JP2004107737A - Circuit board and wiring formation method therefor - Google Patents
Circuit board and wiring formation method therefor Download PDFInfo
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- JP2004107737A JP2004107737A JP2002273093A JP2002273093A JP2004107737A JP 2004107737 A JP2004107737 A JP 2004107737A JP 2002273093 A JP2002273093 A JP 2002273093A JP 2002273093 A JP2002273093 A JP 2002273093A JP 2004107737 A JP2004107737 A JP 2004107737A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、微細な金属配線を有する集積回路などの回路基板とその金属配線の形成方法に関する。
【０００２】
【従来の技術】
従来、回路基板の金属配線を形成する方法としては、金属蒸着法、スパッタ法、ＣＶＤ法などの気相法が主に実施されいたが、最近では電解メッキや無電解メッキなどの液相法も実施されている。
【０００３】
【発明が解決しようとする課題】
集積回路の高密度化の進展に伴って、微細溝やコンタクトホール、スルーホールなどの微細化が進み、回路面にアスペクト比の大きな微細溝やホールが形成されている。このようなアスペクト比の大きな微細溝やホールを有する回路面に配線を形成する場合、気相法ではホールのエッジ部分に膜が生成し易いため、アスペクト比が大きくなるとホール内部に膜が付いていない部分（ボイド）が発生し易くなる。また、電解メッキを行う場合にも微細溝やホール内部に予め気相法でシード層を形成しており、このためアスペクト比の大きい微細溝やホールについて配線不良を生じやすい問題がある。
【０００４】
また、金属パラジウムを回路形成面に付着させた後に無電解メッキを施す場合、パラジウム触媒の粒子サイズが大きいために付着密度が低くなる問題を解消するために、銀活性化処理を行った後にパラジウム活性化処理を行う方法も知られている（特開２０００−３３６４８６）。
【０００５】
しかし、最近の高密度回路における微細溝やホールのように、溝幅やホール径がサブミクロンレベルの場合、パラジウム触媒などの金属粒子径を単に小さいしても溶媒の液性や金属粒子の濃度などの影響によって溝やホールの深部に金属微粒子が十分に付着せず、メッキが不良になる場合がある。
【０００６】
本発明は従来の配線形成方法における上記問題を解消したものであり、アスペクト比の高いサブミクロンレベルの微細な溝やホールについても信頼性の高い配線を形成することができる方法を提供する。
【０００７】
本発明によれば、以下の構成からなる配線形成方法とその回路基板が提供される。
（１）回路基板の配線形成面に金属微粒子を付着させ、この金属微粒子を触媒として無電解メッキ法によって金属配線を形成する方法において、粒径がコロイド粒子以下の金属微粒子を、５０ｋｃａｌ／ｍｏｌ以上の極性値を有する溶媒に、１×１０１７個／ｍ３以上の濃度で分散させた金属コロイド液を上記配線形成面に塗布し乾燥させて無電解メッキを行うことを特徴とする回路基板の配線形成方法。
（２）平均粒径２０ｎｍ以下の金属微粒子を用いる上記（１）の配線形成方法。
（３）金属微粒子の濃度が１×１０１７〜１×１０２２個／ｍ３である金属コロイド液を用いる上記（１）または（２）の方法。
（４）金属微粒子として金、白金、またはパラジウムの微粒子を用いる上記（１）、（２）または（３）の配線形成方法。
（５）上記（１）〜（４）の何れかの方法によって形成された回路基板。
【０００８】
【具体的な説明】
本発明に係る回路基板の配線形成方法は、回路基板の配線形成面に金属微粒子を付着させ、この金属微粒子を触媒として無電解メッキ法によって金属配線を形成する方法において、粒径がコロイド粒子以下の金属微粒子を、５０ｋｃａｌ／ｍｏｌ以上の極性値を有する溶媒に、１×１０１７個／ｍ３以上の濃度で分散させた金属コロイド液を上記配線形成面に塗布し、乾燥させて無電解メッキを行うことを特徴とする方法である。
【０００９】
回路基板の配線形成面は基板の絶縁体面またはシード層などの高融点金属面などである。配線形成面に電極を形成する場合、微細孔やホールに触媒として作用する金属微粒子を付着させ、直に無電解メッキで電極を形成する方法や、触媒の金属微粒子を付着させた後に無電解メッキでシード層を形成し、その上側に電解メッキで電極を形成する方法などが知られているが、本発明の方法は何れの場合にも適用することができる。
【００１０】
配線形成面に付着させる金属微粒子としては触媒作用が強い金、白金、またはパラジウムの微粒子が好適に用いられる。この金属微粒子は粒径がコロイド粒子以下、すなわち１μｍ以下のものが用いられ、サブミクロンレベルのアスペクト比の大きい微細溝やホールに対しては平均粒径２０ｎｍ以下の微粒子ものを用いるのが好ましい。
【００１１】
これらの金属微粒子を分散させる溶媒としては、５０ｋｃａｌ／ｍｏｌ以上の極性値を有するものが用いられる。具体的には、水、エタノール、１−プロパノール、１−ブタノールなどが挙げられる。クロロホルム、ベンゼン、シクロヘキサン、ヘキサンなどは極性値が上記値より小さいので好ましくない。極性値が上記値より大きい溶媒では金属微粒子が凝集せずに分散し易いが、極性値が上記値より小さい溶媒では金属微粒子が凝集し易い。金属微粒子が凝集するとその比表面積が小さくなるので触媒効果が低下し、また凝集粒子径が大きくなるので微細孔やホールに入り込み難くなり、無電解メッキによる電極形成が不十分になる。
