JP2005072425A - Metal foil laminate and method for manufacturing the same, and multilayer substrate using the same - Google Patents
Metal foil laminate and method for manufacturing the same, and multilayer substrate using the same Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 137
- 239000002184 metal Substances 0.000 title claims abstract description 131
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 131
- 239000000758 substrate Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 66
- 238000005530 etching Methods 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000011889 copper foil Substances 0.000 claims abstract description 25
- 239000011229 interlayer Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 38
- 239000010949 copper Substances 0.000 claims description 23
- 238000007747 plating Methods 0.000 claims description 21
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000009713 electroplating Methods 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract 2
- 230000000717 retained effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001096 P alloy Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Multi-Layered Print Wiring Board (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、基板を複数枚積層し、該基板間を、バンプを形成した積層金属箔により接続する多層基板における層間接続用積層金属箔に関するものであり、基板間を接続するバンプを、エッチングにより形成するのに最適な積層金属箔、並びに、該積層金属箔を用いた多層基板を提供するものである。 The present invention relates to a laminated metal foil for interlayer connection in a multilayer substrate in which a plurality of substrates are laminated and the substrates are connected by a laminated metal foil having bumps formed thereon, and the bumps connecting the substrates are etched. The present invention provides a laminated metal foil that is optimal for forming, and a multilayer substrate using the laminated metal foil.
基板を複数枚積層し、該基板間を、バンプを形成した積層金属箔により接続する多層基板を製造するに際し、積層金属箔からエッチングによりバンプを形成する技術として、Ｃｕ／Ｎｉ／Ｃｕなどの３層構造が、東洋鋼鈑株式会社のカタログ「ＦＩＮＥ ＣＬＡＤ」（非特許文献１参照）などで知られている。
これら3層構造の積層金属箔の製造方法としては、回路形成用電解銅箔（または圧延銅箔）の上にエッチングバリアー層として、Ｎｉを電気めっきにて形成した回路形成側金属箔に、バンプ形成用圧延銅箔をクラッドすることで製造されていた。
When manufacturing a multilayer substrate in which a plurality of substrates are laminated and the substrates are connected by a laminated metal foil having bumps formed thereon, as a technique for forming bumps from the laminated metal foil by etching, 3 techniques such as Cu / Ni / Cu are used. The layer structure is known from the catalog “FINE CLAD” (see Non-Patent Document 1) of Toyo Kohan Co., Ltd.
As a manufacturing method of these three-layer laminated metal foils, bumps are formed on the circuit-forming metal foil formed by electroplating Ni as an etching barrier layer on the electrolytic copper foil (or rolled copper foil) for circuit formation. It was manufactured by clad the forming rolled copper foil.
また、技術情報協会のセミナー「実装技術における圧延銅箔および積層金属箔の特性と高機能化」（平成１５年１月２９日、於池袋サンシャインシティ ワールドインポートマート、日立金属株式会社）（非特許文献２参照）では、２コイルを真空室内にて、蒸着しながら接合ロールで接合する方法が発表されている。この発表では、第１層として、９〜５０μｍのＣｕ，Ｉｎｖａｒ，４２アロイ、Ａｌなど、第３層としては、２５〜１００μｍの同上の金属であり、蒸着される第２層として、Ｔｉ，Ａｇ，Ｓｎ，Ａｌなどが挙げられている。 Also, a seminar by the Technical Information Association “Characteristics and advanced functionality of rolled copper foil and laminated metal foil in packaging technology” (January 29, 2003, Ikebukuro Sunshine City World Import Mart, Hitachi Metals, Ltd.) Document 2) discloses a method of joining two coils with a joining roll while depositing them in a vacuum chamber. In this announcement, the first layer is 9-50 μm Cu, Invar, 42 alloy, Al, etc., the third layer is 25-100 μm of the same metal, and the deposited second layer is Ti, Ag. , Sn, Al and the like.
