JP2005072306A - Metal plate/bar for electronic component, and its manufacturing method - Google Patents
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Description
本発明は、半導体装置等の電子部品に用いるＮｉ又はＮｉ合金めっき付き若しくはめっきを省略した金属板・条材（板材又は条材のこと）及びその製造方法に関する。特に樹脂との密着性に優れ、ＢＧＡ（Ball Grid Array）用の放熱板及びリードフレーム等に適し、さらに詳しくは樹脂系接着剤によって樹脂又は半導体素子との接着及び封止樹脂との接着を要するＢＧＡ用の放熱板や、半導体素子との接着及び封止樹脂との接着を要するリードフレーム材料等として好適な電子部品用金属板・条材及びその製造方法に関する。 The present invention relates to a metal plate / strip material (plate material or strip material) with or without Ni or Ni alloy plating used for electronic components such as semiconductor devices and a method for manufacturing the same. In particular, it has excellent adhesion to resin and is suitable for heat sinks and lead frames for BGA (Ball Grid Array). More specifically, it requires adhesion to a resin or semiconductor element and adhesion to a sealing resin with a resin adhesive. The present invention relates to a heat dissipation plate for BGA, a metal plate / strip material for electronic components suitable as a lead frame material that requires adhesion to a semiconductor element and adhesion to a sealing resin, and a manufacturing method thereof.
ＬＳＩの小型化、高集積化にともない、半導体パッケージはＱＦＰ（Quad Flat Package）からＢＧＡへと変化してきている。ＭＰＵ（Micro Processing Unit）、ＡＳＩＣ（Application Specific Integrated Circuit）等の高集積半導体ではパッケージの放熱性が重要な課題となっており、放熱性を向上させるため放熱板を装着したＢＧＡが開発されてきた。この放熱板付きＢＧＡパッケージは、樹脂基板に樹脂系接着剤を用いて放熱板を接着し、半導体素子の接着にも樹脂系接着剤を使用して製造される。また、電子部品用のリードフレーム等においても、半導体素子との接着に樹脂系接着剤を使用する。
放熱板には通常、熱伝導性の高い銅又は銅合金板が使用され、その表面には変色を防止するためのＮｉめっきが施されている（下記特許文献１）。
With the miniaturization and high integration of LSIs, the semiconductor package is changing from QFP (Quad Flat Package) to BGA. In highly integrated semiconductors such as MPUs (Micro Processing Units) and ASICs (Application Specific Integrated Circuits), heat dissipation of the package is an important issue, and BGAs equipped with heat sinks have been developed to improve heat dissipation. . This BGA package with a heat sink is manufactured by bonding a heat sink to a resin substrate using a resin adhesive, and also using a resin adhesive for bonding semiconductor elements. Also, resin-based adhesives are used for bonding with semiconductor elements in lead frames for electronic components.
Usually, a copper or copper alloy plate having a high thermal conductivity is used as the heat radiating plate, and Ni plating for preventing discoloration is applied to the surface thereof (Patent Document 1 below).
ＢＧＡパッケージは、通常、リフローはんだ付けによってプリント基板に実装されるが、その際の熱応力による影響等により樹脂との接着界面で剥離する場合があり、放熱板と樹脂基板の間又は放熱板と半導体素子との間に生じる隙間により放熱性が低下し、部品の機能を失うことになる。そのため現状では、放熱板と樹脂接着剤の接合界面に黒化処理を施し、樹脂との密着性を向上させることで、剥離問題を回避している（下記特許文献２）。
しかし、黒化処理は処理コストが高く、処理が非常に複雑で処理皮膜の安定性が悪い。そこで、皮膜安定性に優れ、低コストかつ樹脂密着性に優れるシラン化合物を皮膜とした表面処理技術が開発された（下記特許文献３，４）。
A BGA package is usually mounted on a printed circuit board by reflow soldering, but may be peeled off at the adhesive interface with the resin due to the influence of thermal stress at that time, and between the heat sink and the resin board or between the heat sink and Due to the gap generated between the semiconductor element and the heat dissipation, the function of the component is lost. Therefore, at present, the blackening process is performed on the bonding interface between the heat radiating plate and the resin adhesive to improve the adhesion with the resin, thereby avoiding the peeling problem (Patent Document 2 below).