【００１２】
上記溶媒中の金属微粒子の濃度は１×１０１７個／ｍ３以上が必要であり、１×１０１７〜１×１０２２個／ｍ３が好ましい。これより金属微粒子の濃度が少ないと、回路形成面に付着する金属量が不足して、十分な触媒作用を得ることができなくなる。なお、溶媒中の金属微粒子の濃度が上記範囲より高くても触媒効果は大差ないので金属微粒子の濃度は上記範囲が適当である。
【００１３】
上記金属微粒子のコロイド液を回路形成面に塗布して乾燥させ、アスペクト比の大きい微細溝やホール内部に金属微粒子を触媒として付着させて無電解メッキを行い、金属配線を形成することにより、微細溝やホール内部にボイドのない金属配線を形成することができる。
【００１４】
無電解メッキの一例として、銅メッキ液の一般的な組成を以下に示す。
〔金属塩〕：無電解銅メッキでは液中の銅イオンの還元によって金属銅を析出させるので、液中に十分な銅イオンが必要となる。この供給源としては一般に硫酸銅（ＣｕＳＯ４・５Ｈ２０）や塩化銅（ＣｕＣ１２・２Ｈ２０）が用いられる。
〔還元剤〕：金属銅を還元析出させるに必要な電子を供給するための還元剤は銅の還元電位より電気化学的に卑な酸化還元電位を持っている必要がある。銅より酸化還元電位が低い還元剤としては、ホルムアルデヒド（ＨＣＨＯ）、ヒドラジン（Ｎ２Ｈ４）、ジメチルアミンボラン（Ｃ２Ｈ１０ＢＮ）、ホスフイン酸塩（Ｈ３ＰＯ２）、グリオキシル酸（ＣＨＯＣＯＯＨ）等が挙げられる。
〔ｐＨ調整剤〕：還元剤の酸化反応を促進させるためには液のｐＨを高くする必要がある。一方、ｐＨが高すぎると反応が活発すぎて液が自己分解反応を起こすので、銅塩溶液から銅を還元析出するには液のｐＨを１１〜１２．５に調整するのが好ましい。一般にｐＨ調整剤には水酸化ナトリウム、水酸化カリウムなどが挙げられるが、これらに含まれるアルカリ土類金属はシリコン中への拡散が速く、シリコンデバイスプロセスには向かない。そこで、シリコン基板の回路形成には水酸化テトラメチルアンモニウム五水和物（ＴＭＡＨ：［ＣＨ３］４ＮＯＨ・５Ｈ２０）が好ましい。
【００１５】
〔錯化剤〕：銅塩溶液は高ｐＨ域で水に不溶性の水酸化銅沈澱（Ｃｕ（ＯＨ）２）を生じるので、錯化剤を添加して銅イオンを錯イオンにして沈殿を防止する必要がある。この錯化剤として−般にはエチレンジアミン四酢酸（Ｃ６Ｈ１６Ｎ２０８）等が使用される。
〔界面活性剤〕：無電解銅メッキでは反応の進行に伴い水素ガスが発生する。この水素ガスがメッキ膜中に拡散して、メッキ膜の物性を悪化する。発生した水素ガスがメッキ面に留まらず速やかに離脱すればメッキ膜の劣化が少なくなる。このためにはメッキ浴の界面張力を下げることが必要であり、この界面活性剤として一般に分子量１０００程度のポリエチレングリコールが使用される。
【００１６】
【実施例】
本発明の実施例および比較例を以下に示す。
表１に示す平均粒径と溶液組成および濃度の金コロイド液を用い、これをシリコン回路基板の配線形成面に滴下し、乾燥した後にメッキ液に浸漬して無電解メッキを行った。形成された配線の状態を表１に示した。またメッキ液の条件を表２に示した。
この結果に示すように、本発明に係る試料Ｎｏ．１〜７は良好な配線が形成される。一方、溶媒の組成、金属微粒子の平均粒径および濃度が本発明の好適な範囲から外れる試料Ｎｏ．８〜１３は、形成された配線が断線しており、良好な配線が形成されない。
【００１７】
【表１】
【表２】
【発明の効果】
本発明の回路形成方法によれば、アスペクト比の大きい微細溝やホール内部にボイドのない金属配線を形成することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a circuit board such as an integrated circuit having fine metal wiring and a method for forming the metal wiring.
[0002]
[Prior art]
Conventionally, as a method of forming metal wiring on a circuit board, a vapor phase method such as a metal vapor deposition method, a sputtering method, and a CVD method has been mainly performed, but recently, a liquid phase method such as electrolytic plating and electroless plating has also been used. It has been implemented.
[0003]
[Problems to be solved by the invention]