バンプは、バンプ形成用圧延銅箔をマスキング使用の選択エッチングにより、突起状にエッチングすることで形成する。エッチングはバリアー層が露出する程度に行なうのが一般的であるが、さらにバリアー層もエッチングにより除去する場合がある。
このようにしてバンプを形成した積層金属箔は、バンプ面に、該バンプの先端が露出するように樹脂基板をラミネートし、対向する回路形成された樹脂付き銅箔などとホットプレスにより接合し、バンプと、対向される銅箔回路とを接続する。
The bump is formed by etching the bump forming rolled copper foil into a protrusion shape by selective etching using masking. Etching is generally performed to such an extent that the barrier layer is exposed, but the barrier layer may also be removed by etching.
The laminated metal foil thus formed with the bump is laminated with a resin substrate on the bump surface so that the tip of the bump is exposed, and bonded with a copper foil with resin formed on the opposite circuit by hot pressing, The bump and the copper foil circuit facing each other are connected.
回路形成用金属箔も、必要によりマスキングとエッチングにより、所望の回路パターンに形成される。
この作業を複数回繰り返して多層基板とする。
The metal foil for circuit formation is also formed into a desired circuit pattern by masking and etching if necessary.
This operation is repeated a plurality of times to obtain a multilayer substrate.
前記エッチングにおいて、Ｎｉなどのバリアー層とバンプ形成用金属箔および回路形成用金属箔とのエッチング速度の差が大きいほど良好な形状のバンプおよび回路が形成される。
なお、これらの従来方法では、Ｎｉなどをバリアー層とした被覆回路形成用金属箔（Ｎｉ被覆Ｃｕ板など）と、バンプ形成用としての銅箔をクラッドしていたため、クラッド面はＣｕなどとＮｉなどの接合となり、基本的に密着力を充分に引き出し難く、そのため真空中や、イオンエッチング装置などを使用し、表面の汚染を防止または、除去することで、密着性を出していた。または、これに替えて、進行室内での接合することが必要であった。
これらのため、設備が大掛かりになるばかりか、条件によって、密着力のバラツキが生じ、後工程での加熱時などで、フクレや剥がれが発生する欠陥が多々生じた。
In the etching, bumps and circuits having better shapes are formed as the etching rate difference between the barrier layer such as Ni, the metal foil for bump formation, and the metal foil for circuit formation increases.
In these conventional methods, since a coated circuit forming metal foil (Ni coated Cu plate or the like) using Ni or the like as a barrier layer and a copper foil for bump formation are clad, the clad surface is made of Cu or Ni and Ni. As a result, it is difficult to draw out the adhesive force sufficiently. Therefore, the adhesion is achieved by preventing or removing the contamination of the surface in a vacuum or using an ion etching apparatus. Alternatively, it was necessary to join in the traveling chamber instead.
For these reasons, not only the equipment becomes large, but also the adhesive force varies depending on the conditions, and many defects such as blistering or peeling occur during heating in the subsequent process.
本発明は、上記課題を解決すべく鋭意研究を行った結果、フクレや剥がれなどの発生を抑制し、かつ、バリアー層とのエッチング性を保持したものであり、多層基板の用途に最適な積層金属箔並びにその製造方法、および該積層金属箔を用いた多層基板を提供するものである。 As a result of intensive studies to solve the above-mentioned problems, the present invention suppresses the occurrence of swelling and peeling and retains the etching property with the barrier layer, and is an optimum laminated layer for multilayer board applications. The present invention provides a metal foil, a method for producing the same, and a multilayer substrate using the laminated metal foil.
本発明の基本的な考え方は、次のとおりである。
クラッド接合する直前の材料の両者表面が拡散接合しやすい組み合わせを選ぶことにより、接合の安定性を向上させるものである。ここで、拡散接合しやすい組み合わせとは同じ金属を含む組み合わせや、合金化しやすさを基準として選定することである。
The basic idea of the present invention is as follows.
The combination stability is improved by selecting a combination in which both surfaces of the material immediately before clad bonding are easily diffusion bonded. Here, the combination that facilitates diffusion bonding refers to selection based on the combination including the same metal or the ease of alloying.
本願の積層金属箔の発明は、エッチングにより形成されたバンプにて層間接続を行う積層金属箔であって、該積層金属箔は回路形成用金属箔、エッチングバリアー層、密着性向上層、バンプ形成用金属箔が順次積層されて構成されていることを特徴とする積層金属箔である。 The invention of the laminated metal foil of the present application is a laminated metal foil that performs interlayer connection with bumps formed by etching, wherein the laminated metal foil is a metal foil for circuit formation, an etching barrier layer, an adhesion improving layer, a bump formation It is a laminated metal foil characterized in that the metal foil is laminated in order.