However, the blackening treatment is expensive, the treatment is very complicated, and the stability of the treatment film is poor. Therefore, a surface treatment technique using a silane compound having excellent film stability, low cost, and excellent resin adhesion as a film has been developed (Patent Documents 3 and 4 below).
前記シラン処理皮膜は無色透明であり、皮膜厚さもミクロンオーダー以下であるため、目視での付着の確認は難しく、蛍光Ｘ線等の測定器を用いて確認する必要があった。また、電子部品用の金属板・条材の信頼性の要求は高く、全長全幅方向に対する付着の確認が求められるが、このような確認は測定器を用いても精度的に困難であり、簡便な確認方法が求められていた。
従って、本発明は、樹脂密着性に優れるシラン処理皮膜を有する電子部品用金属板・条材において、シラン処理皮膜の付着の有無を簡便に確認できるようにすることを目的とする。
Since the silane-treated film is colorless and transparent and the film thickness is less than a micron order, it is difficult to visually confirm adhesion, and it was necessary to confirm using a measuring instrument such as fluorescent X-ray. In addition, there is a high demand for reliability of metal plates and strips for electronic parts, and confirmation of adhesion in the full width direction is required, but such confirmation is difficult even with a measuring instrument and is easy to use. A new confirmation method was required.
Accordingly, an object of the present invention is to make it possible to easily check whether or not a silane-treated film adheres in a metal plate / strip for an electronic component having a silane-treated film having excellent resin adhesion.
本発明に係る電子部品用金属板・条材は、最表面にシラン化合物と色素物質からなる皮膜を有する。
シラン化合物被膜は、通常、それ自体は無色透明であるが、本発明では皮膜中に色素物質を分散して取り込んでいるため、色素物質の種類に応じて、通常環境下での目視観察、蛍光染料等を用いた場合の暗黒化での目視観察、あるいは光照射による目視観察が可能となる。シラン化合物皮膜は、その効果を損なわない範囲で、シラン化合物及び色素物質以外の物質を含むこともできる。
本発明に用いる金属板・条材の材質としては銅又は銅合金が適し、前記皮膜の下地にＮｉ又はＮｉ合金めっき層を有することが望ましいが、前記めっき層は省略されていてもよい。
The metal plate / strip material for electronic parts according to the present invention has a coating made of a silane compound and a pigment substance on the outermost surface.
The silane compound coating is usually colorless and transparent per se, but in the present invention, since the pigment material is dispersed and incorporated in the coating, visual observation under normal circumstances, fluorescence depending on the type of the pigment material. Visual observation in darkening using a dye or the like, or visual observation by light irradiation is possible. The silane compound film may contain a substance other than the silane compound and the dye substance as long as the effect is not impaired.
As the material of the metal plate / strip used in the present invention, copper or a copper alloy is suitable, and it is desirable to have a Ni or Ni alloy plating layer on the base of the film, but the plating layer may be omitted.
前記被膜付き電子部品用金属板・条材を製造するには、Ｎｉ又はＮｉ合金めっきを有し若しくはそのめっきが省略された金属板・条材を、シランカップリング剤と色素物質を含む混合液に接触させる。色素物質としては、顔料又は染料を用いることができる。顔料としては、例えば酸化鉄又はカーボンを用いることができ、その場合、０．５％以上のシランカップリング剤と５％以上の酸化鉄又はカーボンを含む混合液に接触させる。色素物質として染料を用いる場合、０．１％以上のシランカップリング剤と２％以上の染料を含む混合液に接触させる。接触後乾燥させることにより、金属板・条材の最表面に、シラン化合物と酸化鉄又はカーボンを含む皮膜、あるいはシラン化合物と染料を含む皮膜を形成することができる。 In order to manufacture the metal plate / strip material for electronic parts with a coating, a mixed solution containing a silane coupling agent and a dye substance is used for the metal plate / strip material having Ni or Ni alloy plating or omitting the plating. Contact. A pigment or dye can be used as the coloring matter. As the pigment, for example, iron oxide or carbon can be used. In that case, the pigment is brought into contact with a mixed solution containing 0.5% or more of a silane coupling agent and 5% or more of iron oxide or carbon. When a dye is used as the coloring matter, it is brought into contact with a mixed solution containing 0.1% or more of a silane coupling agent and 2% or more of the dye. By drying after contact, a film containing a silane compound and iron oxide or carbon or a film containing a silane compound and a dye can be formed on the outermost surface of the metal plate / strip.