As the density of integrated circuits has increased, miniaturization of fine grooves, contact holes, and through holes has progressed, and fine grooves and holes having a large aspect ratio have been formed on the circuit surface. When wiring is formed on a circuit surface having such fine grooves and holes having a large aspect ratio, a film is easily formed at the edge portion of the hole by the vapor phase method. Missing portions (voids) are likely to occur. Also, in the case of performing electrolytic plating, a seed layer is formed in advance in a fine groove or hole by a vapor phase method, and therefore, there is a problem that a wiring failure easily occurs in the fine groove or hole having a large aspect ratio.
[0004]
Also, when electroless plating is performed after metal palladium is adhered to the circuit formation surface, in order to eliminate the problem that the adhesion density is low due to the large particle size of the palladium catalyst, palladium is activated after performing silver activation treatment. A method of performing an activation process is also known (JP-A-2000-336486).
[0005]
However, when the groove width and hole diameter are on the submicron level, such as fine grooves and holes in recent high-density circuits, even if the metal particle diameter of a palladium catalyst or the like is simply reduced, the solvent properties and the concentration of the metal particles can be reduced. In some cases, metal fine particles do not sufficiently adhere to the deep portion of the groove or hole due to the influence of the above, and plating may be defective.
[0006]
The present invention has solved the above-mentioned problem in the conventional wiring forming method, and provides a method capable of forming a highly reliable wiring even in a sub-micron level fine groove or hole having a high aspect ratio.
[0007]
According to the present invention, a wiring forming method having the following configuration and a circuit board thereof are provided.
(1) In a method in which metal fine particles are adhered to a wiring forming surface of a circuit board and metal wiring is formed by electroless plating using the metal fine particles as a catalyst, the metal fine particles having a particle size of not more than colloid particles are reduced to 50 kcal / mol or more. A metal colloid liquid dispersed in a solvent having a polarity value of 1 × 10 17 particles / m 3 or more on the wiring forming surface, followed by drying to perform electroless plating. Wiring formation method.
(2) The wiring forming method according to the above (1), wherein metal fine particles having an average particle diameter of 20 nm or less are used.
(3) The method according to the above (1) or (2), wherein a metal colloid liquid having a metal fine particle concentration of 1 × 10 17 to 1 × 10 22 particles / m 3 is used.