前記密着性向上層とバンプ形成用金属箔との接合表面が拡散接合しやすい金属で構成されていることことが好ましく、特に、前記密着性向上層とバンプ形成用金属箔は、銅または銅合金で形成されていることが好ましい。
また、前記回路形成用金属箔または／およびバンプ形成用金属箔は銅箔または銅合金箔であり、電解銅箔あるいは圧延銅箔であることが望ましい。
さらに、前記密着性向上層およびバンプ形成用金属箔は同一のエッチング液で溶解できる材料で形成されていると良い。
It is preferable that the bonding surface between the adhesion improving layer and the bump forming metal foil is made of a metal that is easily diffusion bonded. In particular, the adhesion improving layer and the bump forming metal foil are made of copper or a copper alloy. It is preferable that it is formed.
The circuit-forming metal foil and / or bump-forming metal foil is a copper foil or a copper alloy foil, and is preferably an electrolytic copper foil or a rolled copper foil.
Further, the adhesion improving layer and the bump forming metal foil are preferably formed of a material that can be dissolved by the same etching solution.
回路形成用金属箔の厚みは回路のファインパターン化の進行により、７μｍ以下とすることが好ましが、クラッド時の強度不足から箔の切れやシワ発生などにより、生産性が劣るため、７μｍ以下とするにはクラッド後にハーフエッチングにより厚さを調整する方法を採用することもできる。 The thickness of the metal foil for circuit formation is preferably 7 μm or less due to the progress of fine patterning of the circuit. However, because the productivity is inferior due to the lack of strength at the time of clad and the occurrence of foil cuts and wrinkles, the thickness is 7 μm or less. To achieve this, a method of adjusting the thickness by half etching after cladding can be employed.
本願の積層金属箔製造方法の発明は、回路形成用金属箔表面にエッチングバリアー層、密着性向上層を電気めっきまたは乾式めっきで形成した回路形成側金属箔と、バンプ形成用金属箔とをクラッドすることを特徴とする積層金属箔の製造方法である。 The invention of the method for producing a laminated metal foil according to the present application includes clad a metal foil for circuit formation and a metal foil for bump formation formed by forming an etching barrier layer and an adhesion improving layer on the surface of the metal foil for circuit formation by electroplating or dry plating. It is the manufacturing method of the laminated metal foil characterized by doing.
前記回路形成用金属箔および／またはバンプ形成用金属箔は、銅または銅合金であり、電解銅箔あるいは圧延銅箔であることが望ましい。
また、前記密着性向上層は、銅または銅合金による電気めっきまたは乾式めっきで形成することが好ましい。
さらに、前記エッチングバリアー層は、Ｎｉ、ＣｏまたはＣｒのいずれか、またはこれらを含む合金による電気めっきまたは乾式めっきで形成すると良い。
前記回路形成側金属箔と、前記バンプ形成用金属箔とをクラッド後、圧延加工を施すこし、厚さを調整することもできる。
The metal foil for circuit formation and / or the metal foil for bump formation is preferably copper or a copper alloy, and is preferably an electrolytic copper foil or a rolled copper foil.
The adhesion improving layer is preferably formed by electroplating or dry plating with copper or a copper alloy.
Further, the etching barrier layer may be formed by electroplating or dry plating with Ni, Co, Cr, or an alloy containing these.
The thickness of the circuit-forming metal foil and the bump-forming metal foil can be adjusted after being clad and then rolled.
本願の多層基板の発明は、前記本発明の積層金属箔、あるいは本発明積層金属箔の製造方法により製造した積層金属箔を用いて作成した多層基板である。 The invention of the multilayer substrate of the present application is a multilayer substrate prepared using the multilayer metal foil of the present invention or the multilayer metal foil produced by the method for producing the multilayer metal foil of the present invention.