本発明によれば、樹脂密着性に優れた電子部品用金属板・条材を提供することが可能となると同時に、表面に形成された有機皮膜を目視で容易に確認できるようになる。従って、樹脂密着性に関して品質保証可能な、信頼性の高いリードフレームや放熱板等の電子部品を作製することができる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the metal plate and strip | belt material for electronic components excellent in resin adhesiveness, and at the same time, the organic membrane formed on the surface can be easily confirmed visually. Therefore, it is possible to manufacture highly reliable electronic components such as lead frames and heat sinks that can guarantee the quality of resin adhesion.
シラン化合物は、下地の金属、特に銅又は銅合金母材若しくはＮｉ又はＮｉめっきと化学的な結合（共有結合）を形成することが可能であり、さらにシラン化合物皮膜がもつ有機官能基は樹脂とも共有結合を形成し得るので、結果的に樹脂と下地金属との密着性が向上する。このシラン化合物皮膜はアミノ基を有するアミノシラン化合物であるとより効果が高い。
金属板・条材の最表層にこのシラン化合物皮膜が形成されることにより、高い密着性が得られ、高いダイシェア強度値が得られ、シェア強度測定時の樹脂破壊モードが樹脂内破壊となる。さらに皮膜中に色素物質が存在することにより、金属板・条材表面への皮膜付着の有無の確認が目視で可能となる。
なお、皮膜中におけるシラン化合物のＳｉ換算付着量は０．５ｍｇ／ｍ２ 以上が望ましい。Ｓｉ換算付着量が０．５ｍｇ／ｍ２ に満たない場合、十分な皮膜が形成されず、樹脂との密着性が低下し、シェア強度測定時の樹脂の破壊が樹脂内破壊と界面剥離が混じった状態（一部界面剥離状態）になるおそれがある。
The silane compound can form a chemical bond (covalent bond) with the underlying metal, particularly copper or copper alloy base material or Ni or Ni plating, and the organic functional group possessed by the silane compound film is also a resin. Since a covalent bond can be formed, the adhesion between the resin and the base metal is improved as a result. This silane compound film is more effective when it is an aminosilane compound having an amino group.
By forming this silane compound film on the outermost layer of the metal plate / strip, high adhesion can be obtained, a high die shear strength value can be obtained, and the resin failure mode at the time of shear strength measurement is in-resin failure. Further, the presence of the pigment substance in the film makes it possible to visually confirm whether or not the film adheres to the surface of the metal plate / strip.
The Si equivalent adhesion amount of the silane compound in the film is preferably 0.5 mg / m 2 or more. When the Si equivalent adhesion amount is less than 0.5 mg / m 2 , a sufficient film is not formed, the adhesiveness with the resin is lowered, and the destruction of the resin at the time of measuring the shear strength is mixed with the destruction in the resin and the interface peeling. There is a risk that it will be in a wet state (partially delaminated state).
