JP4425453B2 - Method for improving adhesion between metal films - Google Patents
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- JP4425453B2 JP4425453B2 JP2000357159A JP2000357159A JP4425453B2 JP 4425453 B2 JP4425453 B2 JP 4425453B2 JP 2000357159 A JP2000357159 A JP 2000357159A JP 2000357159 A JP2000357159 A JP 2000357159A JP 4425453 B2 JP4425453 B2 JP 4425453B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、導電層となる金属薄膜の付いた基板に対し、金属補足能を有するカップリング剤を含む液への浸漬処理を行うことにより、導電層となる金属薄膜とその後行う電気金属めっき膜との密着性を向上させる前処理方法に関する。なお、本明細書に記載する基板は、半導体ウェハー、ガラス基板、プリント基板、ビルドアップ基板などを言う。
【０００２】
【従来の技術】
従来、基板上に導電性の金属薄膜を形成し、この上にさらに電気めっきにより銅やニッケル等の金属薄膜を形成することが行われている。
一般に、基板に形成した金属薄膜上に電気金属めっき膜を数μｍ程度付けた程度では、十分な密着性を出すことは困難である。この場合、密着性を向上させる方法として、導電層の表面をエッチング等で粗化処理して密着性を高める方法が考えられる。
しかし、従来、導電層となる金属薄膜上に電気金属めっきを行う場合、厚さが数μｍ程度になると密着性が十分に取れないという問題があった。これは、導電層となる金属薄膜の膜厚が非常に薄い（１μｍ以下程度）場合、表面粗化が困難であるため、めっきが付きにくいことが原因である。
すなわち、基板上に形成した金属薄膜の厚さが非常に薄い（１μｍ以下程度）場合には、上記粗化処理によって金属薄膜自体が無くなってしまい、次に実施される電気めっきが適切に行われず、不均一なめっき又は斑（まだら）にめっきされるということが起こり、有効なめっきができないからである。
【０００３】
【発明が解決しようとする課題】
本発明は、基板上に形成した金属薄膜の厚さが非常に薄い場合でも、その後に実施される電気金属めっき膜との密着性を向上させることのできる方法を得ることを課題とする。
【０００４】
【課題を解決するための手段】
以上の問題点に鑑み、金属イオンを補足する機能と金属薄膜上に固定する機能を同一分子内に有する特定の化合物を用いて表面処理することで、その後の電気めっき膜との密着性を向上させることが可能であるとの知見を得た。
本発明は、このような知見に基づき下記を提供するものである。
１．導電層となる金属薄膜の付いた基板に対し、下記濃度の金属補足能を有するカップリング剤を含むｐＨ２．０以下の液へ浸漬処理を行い、その後に電気金属めっきを行うことを特徴とする導電層となる金属薄膜と電気めっき膜との密着性を向上させる金属膜間密着性向上方法
カップリング剤濃度：０．００１〜１０重量％
２．導電層となる金属薄膜の付いた基板を、カップリング剤を含む液へ浸漬処理する前に１〜１０％の酸で酸洗することを特徴とする上記１記載の金属膜間密着性向上方法
３．酸洗に使用する酸が塩酸、硫酸、硝酸のいずれか又はこれらの混合酸であることを特徴とする上記２記載の金属膜間密着性向上方法
４．導電層となる金属薄膜の素材がニッケルであることを特徴とする上記１〜３のそれぞれに記載の金属膜間密着性向上方法
【０００５】
【発明の実施の形態】
本発明はカップリング剤（例えばシランカップリング剤、チタンカップリング剤など）を用いていることが特徴である。
すなわち、金属薄膜に吸着し、金属補足能を持つ官能基が分子内に存在するカップリング剤を使用することによりことにより、めっき液中の金属イオンがその官能基に補足され、その結果電気めっきの際に密着性の発現可能とするものである。
【０００６】
金属補足能を持つ官能基としては、アミノ基、カルボキシル基、アゾール基、水酸基、メルカプト基などが挙げられる。しかし、これらの基に制限されず、他の官能基を持つものであっても良い。
これらの中でもアゾール基が好ましい。アゾール基としては、イミダゾ−ル、オキサゾール、チアゾール、セレナゾール、ピラゾール、イソオキサゾール、イソチアゾール、トリアゾール、オキサジアゾール、チアジアゾール、テトラゾール、オキサトリアゾール、チアトリアゾール、ベンダゾール、インダゾール、ベンズイミダゾール、ベンゾトリアゾールなどが挙げられる。中でもイミダゾ−ル基が特に好ましい。
【０００７】
また、前記シランカップリング剤とは−ＳｉＸ１Ｘ２Ｘ３基を有する化合物であり、Ｘ１、Ｘ２、Ｘ３はアルキル基、ハロゲンやアルコキシ基などを意味し、被めっき物への固定が可能な官能基であれば良い。
Ｘ１、Ｘ２、Ｘ３は同一でもまた異なっていても良い。例えば、アゾール系化合物とエポキシシラン系化合物との反応で得られたシランカップリング剤を例示することができる（特開平６−２５６３５８号公報参照）。
【０００８】
本発明に使用する金属補足能を有するシランカップリング剤のその他の例として、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン等を挙げることができる。
【０００９】