本発明は、回路形成側金属箔とバンプ形成用金属箔の接合強度を高めたことにより、回路形成側金属箔のエッチングバリアー層からバンプが剥離するのを有効に防止できるため後工程による剥離やフクレの問題が解決され、工業上非常に優れたものである。 In the present invention, by increasing the bonding strength between the circuit forming side metal foil and the bump forming metal foil, it is possible to effectively prevent the bump from peeling from the etching barrier layer of the circuit forming side metal foil. The problem of blistering is solved and it is very excellent in industry.
バンプ形成用金属箔としては、抵抗値の低い金属、または合金からなる箔であればいずれでも良いが、銅または銅合金箔が抵抗値、エッチングし易さ、強度、コストの点で最も優れている。
また、バンプ形成用金属箔としては電解箔、圧延箔のいずれでも良い。バンプの強度を重視すれば、銅合金の圧延箔が優れ、製造幅による加工コストの上昇や、表面の凹凸により相手側の導体金属との接合信頼性の面からは、電解銅箔が優れている。
圧延箔、電解箔にかかわらず、バンプの先端面となる面を焼けめっきや電解または化学溶解による粗化処理を施し、また、防錆処理を施こし、接触の安定性を図ることが好ましい。
バンプ形成用金属箔の厚みは、所望のバンプ高さにより決定すればよく、通常２０〜２００μｍである。
The metal foil for bump formation may be any foil made of a metal or alloy having a low resistance value, but copper or copper alloy foil is the most excellent in terms of resistance value, ease of etching, strength, and cost. Yes.
The bump forming metal foil may be either electrolytic foil or rolled foil. If the emphasis is placed on the strength of the bump, the copper alloy rolled foil is superior, and the electrolytic copper foil is superior from the viewpoint of increased processing costs due to the manufacturing width and the reliability of bonding with the other conductor metal due to surface irregularities. Yes.
Regardless of the rolled foil or electrolytic foil, it is preferable that the surface to be the tip of the bump is subjected to a roughening treatment by baking plating, electrolysis or chemical dissolution, and a rust-proofing treatment to achieve contact stability.
What is necessary is just to determine the thickness of the metal foil for bump formation by the desired bump height, and it is 20-200 micrometers normally.
密着性向上層は、バンプ形成用金属箔とのクラッド時での密着性を向上させる層であって、バンプ形成用金属箔と拡散接合しやすい金属・合金により形成される。
バンプ形成用金属箔が銅または銅合金の時には、銅や銀、錫、亜鉛などまたはこれらの合金が望ましい。特には、銅または銅合金が後工程での加熱やエッチングなどに対して優れており、好ましい。
この密着性向上層は、回路形成用金属箔上にエッチングバリアー層を設けた後に電気めっきなどの湿式または乾式めっきで形成し、クラッド工程での前処理を施した後にバンプ形成用金属箔と積層される。
この前処理としては、真空中でのイオンエッチング処理や、非酸化性雰囲気下でのバフ研磨などが施される。
この密着性向上層の厚みは、施される前処理方法により異なるが、一般に０．５μｍ以上、特には２μｍ以上あることが望ましい。
The adhesion improving layer is a layer that improves adhesion when clad with the bump forming metal foil, and is formed of a metal / alloy that is easily diffusion bonded to the bump forming metal foil.
When the bump forming metal foil is copper or a copper alloy, copper, silver, tin, zinc or the like or an alloy thereof is desirable. In particular, copper or a copper alloy is preferable because it is excellent for heating and etching in a later process.
This adhesion improving layer is formed by wet etching such as electroplating or dry plating after providing an etching barrier layer on the metal foil for circuit formation, and is laminated with the metal foil for bump formation after pretreatment in the cladding process. Is done.
As the pretreatment, ion etching treatment in a vacuum, buffing in a non-oxidizing atmosphere, or the like is performed.
The thickness of the adhesion improving layer varies depending on the pretreatment method to be applied, but is generally 0.5 μm or more, particularly 2 μm or more.