(4) The wiring forming method according to the above (1), (2) or (3), wherein fine particles of gold, platinum or palladium are used as the metal fine particles.
(5) A circuit board formed by any one of the above (1) to (4).
[0008]
[Specific explanation]
The method for forming a wiring on a circuit board according to the present invention is a method for forming metal wiring by electroless plating using metal fine particles as a catalyst by attaching metal fine particles to the wiring forming surface of the circuit board. A metal colloid liquid obtained by dispersing metal fine particles in a solvent having a polarity value of 50 kcal / mol or more at a concentration of 1 × 10 17 particles / m 3 or more is applied to the wiring forming surface, dried, and subjected to electroless plating. Is performed.
[0009]
The wiring formation surface of the circuit board is an insulator surface of the substrate or a high melting point metal surface such as a seed layer. When forming an electrode on the wiring formation surface, a method of attaching metal fine particles acting as a catalyst to the fine holes and holes and directly forming the electrode by electroless plating, or electroless plating after attaching the metal fine particles of the catalyst A method is known in which a seed layer is formed on the substrate and an electrode is formed on the seed layer by electrolytic plating. However, the method of the present invention can be applied to any case.
[0010]
As the metal fine particles adhered to the wiring forming surface, fine particles of gold, platinum, or palladium having a strong catalytic action are preferably used. The metal fine particles have a particle size equal to or less than colloidal particles, that is, 1 μm or less, and it is preferable to use fine particles having an average particle size of 20 nm or less for fine grooves and holes having a large aspect ratio on the submicron level.
[0011]
As a solvent for dispersing these metal fine particles, a solvent having a polarity value of 50 kcal / mol or more is used. Specific examples include water, ethanol, 1-propanol, 1-butanol and the like. Chloroform, benzene, cyclohexane, hexane and the like are not preferred because their polar values are smaller than the above values. In a solvent having a polarity value larger than the above value, the metal fine particles are easily dispersed without being aggregated, but in a solvent having a polarity value smaller than the above value, the metal fine particles are easily aggregated. When the metal fine particles are aggregated, the specific surface area is reduced, so that the catalytic effect is reduced. In addition, since the aggregated particle diameter is large, it is difficult to enter fine holes or holes, and electrode formation by electroless plating becomes insufficient.
[0012]
The concentration of the metal fine particles in the solvent should be 1 × 10 17 particles / m 3 or more, and preferably 1 × 10 17 to 1 × 10 22 particles / m 3 . If the concentration of the metal fine particles is lower than this, the amount of metal adhering to the circuit forming surface becomes insufficient, and it becomes impossible to obtain a sufficient catalytic action. In addition, even if the concentration of the metal fine particles in the solvent is higher than the above range, the catalytic effect is not significantly different, so the concentration of the metal fine particles is appropriate in the above range.
[0013]
The colloidal liquid of the metal fine particles is applied to the circuit forming surface and dried, and the fine metal particles are adhered to the inside of the fine grooves and holes having a large aspect ratio as a catalyst, and electroless plating is performed to form metal wiring. A metal wiring without voids can be formed inside a groove or a hole.
[0014]
As an example of electroless plating, a general composition of a copper plating solution is shown below.
[Metal salt]: In electroless copper plating, metallic copper is precipitated by reduction of copper ions in the liquid, so that sufficient copper ions are required in the liquid. The general copper sulfate (CuSO 4 · 5H 2 0) and copper chloride (CuC1 2 · 2H 2 0) is used as a source.
[Reducing agent]: A reducing agent for supplying electrons required for reducing and depositing metallic copper needs to have an oxidation-reduction potential electrochemically lower than that of copper. As a reducing agent having a redox potential lower than that of copper, formaldehyde (HCHO), hydrazine (N 2 H 4 ), dimethylamine borane (C 2 H 10 BN), phosphinate (H 3 PO 2 ), glyoxylic acid (CHOCOOH) ) And the like.