また、前記チタンカップリング剤とは−ＴｉＸ１Ｘ２Ｘ３基またはＴｉＸ１Ｘ２Ｘ３Ｘ４Ｘ５基を有する化合物であり、Ｘ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５はアルキル基、ハロゲンやアルコキシ基などを意味し、被めっき物への固定が可能な官能基であれば良い。Ｘ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５は同一でもまた異なっていても良い。
例えば、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジ−トリデシル）ホスファイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリ（Ｎ−アミドエチル・アミノエチル）チタネート等を例示することができる。
【００１０】
また、導電層となる金属薄膜の素材は特に制限されないが、例としてニッケル・銅等が挙げられる。この中で、ニッケルは適度な耐食性を有することから、カップリング剤の金属補足能を有する官能基に補足されやすく導電層として特に好ましい。また、導電層となる金属薄膜の付いた基板を前記カップリング剤で処理する前に、１〜１０％程度の塩酸・硫酸・硝酸などの酸で酸洗することにより、カップリング剤の効果を大きくすることができる。
酸洗の際の酸濃度が１％未満では酸洗の効果はなく、また１０％を超えると効果が飽和し、それ以上は無駄となるので１〜１０％程度の酸を使用するのが好適である。
【００１１】
カップリング剤を含む液で表面処理する場合、この液は適当な溶媒、例えば、水、メチルアルコール、エチルアルコール、２−プロパノール、アセトン、トルエン、エチレングリコール、ポリエチレングリコール、ジメチルホルムアミド、ジメチルスルホキシド、ジオキサンなどや、これらを混合した溶液などに溶解させた溶液で使用できる。
【００１２】
金属膜に対しては、浸漬処理で表面コートした後に溶媒を揮発させる方法が一般的であるが、必ずしもこれに限定されるものではなく、表面に均一にカップリング剤を付着させる方法であればよい。付着状態によっては水洗のみで、乾燥工程を省略できる場合もある。
カップリング剤の濃度はこれに限ったものではないが、０．００１〜１０重量％が使用に適している。
０．００１重量％未満の場合、基材の表面に付着する化合物量が低くなりやすく、効果が得にくい。また、１０重量％を超えると付着量が多すぎて乾燥し難かったり、被膜が厚すぎてかえって密着力を低下させることがある。
カップリング剤を含む溶液のｐＨが２．０以下の場合に特にカップリング剤の効果を大きくすることができる。
【００１３】
表面処理後に使用した溶剤を揮発させるには、この溶媒の揮発温度以上に加熱して表面を乾燥すれば十分であるが、さらに６０〜１２０°Ｃで３〜６０分間加熱することが好ましい。
溶剤として水を用いた場合は乾燥工程を省略し、表面処理後水洗するだけでめっきを行うことも可能である。
前処理を行う温度は室温でも十分であるが、加熱することによって付着速度、付着量を増やすことができる。加熱する場合の温度は３０〜８０℃がよい。金属薄膜上に行う電気めっき金属は特に制限されないが、例としてニッケル・銅・金又はこれらの合金等が挙げられる。
【００１４】
【実施例及び比較例】
次に、本発明の実施例及び比較例について説明する。なお、本実施例は好適な例を示すものであって、本実施例により発明を制限するものではない。本発明はその技術思想の範囲に含まれる変形及び他の例を当然含むものである。
（実施例及び比較例）
被めっき素材として、シリコンウェハーの最表面にニッケル（２００ｎｍ）をスパッタリングしたものを用いた。めっき被膜の密着性は、スパッタニッケル膜と膜界面の劈開断面ＳＥＭ観察を行うことにより確認した。
【００１５】
（実施例１）
前記シリコンウェハーを１％−塩酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、イミダゾールとγ−グリシドキシプロピルトリメトキシシランとの等モル反応生成物であるシランカップリング剤を０．０１重量％含んだ水溶液（ｐＨ１．５）に５０°Ｃで５分間浸漬し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。
電気ニッケルめっきの条件は次の通りである。
浴温：５０°Ｃ
ｐＨ：４．０
カソード電流密度：３Ａ／ｄｍ２
めっき時間：５００ｓｅｃ
攪拌：空気攪拌
めっき膜界面を断面観察した結果、隙間は全く見られず、ニッケルはシリコンウェハー全面に密着性良好にめっきされた。（図１参照）
【００１６】
（実施例２）
前記シリコンウェハーを１％−塩酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、γ−アミノプロピルトリエトキシシラン（関東化学（株）製）を０．０２重量％含んだ水溶液（ｐＨ１．２）に５０°Ｃで５分間浸漬し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。ニッケルめっきは実施例１と同様の条件で実施した。
めっき膜界面を断面観察した結果、隙間は全く見られず、ニッケルはシリコンウェハー全面に密着性良好にめっきされた。
【００１７】
（実施例３）
前記シリコンウェハーを５％−硫酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、実施例１で調整したシランカップリング剤を０．０５重量％含んだ水溶液（ｐＨ１．０）に５０°Ｃで５分間浸漬し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。ニッケルめっきは実施例１と同様の条件で実施した。
めっき膜界面を断面観察した結果、隙間は全く見られず、ニッケルはシリコンウェハー全面に密着性良好にめっきされた。
【００１８】
（実施例４）