エッチングバリアー層は、バンプ形成用金属箔および回路形成用金属箔をそれぞれ独立にエッチングするために設けられる層であり、これら上下２層の箔をエッチングするエッチング液に対してエッチングされ難い金属層であり、一方の箔に対するエッチングによって、他方の箔がエッチングされるのを阻む役割を果たす。
銅または銅合金のバンプ形成用金属箔や回路形成用金属箔を用いる場合には、エッチングバリアー層はＮｉ，Ｃｒ，Ｃｏまたはこれらの合金層が望ましい。
エッチングバリアー層の厚さは、エッチングバリアーとして有効であれば良く、通常０．５μｍ以上あればよい。
エッチングバリアー層の形成方法としては、電気めっき、無電解めっきなどの湿式めっきや、蒸着などの乾式めっきのいずれでも良く、密着性やコストの点から電気めっきが優れている。
The etching barrier layer is a layer provided for independently etching the metal foil for bump formation and the metal foil for circuit formation, and is a metal layer which is difficult to be etched with respect to the etching solution for etching these two upper and lower foils. In addition, the etching of one foil serves to prevent the other foil from being etched.
In the case of using copper or copper alloy bump forming metal foil or circuit forming metal foil, the etching barrier layer is preferably Ni, Cr, Co or an alloy layer thereof.
The thickness of the etching barrier layer only needs to be effective as an etching barrier, and is usually 0.5 μm or more.
As a method for forming the etching barrier layer, any of wet plating such as electroplating and electroless plating and dry plating such as vapor deposition may be used, and electroplating is excellent in terms of adhesion and cost.
回路形成用金属箔としては、抵抗が低く、エッチングにより回路形成しうる金属または合金であれば良いが、これらの内、銅または銅合金の圧延または電解箔を用いることが良く、特には、電解銅箔が優れている。
この回路形成用金属箔上に、エッチングバリアー層、さらに密着性向上層を形成し回路形成側金属箔とする。
回路形成側金属箔のバンプ形成用金属箔と接合する面と反対側の面に防錆処理、シランカップリング剤処理を施すことが好ましい。防錆処理としては、一般的にＮｉ，Ｚｎ，Ｃｒやこれらの合金めっき、クロメート処理または、ＢＴＡなどの有機防錆処理を施す。
シランカップリング剤処理としては、ビニル系、エポキシ系など使用される基板により適宜選択する。
The metal foil for circuit formation may be any metal or alloy having low resistance and capable of forming a circuit by etching. Of these, copper or a copper alloy rolled or electrolytic foil is preferably used. Copper foil is excellent.
On this circuit-forming metal foil, an etching barrier layer and an adhesion improving layer are formed to form a circuit-forming metal foil.
It is preferable to perform a rust prevention treatment and a silane coupling agent treatment on the surface of the circuit forming side metal foil opposite to the surface to be bonded to the bump forming metal foil. As the antirust treatment, Ni, Zn, Cr, alloy plating thereof, chromate treatment, or organic antirust treatment such as BTA is generally performed.
The silane coupling agent treatment is appropriately selected depending on the substrate used, such as vinyl or epoxy.
回路形成用金属箔の厚みは、安定してクラッドするために最低限の厚み（１０μｍ前後）が必要であるが、ファインパターン化の動向により、回路形成用金属箔は薄いことが望まれており、７μｍ以下、とくには、５μｍ以下になるように平滑エッチング（ハーフエッチング）することでファインパターンへの対応が可能となる。なお、この工程は、回路形成用金属箔＋エッチングバリアー層＋密着性向上層の３層材を形成後に施しても良いが、バンプ形成用金属箔とのクラッド後に行っても良い。 The metal foil for circuit formation needs to have a minimum thickness (around 10 μm) in order to stably clad, but the metal foil for circuit formation is desired to be thin due to the trend of fine patterning. By applying smooth etching (half etching) to 7 μm or less, particularly 5 μm or less, it is possible to cope with fine patterns. This step may be performed after the formation of the three-layer material of the circuit forming metal foil + the etching barrier layer + the adhesion improving layer, or may be performed after the clad with the bump forming metal foil.
