社 | Electroless plating pretreatment agent, electroless plating method using same, and electroless plated object |
| WO2022055426A1 (en) * | 2020-09-08 | 2022-03-17 | Nanyang Technological University | Surface conditioner for electroless deposition |
-
1982
- 1982-12-24 JP JP22603782A patent/JPS59116363A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02178990A (en) * | 1988-11-02 | 1990-07-11 | Schering Ag | Substrate material conditioner for manufacturing printed circuit |
| JPH06279602A (en) * | 1993-03-26 | 1994-10-04 | Idemitsu Petrochem Co Ltd | Polyolefin resin molded product capable of being plated in electroless state |
| JP2005206905A (en) * | 2004-01-23 | 2005-08-04 | Ebara Corp | Substrate treatment method and device, and treatment liquid |
| WO2011118439A1 (en) * | 2010-03-23 | 2011-09-29 | Jx日鉱日石金属株式会社 | Electroless plating pretreatment agent, electroless plating method using same, and electroless plated object |
| JP5518998B2 (en) * | 2010-03-23 | 2014-06-11 | Ｊｘ日鉱日石金属株式会社 | Electroless plating pretreatment agent, electroless plating method and electroless plated product using the same |
| US8814997B2 (en) | 2010-03-23 | 2014-08-26 | Jx Nippon Mining & Metals Corporation | Electroless plating pretreatment agent, electroless plating method using same, and electroless plated object |
| WO2022055426A1 (en) * | 2020-09-08 | 2022-03-17 | Nanyang Technological University | Surface conditioner for electroless deposition |
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