前記シリコンウェハーを１０％−硝酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、実施例１で調整したシランカップリング剤を０．１重量％含んだ水溶液（ｐＨ１．７）に５０°Ｃで５分間浸漬し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。ニッケルめっきは実施例１と同様の条件で実施した。
めっき膜界面を断面観察した結果、隙間は全く見られず、ニッケルはシリコンウェハー全面に密着性良好にめっきされた。
【００１９】
（比較例１）
前記シリコンウェハーを１％−塩酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。ニッケルめっきは実施例１と同様の条件で実施した。
めっき膜界面を断面観察した結果、界面全体に隙間が見られた（図２参照）。
この例に示すように、本発明のカップリング剤を含む液へ浸漬処理を行わない場合には、電気ニッケルめっき皮膜の密着性は不良となった。
【００２０】
（比較例２）
前記シリコンウェハーを５％−塩酸溶液に１分間浸漬洗浄し、流水で十分に水洗後、実施例１で調整したシランカップリング剤を０．１重量％含んだ水溶液（ｐＨ５．０）に５０°Ｃで５分間浸漬し、流水で十分に水洗後、電気ニッケルめっき液（日鉱メタルプレーティング（株）製スルファミン酸ニッケルめっき液）を用いて、厚さ５μｍ相当のめっきを行った。ニッケルめっきは実施例１と同様の条件で実施した。
めっき膜界面を断面観察した結果、界面の一部に隙間が見られた（図３参照）。このようにｐＨが高いと実施例と同一のシランカップリング剤を使用した場合でも、めっきが適切に行われない場合があることが分かった。
【００２１】
上記実施例では、γ−アミノプロピルトリエトキシシランを使用したが、これ以外、すなわち上記に挙げた例に示す種々のカップリング剤を使用した場合も同様の結果が得られた。
また、対比の例（比較例）を特に示していないが、カップリング剤で処理する前に、１〜１０％程度の塩酸・硫酸・硝酸などの酸で酸洗することにより、カップリング剤の効果を大きくすることが確認できた。さらに、カップリング剤を含む液のｐＨが２．０以下である場合に、特に密着性を向上させる効果があった。
【００２２】
【発明の効果】
導電層となる金属薄膜の付いた基板上への電気めっきに際し、金属イオンを補足する機能と金属薄膜上に固定する機能を同一分子内に有するカップリング剤を用いて表面処理するという比較的簡便な処理により、その後の電気めっき膜との密着性を著しく向上させることができるという優れた効果を有する。
【図面の簡単な説明】
【図１】実施例１におけるめっき膜界面の断面顕微鏡写真である。
【図２】比較例１におけるめっき膜界面の断面顕微鏡写真である。
【図３】比較例２におけるめっき膜界面の断面顕微鏡写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal thin film to be a conductive layer and a subsequent electrometal plating film by immersing the substrate with the metal thin film to be a conductive layer in a liquid containing a coupling agent having a metal-capturing ability. It is related with the pre-processing method which improves adhesiveness. In addition, the board | substrate described in this specification says a semiconductor wafer, a glass substrate, a printed circuit board, a buildup board | substrate.
[0002]
[Prior art]
Conventionally, a conductive metal thin film is formed on a substrate, and a metal thin film such as copper or nickel is further formed thereon by electroplating.
In general, it is difficult to obtain sufficient adhesion when an electrometal plating film is formed on a metal thin film formed on a substrate by about several μm. In this case, as a method for improving the adhesion, a method for improving the adhesion by roughening the surface of the conductive layer by etching or the like can be considered.