シラン化合物皮膜と樹脂とは化学的な結合を形成するが、結合に寄与するシランカップリング剤の有機官能基は、ビニル基、エポキシ基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、クロロプロピル基、メルカプト基、スルフィド基、イソシアーネ基のいずれでもよく、望ましくはアミノ基を有するシランカップリング剤がより効果が高い。アミノシラン化合物としては、３-アミノプロピルトリエトキシシラン、Ｎ-（２-アミノエチル）-３-アミノプロピルトリメトキシシラン、ｐ-［Ｎ-（２-アミノエチル）アミノメチル］フェネチルトリメトキシシラン、３-［Ｎ-アリル-Ｎ（２-アミノエチル）］アミノプロピルトリメトキシシラン等を用いることができる。 The silane compound film and the resin form a chemical bond, but the organic functional groups of the silane coupling agent that contribute to the bond are vinyl, epoxy, methacryloxy, acryloxy, amino, ureido, and chloropropyl. Any of a group, a mercapto group, a sulfide group, and an isocyanate group is desirable, and a silane coupling agent having an amino group is more effective. Examples of aminosilane compounds include 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, 3 -[N-allyl-N (2-aminoethyl)] aminopropyltrimethoxysilane or the like can be used.
本発明に用いられる色素物質には顔料と染料があり、前者は水やアルコール等に不溶な白色又は有色の粉体であり、無機顔料と有機顔料に大別される。無機顔料の例として酸化鉄及びカーボン、有機顔料の例としてアゾ系顔料、フタロシアニン系顔料、ペリレン系顔料が挙げられる。染料は水やアルコール等に可溶なものと不溶なものがあり、また、蛍光染料と蛍光を発しない染料という分類も可能であり、いずれも用いることができる。
色素物質を含むシラン化合物皮膜の形成方法は、温度４０℃〜６０℃のシランカップリング剤溶液中に色素物質を混ぜて、均一分散させた混合液に対し、１秒以上浸漬させればよい。また、スプレー、塗布等、他の方法で皮膜を形成することもできる。この混合液は、シランカップリング剤の作用を損なわない範囲で、シランカップリング剤及び色素物質以外の物質を含むことも可能である。シランカップリング剤の溶媒としては、水及びアルコール等を用いることが可能である。コスト面で水が望ましく、その場合、液安定性付与のためアルコール等を添加することもできる。
The coloring substances used in the present invention include pigments and dyes. The former are white or colored powders that are insoluble in water or alcohol, and are roughly classified into inorganic pigments and organic pigments. Examples of inorganic pigments include iron oxide and carbon, and examples of organic pigments include azo pigments, phthalocyanine pigments, and perylene pigments. There are dyes that are soluble or insoluble in water, alcohol, and the like, and the dyes can be classified as fluorescent dyes and dyes that do not emit fluorescence, and both can be used.
A method for forming a silane compound film containing a dye substance may be soaked in a mixed solution in which a dye substance is mixed in a silane coupling agent solution at a temperature of 40 ° C. to 60 ° C. and uniformly dispersed for 1 second or more. The film can also be formed by other methods such as spraying and coating. This mixed solution can also contain substances other than the silane coupling agent and the dye substance as long as the action of the silane coupling agent is not impaired. As a solvent for the silane coupling agent, water, alcohol and the like can be used. In view of cost, water is desirable. In that case, alcohol or the like can be added to impart liquid stability.