[PH adjuster]: It is necessary to increase the pH of the solution in order to promote the oxidation reaction of the reducing agent. On the other hand, if the pH is too high, the reaction becomes too active and the liquid undergoes a self-decomposition reaction. Therefore, in order to reduce and precipitate copper from the copper salt solution, it is preferable to adjust the pH of the liquid to 11 to 12.5. Generally, pH adjusters include sodium hydroxide, potassium hydroxide and the like, but the alkaline earth metal contained therein diffuses rapidly into silicon and is not suitable for silicon device processes. Therefore, tetramethylammonium hydroxide pentahydrate in circuit formation of the silicon substrate (TMAH: [CH 3] 4NOH · 5H 2 0) is preferable.
[0015]
[Complexing agent]: Since a copper salt solution produces a water-insoluble copper hydroxide precipitate (Cu (OH) 2 ) in a high pH range, a complexing agent is added to convert copper ions into complex ions to prevent precipitation. There is a need to. As the complexing agent - ethylenediaminetetraacetic acid (C 6 H 16 N 2 0 8) or the like is used for the general.
[Surfactant]: In electroless copper plating, hydrogen gas is generated as the reaction proceeds. This hydrogen gas diffuses into the plating film and deteriorates the physical properties of the plating film. If the generated hydrogen gas does not stay on the plating surface and is quickly released, the deterioration of the plating film is reduced. For this purpose, it is necessary to lower the interfacial tension of the plating bath, and polyethylene glycol having a molecular weight of about 1,000 is generally used as the surfactant.
[0016]
【Example】
Examples of the present invention and comparative examples are shown below.
A gold colloid solution having an average particle diameter, a solution composition and a concentration shown in Table 1 was dropped on a wiring forming surface of a silicon circuit board, dried, immersed in a plating solution, and subjected to electroless plating. Table 1 shows the state of the formed wiring. Table 2 shows the conditions of the plating solution.
As shown in the results, the sample No. Nos. 1 to 7 form good wiring. On the other hand, the sample No. 3 in which the composition of the solvent, the average particle diameter and the concentration of the metal fine particles are out of the preferred ranges of the present invention. In Nos. 8 to 13, the formed wiring is broken, and good wiring is not formed.
[0017]
[Table 1]
[Table 2]
【The invention's effect】
According to the circuit forming method of the present invention, it is possible to form a metal wiring having no void inside a fine groove or hole having a large aspect ratio.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002273093A JP3870883B2 (en) | 2002-09-19 | 2002-09-19 | Circuit board and wiring formation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002273093A JP3870883B2 (en) | 2002-09-19 | 2002-09-19 | Circuit board and wiring formation method thereof |
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| Publication Number | Publication Date |
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| JP2004107737A true JP2004107737A (en) | 2004-04-08 |
| JP3870883B2 JP3870883B2 (en) | 2007-01-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007154307A (en) * | 2005-11-08 | 2007-06-21 | Univ Waseda | Electroless copper plating liquid, electroless copper plating method, and ulsi copper wiring formation method |
| WO2013035480A1 (en) * | 2011-09-09 | 2013-03-14 | 学校法人 関西大学 | Catalyst adsorption method and adsorption device |
| KR101783163B1 (en) | 2014-07-17 | 2017-09-28 | 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 | Pretreatment solution for electroless plating and electroless plating method |
| CN108463576A (en) * | 2016-01-29 | 2018-08-28 | 株式会社杰希优 | The method that circuit is formed on substrate |
-
2002
- 2002-09-19 JP JP2002273093A patent/JP3870883B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007154307A (en) * | 2005-11-08 | 2007-06-21 | Univ Waseda | Electroless copper plating liquid, electroless copper plating method, and ulsi copper wiring formation method |
| WO2013035480A1 (en) * | 2011-09-09 | 2013-03-14 | 学校法人 関西大学 | Catalyst adsorption method and adsorption device |
| KR101783163B1 (en) | 2014-07-17 | 2017-09-28 | 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 | Pretreatment solution for electroless plating and electroless plating method |
| CN108463576A (en) * | 2016-01-29 | 2018-08-28 | 株式会社杰希优 | The method that circuit is formed on substrate |
| CN108463576B (en) * | 2016-01-29 | 2021-07-23 | 株式会社杰希优 | Method of forming circuit on substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3870883B2 (en) | 2007-01-24 |
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