However, conventionally, when electrometal plating is performed on a metal thin film serving as a conductive layer, there is a problem that sufficient adhesion cannot be obtained when the thickness is about several μm. This is because when the thickness of the metal thin film serving as the conductive layer is very thin (about 1 μm or less), it is difficult to roughen the surface, and thus plating is difficult to adhere.
That is, when the thickness of the metal thin film formed on the substrate is very thin (about 1 μm or less), the metal thin film itself is lost by the roughening treatment, and the subsequent electroplating is not performed appropriately. This is because non-uniform plating or plating on mottles occurs, and effective plating cannot be performed.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to obtain a method capable of improving the adhesion with an electrometal plating film to be performed thereafter even when the thickness of a metal thin film formed on a substrate is very thin.
[0004]
[Means for Solving the Problems]
In view of the above problems, surface treatment using a specific compound having the function of capturing metal ions and the function of fixing on a metal thin film in the same molecule improves the adhesion to the subsequent electroplated film The knowledge that it was possible to get it.
The present invention provides the following based on such findings.
1. A substrate with a metal thin film serving as a conductive layer is subjected to an immersion treatment in a solution having a pH of 2.0 or less containing a coupling agent having a metal-capturing ability with the following concentration, and then electrometal plating is performed. Method for improving adhesion between metal films for improving adhesion between a metal thin film serving as a conductive layer and an electroplating film Coupling agent concentration: 0.001 to 10% by weight
2. 2. The method for improving adhesion between metal films according to 1 above, wherein the substrate with a metal thin film to be a conductive layer is pickled with 1 to 10% acid before being immersed in a liquid containing a coupling agent. 3. 3. The method for improving adhesion between metal films according to 2 above, wherein the acid used for pickling is any one of hydrochloric acid, sulfuric acid, nitric acid, or a mixed acid thereof. The method for improving adhesion between metal films according to each of the above 1 to 3, wherein the material of the metal thin film to be the conductive layer is nickel.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is characterized by using a coupling agent (for example, a silane coupling agent, a titanium coupling agent, etc.).