シランカップリング剤の処理濃度は、混合する色素物質及び溶媒の種類にもよるが、濃度０．１％以上が適しており、これによりＳｉ換算付着量が０．５ｍｇ／ｍ２以上の皮膜を形成することが可能となる。濃度０．１％未満では、Ｓｉ換算付着量が０．５ｍｇ／ｍ２以上のシラン化合物皮膜を得るのが難しくなり、高いシェア強度が得られないなど、樹脂密着性が低下する。望ましくは１０％以下である。ただし、色素物質として無機顔料である酸化鉄又はカーボンを用いたとき、樹脂密着性に優れたシラン化合物皮膜で表面全体を覆うには、シランカップリング剤の濃度は０．５％以上にする必要がある。この場合、望ましくは４０％以下である。
顔料又は染料の濃度は、付着後の皮膜において目視にて着色が確認できる濃度であることが必要があり、顔料又は染料の種類によって適宜決められる。例えば染料の場合は２％以上、酸化鉄又はカーボンの場合は５％以上が望ましい。また、染料の場合は５％以下、酸化鉄又はカーボンの場合は４０％以下が望ましい。
また、処理温度が４０℃よりも低温あるいは６０℃よりも高温の場合、安定した樹脂密着性が得られない。
なお、色素物質として染料を用いたとき、皮膜の付着を確認した後、水洗により染料を洗い落とせるならこれを洗い落とす（シラン化合物は落ちない）ことが望ましい。染料が樹脂密着性を低下させる場合があり（例えば蛍光染料）、これを洗い落とすことにより樹脂密着性が改善されるからである。
The treatment concentration of the silane coupling agent depends on the pigment substance and the type of the solvent to be mixed, but a concentration of 0.1% or more is suitable, so that a coating having a Si equivalent adhesion amount of 0.5 mg / m 2 or more can be obtained. It becomes possible to form. If the concentration is less than 0.1%, it becomes difficult to obtain a silane compound film having a Si equivalent adhesion amount of 0.5 mg / m 2 or more, and the resin adhesiveness is deteriorated such that high shear strength cannot be obtained. Desirably, it is 10% or less. However, when iron oxide or carbon, which is an inorganic pigment, is used as the pigment material, the concentration of the silane coupling agent must be 0.5% or more to cover the entire surface with a silane compound film having excellent resin adhesion. There is. In this case, it is desirably 40% or less.
The concentration of the pigment or dye needs to be a concentration at which coloring can be visually confirmed in the film after adhesion, and is appropriately determined depending on the type of the pigment or dye. For example, 2% or more is desirable for dyes, and 5% or more is desirable for iron oxide or carbon. Further, in the case of a dye, 5% or less, and in the case of iron oxide or carbon, 40% or less is desirable.
Further, when the processing temperature is lower than 40 ° C. or higher than 60 ° C., stable resin adhesion cannot be obtained.
In addition, when a dye is used as the pigment substance, it is desirable that after confirming the adhesion of the film, if the dye can be washed away with water, it is washed away (the silane compound does not fall off). This is because the dye may lower the resin adhesion (for example, a fluorescent dye), and the resin adhesion is improved by washing it off.
Ｎｉ合金めっきは、Ｎｉ−Ｓｎ、Ｎｉ−Ｆｅ、Ｎｉ−Ｐ、Ｎｉ−Ｃｏ等の２元系、あるいはＮｉ−Ｃｕ−Ｓｎ、Ｎｉ−Ｃｕ−Ｆｅ、Ｎｉ−Ｃｏ−Ｐなどの三元系、さらには多元系であってもよい。電子部品用金属板・条材としては、熱伝導性及び電気伝導性が必要であるため銅又は銅合金が望ましく、例えば純銅、Ｃｕ−Ｆｅ−Ｐ系合金、Ｃｕ−Ｎｉ−Ｓｉ系合金、Ｃｕ−Ｃｒ−Ｚｒ系合金など、必要とされる用途に合わせて適当なものを用いればよく、特に制限はない。 Ni alloy plating is a binary system such as Ni-Sn, Ni-Fe, Ni-P, Ni-Co, or a ternary system such as Ni-Cu-Sn, Ni-Cu-Fe, Ni-Co-P, Furthermore, a multi-component system may be used. As the metal plate / strip material for electronic parts, copper or a copper alloy is desirable because it requires thermal conductivity and electrical conductivity. For example, pure copper, Cu—Fe—P alloy, Cu—Ni—Si alloy, Cu A suitable material such as a -Cr-Zr alloy may be used according to the required application, and there is no particular limitation.