That is, by using a coupling agent that adsorbs to a metal thin film and has a functional group having a metal-capturing ability in the molecule, the metal ion in the plating solution is captured by the functional group, and as a result, electroplating In this case, adhesion can be expressed.
[0006]
Examples of the functional group having a metal-capturing ability include an amino group, a carboxyl group, an azole group, a hydroxyl group, and a mercapto group. However, it is not limited to these groups and may have other functional groups.
Among these, an azole group is preferable. Examples of the azole group include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, bendazole, indazole, benzimidazole, benzotriazole, and the like. Can be mentioned. Of these, an imidazole group is particularly preferred.
[0007]
Further, with the silane coupling agent is a compound having a -SiX 1 X 2 X 3 group, X 1, X 2, X 3 means an alkyl group, a halogen or an alkoxy group, fixed to the object to be plated Any functional group can be used.
X 1, X 2 and X 3 may be the same or different. For example, a silane coupling agent obtained by the reaction of an azole compound and an epoxy silane compound can be exemplified (see JP-A-6-256358).
[0008]
Other examples of the silane coupling agent having a metal scavenging ability used in the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane. N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like.
[0009]
The titanium coupling agent is a compound having a -TiX 1 X 2 X 3 group or a TiX 1 X 2 X 3 X 4 X 5 group, and X 1 , X 2 , X 3 , X 4 and X 5 are It means an alkyl group, a halogen or an alkoxy group, and any functional group that can be fixed to an object to be plated. X 1, X 2, X 3 , X 4 , and X 5 may be the same or different.
For example, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-) Examples include tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltri (N-amidoethylaminoethyl) titanate, and the like.
[0010]
Moreover, the material of the metal thin film used as the conductive layer is not particularly limited, and examples thereof include nickel and copper. Among these, nickel has a moderate corrosion resistance and is therefore particularly preferable as a conductive layer because it is easily captured by a functional group having a metal-capturing ability of a coupling agent. In addition, before the substrate with the metal thin film to be a conductive layer is treated with the coupling agent, the effect of the coupling agent is obtained by pickling with an acid such as about 1 to 10% hydrochloric acid, sulfuric acid, nitric acid. Can be bigger.
If the acid concentration during pickling is less than 1%, there is no effect of pickling, and if it exceeds 10%, the effect is saturated, and more than that is wasted, so it is preferable to use about 1 to 10% acid. It is.
[0011]
When the surface treatment is performed with a liquid containing a coupling agent, this liquid may be an appropriate solvent such as water, methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethylformamide, dimethyl sulfoxide, dioxane. Or a solution obtained by dissolving them in a mixed solution.
[0012]
For metal films, the method of volatilizing the solvent after surface coating by dipping is common, but the method is not necessarily limited to this, and any method that uniformly attaches a coupling agent to the surface can be used. Good. Depending on the state of adhesion, there may be a case where the drying step can be omitted only by washing with water.
The concentration of the coupling agent is not limited to this, but 0.001 to 10% by weight is suitable for use.
If it is less than 0.001% by weight, the amount of the compound adhering to the surface of the substrate tends to be low, and the effect is difficult to obtain. On the other hand, if it exceeds 10% by weight, the amount of adhesion may be too large to be dried, or the coating may be too thick, which may reduce the adhesion.
The effect of the coupling agent can be particularly enhanced when the pH of the solution containing the coupling agent is 2.0 or less.
[0013]
In order to volatilize the solvent used after the surface treatment, it is sufficient to heat the solvent to a temperature higher than the volatilization temperature and dry the surface, but it is preferable to further heat at 60 to 120 ° C. for 3 to 60 minutes.
When water is used as a solvent, it is possible to omit the drying step and perform plating only by washing with water after the surface treatment.
Although the room temperature is sufficient for the pretreatment, the deposition rate and the deposition amount can be increased by heating. The temperature for heating is preferably 30 to 80 ° C. The electroplating metal performed on the metal thin film is not particularly limited, and examples thereof include nickel, copper, gold, and alloys thereof.
[0014]
[Examples and Comparative Examples]
Next, examples and comparative examples of the present invention will be described. In addition, a present Example shows a suitable example, Comprising: This invention does not restrict | limit this invention. The present invention naturally includes modifications and other examples included in the scope of the technical idea.
(Examples and Comparative Examples)
As a material to be plated, a material obtained by sputtering nickel (200 nm) on the outermost surface of a silicon wafer was used. The adhesion of the plated coating was confirmed by performing a cleaved cross-sectional SEM observation of the sputtered nickel film and the film interface.
[0015]
Example 1
The silicon wafer was immersed and washed in a 1% -hydrochloric acid solution for 1 minute, washed thoroughly with running water, and then a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, was added in an amount of 0.00. Immerse in an aqueous solution (pH 1.5) containing 01% by weight at 50 ° C. for 5 minutes, thoroughly wash with running water, and then use an electro nickel plating solution (a nickel sulfamate plating solution manufactured by Nikko Metal Plating Co., Ltd.). Then, plating corresponding to a thickness of 5 μm was performed.
The conditions for electro nickel plating are as follows.
Bath temperature: 50 ° C
pH: 4.0
Cathode current density: 3 A / dm 2
Plating time: 500 sec
Stirring: As a result of cross-sectional observation of the air stirring plating film interface, no gap was observed, and nickel was plated on the entire surface of the silicon wafer with good adhesion. (See Figure 1)
[0016]
(Example 2)
The silicon wafer was immersed and washed in a 1% -hydrochloric acid solution for 1 minute, washed thoroughly with running water, and then an aqueous solution containing 0.02% by weight of γ-aminopropyltriethoxysilane (manufactured by Kanto Chemical Co., Inc.) (pH 1. 2) Immerse in 50 ° C for 5 minutes, rinse thoroughly with running water, and then perform plating equivalent to a thickness of 5μm using an electric nickel plating solution (Nikko Metal Plating Co., Ltd. sulfamate plating solution). It was. Nickel plating was performed under the same conditions as in Example 1.
As a result of cross-sectional observation of the plating film interface, no gap was found, and nickel was plated on the entire surface of the silicon wafer with good adhesion.
[0017]
(Example 3)
The silicon wafer was immersed and washed in a 5% -sulfuric acid solution for 1 minute, sufficiently washed with running water, and then washed with an aqueous solution (pH 1.0) containing 0.05% by weight of the silane coupling agent prepared in Example 1 at 50 °. After being immersed in C for 5 minutes and sufficiently washed with running water, plating corresponding to a thickness of 5 μm was performed using an electro nickel plating solution (nickel sulfamate plating solution manufactured by Nikko Metal Plating Co., Ltd.). Nickel plating was performed under the same conditions as in Example 1.
As a result of cross-sectional observation of the plating film interface, no gap was found, and nickel was plated on the entire surface of the silicon wafer with good adhesion.
[0018]
Example 4
The silicon wafer was immersed and washed in a 10% -nitric acid solution for 1 minute, washed thoroughly with running water, and then washed with an aqueous solution (pH 1.7) containing 0.1% by weight of the silane coupling agent prepared in Example 1 at 50 °. After being immersed in C for 5 minutes and sufficiently washed with running water, plating corresponding to a thickness of 5 μm was performed using an electro nickel plating solution (nickel sulfamate plating solution manufactured by Nikko Metal Plating Co., Ltd.). Nickel plating was performed under the same conditions as in Example 1.