板厚０．４ｍｍのＣｕ−０．１ｗｔ％Ｆｅ−０．０３ｗｔ％Ｐ（Ｃ１９２１０）からなる銅合金板に、Ｎｉ又はＮｉ合金めっきを行い、シランカップリング剤水溶液に色素物質を混合して、この混合液に銅合金板を浸漬し、銅合金板の最表面にシラン化合物と色素物質からなる皮膜を形成した。表１に、めっきの種類（Ｎｏ．９，１６はめっき無し）、シランカップリング剤の種類及びその濃度（Ｎｏ．１５はシランカップリング剤無し）、色素物質の種類及びその濃度（Ｎｏ．１４は色素物質無し）を示す。浸漬温度は５０℃、浸漬時間は１秒とした。なお、Ｎｏ．１６は黒化処理を行った。
Ｎｏ．１〜１６のそれぞれについて、下記要領で皮膜色調観察と樹脂密着性試験を行った。なお、Ｎｏ．４は、水洗した後、樹脂密着性試験を行った。
その結果を表１にあわせて示す。
A copper alloy plate made of Cu-0.1 wt% Fe-0.03 wt% P (C19210) with a plate thickness of 0.4 mm is subjected to Ni or Ni alloy plating, and a dye substance is mixed into the silane coupling agent aqueous solution. A copper alloy plate was immersed in this mixed solution, and a film composed of a silane compound and a dye substance was formed on the outermost surface of the copper alloy plate. Table 1 shows the types of plating (No. 9 and 16 are no plating), the types and concentrations of silane coupling agents (No. 15 is no silane coupling agents), the types of coloring substances and their concentrations (No. 14). Indicates no pigment substance). The immersion temperature was 50 ° C. and the immersion time was 1 second. In addition, No. No. 16 was blackened.
No. About each of 1-16, the film color tone observation and the resin adhesiveness test were done in the following way. In addition, No. No. 4 was subjected to a resin adhesion test after washing with water.
The results are also shown in Table 1.
皮膜色調観察；得られた試験材について、Ｎｏ．４を除いて通常環境下（白色光の下）での目視観察を行い、Ｎｏ．４はブラックライトを照射して目視観察を行った。試験材表面の色調の変化すなわち色素物質を含む皮膜の付着が確認できたものを○、できなかったものを×と評価した。
樹脂密着性試験；得られた試験材にＳｉチップをフィルムタイプのエポキシ系接着剤（エイブルスティック社製５６１Ｋ）を用いて接着し、２００℃にてせん断強度（シェア強度）を測定した。シェア強度が１．５Ｎ／ｍｍ２以上のものを○と評価し、それに満たないものを×と評価した。
Film color tone observation; No. 4 was observed visually under normal environment (under white light). No. 4 was visually observed by irradiating with black light. The case where the change in the color tone of the surface of the test material, that is, the adhesion of the film containing the pigment substance could be confirmed was evaluated as ◯, and the case where it was not evaluated as ×.
Resin adhesion test: A Si chip was bonded to the obtained test material using a film-type epoxy adhesive (561K manufactured by Able Stick Co., Ltd.), and the shear strength (shear strength) was measured at 200 ° C. Those having a shear strength of 1.5 N / mm 2 or more were evaluated as ◯, and those less than that were evaluated as ×.
表１に示すように、本発明に規定する条件で皮膜の付着を行ったＮｏ．１〜９は、いずれも目視で確認が可能で、樹脂密着性も優れていた。一方、色素物質としてカーボンを用いたＮｏ．１０，１１では、カーボン濃度が低いＮｏ．１０は目視で確認ができず、シラン化合物濃度が低いＮｏ．１１は樹脂密着性が劣っていた。色素物質として染料を用いたＮｏ．１２，１３では、染料濃度が低いＮｏ．１２は目視で確認ができず、シランカップリング剤濃度が低いＮｏ．１３は樹脂密着性が劣っていた。また、染料のみの処理液を用いたＮｏ．１５は、目視で確認はできたが密着性が劣っていた。 As shown in Table 1, No. 1 was attached to the film under the conditions specified in the present invention. Nos. 1 to 9 could be visually confirmed, and the resin adhesion was excellent. On the other hand, no. Nos. 10 and 11 have a low carbon concentration. No. 10 could not be visually confirmed, and the silane compound concentration was low. No. 11 was inferior in resin adhesion. No. using a dye as a pigment substance. Nos. 12 and 13 are dyes having a low dye concentration. No. 12 could not be visually confirmed, and No. 12 having a low silane coupling agent concentration. No. 13 had poor resin adhesion. No. 1 using a dye-only treatment solution. No. 15 could be confirmed visually, but the adhesion was poor.
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