As a result of cross-sectional observation of the plating film interface, no gap was found, and nickel was plated on the entire surface of the silicon wafer with good adhesion.
[0019]
(Comparative Example 1)
The silicon wafer is immersed and washed in a 1% -hydrochloric acid solution for 1 minute, thoroughly washed with running water, and then with an electro nickel plating solution (nickel sulfamate plating solution manufactured by Nikko Metal Plating Co., Ltd.), equivalent to a thickness of 5 μm. Was plated. Nickel plating was performed under the same conditions as in Example 1.
As a result of cross-sectional observation of the plating film interface, a gap was found throughout the interface (see FIG. 2).
As shown in this example, when the immersion treatment was not performed in the liquid containing the coupling agent of the present invention, the adhesion of the electro nickel plating film was poor.
[0020]
(Comparative Example 2)
The silicon wafer was immersed and washed in a 5% -hydrochloric acid solution for 1 minute, washed thoroughly with running water, and then washed with an aqueous solution (pH 5.0) containing 0.1% by weight of the silane coupling agent prepared in Example 1 at 50 °. After being immersed in C for 5 minutes and sufficiently washed with running water, plating corresponding to a thickness of 5 μm was performed using an electro nickel plating solution (nickel sulfamate plating solution manufactured by Nikko Metal Plating Co., Ltd.). Nickel plating was performed under the same conditions as in Example 1.
As a result of observing a cross section of the plating film interface, a gap was found in a part of the interface (see FIG. 3). Thus, when pH was high, even when the same silane coupling agent as the Example was used, it turned out that plating may not be performed appropriately.
[0021]
In the above examples, γ-aminopropyltriethoxysilane was used, but similar results were obtained when other than this, that is, when various coupling agents shown in the above examples were used.
Moreover, although the example of comparison (comparative example) is not shown in particular, before processing with a coupling agent, it pickles with about 1-10% of acid, such as hydrochloric acid, sulfuric acid, nitric acid, It was confirmed that the effect was increased. Further, when the pH of the liquid containing the coupling agent is 2.0 or less, there is an effect of improving the adhesion particularly.
[0022]
【The invention's effect】
When electroplating onto a substrate with a metal thin film that becomes a conductive layer, surface treatment is performed using a coupling agent that has the function of capturing metal ions and the function of fixing on the metal thin film in the same molecule. By this process, it has an excellent effect that the adhesion with the subsequent electroplating film can be remarkably improved.
[Brief description of the drawings]
1 is a cross-sectional micrograph of a plating film interface in Example 1. FIG.
2 is a cross-sectional micrograph of a plating film interface in Comparative Example 1. FIG.
3 is a cross-sectional micrograph of a plating film interface in Comparative Example 2. FIG.
Claims (4)
カップリング剤濃度：０．００１〜１０重量％A substrate with a metal thin film serving as a conductive layer is subjected to an immersion treatment in a solution having a pH of 2.0 or less containing a coupling agent having a metal-capturing ability with the following concentration, followed by electrometal plating. A method for improving adhesion between metal films, which improves adhesion between a metal thin film serving as a conductive layer and an electroplating film.
Coupling agent concentration: 0.001 to 10% by weight
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| JP2000357159A JP4425453B2 (en) | 2000-11-24 | 2000-11-24 | Method for improving adhesion between metal films |
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| JP2000357159A JP4425453B2 (en) | 2000-11-24 | 2000-11-24 | Method for improving adhesion between metal films |
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| EP1538237B1 (en) | 2002-09-10 | 2009-09-30 | Nippon Mining & Metals Co., Ltd. | Method for metal plating and pre-treating agent |
| JP2011179085A (en) * | 2010-03-02 | 2011-09-15 | C Uyemura & Co Ltd | Pretreatment agent and pretreatment method for electroplating and electroplating method |
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