クラッド工程では、回路形成用金属箔にエッチングバリアー層および密着性向上層を形成した回路形成側金属箔とバンプ形成用金属箔をクラッドするが、これらをそれぞれ、真空中にてイオンエッチングして、真空中にて圧接圧延して巻き取るなどの方法で実施される。このような方法で行うと、密着強度の点から非常に優れ、従来材料よりも格段にフクレなどの発生が抑制され、優れた積層金属箔となる。
また、本発明においては、上記従来の材料と比較して密着性に優れるため、前処理として、大気中でのバフ研磨および非酸化性雰囲気下での圧接圧延などのように、設備コストを削減しても密着性を充分確保しうるものである。
また、より密着性を向上することや、強度の向上、ファインパターンへ対応する厚みの低減を狙って、クラッド後に圧延処理を施しても良い。
In the cladding process, the circuit forming side metal foil and the bump forming metal foil in which the etching barrier layer and the adhesion improving layer are formed on the circuit forming metal foil are clad, and each of these is ion-etched in a vacuum, It is carried out by a method such as pressure rolling in a vacuum and winding up. When carried out by such a method, it is very excellent in terms of adhesion strength, the occurrence of blistering and the like is significantly suppressed as compared with conventional materials, and an excellent laminated metal foil is obtained.
In the present invention, since the adhesion is superior compared to the above conventional materials, the equipment cost is reduced as pretreatment such as buffing in the air and pressure rolling in a non-oxidizing atmosphere. Even so, sufficient adhesion can be secured.
Moreover, you may perform a rolling process after clad | crud aiming at the adhesiveness improvement, the improvement of intensity | strength, and the reduction | decrease of the thickness corresponding to a fine pattern.
次に、本発明の実施例を用いて詳細に説明する。
なお、この説明は、本発明の一般的な説明をする目的でなされたものであり、何ら限定的意味を持つものではない。
（実施例１）
Next, it demonstrates in detail using the Example of this invention.
This description is made for the purpose of general description of the present invention, and has no limiting meaning.
(Example 1)
回路形成用金属箔として１２μｍの電解銅箔を用い、そのマット面にエッチングバリアー層としてＮｉを１μｍの厚さに、密着性向上層としてＣｕを３μｍの厚さに順次電解めっきして回路形成側金属箔を作成し、この回路形成側金属箔と１２０μｍ厚の圧延銅からなるバンプ形成用金属箔とをクラッド加工した。
Ｎｉのめっきは、
浴組成：
スルファミン酸ニッケル：３００ｇ／Ｌ
塩化ニッケル ： ２０ｇ／Ｌ
ほう酸 ： ３５ｇ／Ｌ
めっき条件：
温度 ：５０℃
電流密度 ：５Ａ／ｄｍ２
A circuit forming side is formed by using electrolytic copper foil of 12 μm as a metal foil for circuit formation, electrolytic plating of Ni as a thickness of 1 μm as an etching barrier layer and Cu as a layer of 3 μm as an adhesion improving layer on the mat surface. A metal foil was prepared, and this circuit-forming metal foil and a bump-forming metal foil made of rolled copper having a thickness of 120 μm were clad.
Ni plating
Bath composition:
Nickel sulfamate: 300 g / L
Nickel chloride: 20 g / L
Boric acid: 35 g / L
Plating conditions:
Temperature: 50 ° C
Current density: 5 A / dm 2
Ｃｕのめっきは、
浴組成：
硫酸銅 ：１２５ｇ／Ｌ
硫酸 ： ４０ｇ／Ｌ
にかわ ：１００ｐｐｍ
めっき条件：
温度 ：４０℃で
電流密度 ：３Ａ／ｄｍ２
Cu plating
Bath composition:
Copper sulfate: 125 g / L
Sulfuric acid: 40 g / L
Chicken: 100ppm
Plating conditions:
Temperature: 40 ° C. Current density: 3 A / dm 2
クラッド工程は、両者の箔の接合面を窒素雰囲気中にて研磨して圧接圧延を行い、大気中へ取り出して巻き取った。研磨は、＃２０００のバフを用い、研磨粉を窒素にて吹き飛ばしながら吸引することで粉の介在を防止した。
（実施例２）
In the clad process, the joint surfaces of the two foils were polished in a nitrogen atmosphere and subjected to pressure rolling, taken out into the atmosphere and wound up. Polishing was performed by using a # 2000 buff and sucking the polishing powder while blowing it with nitrogen to prevent the inclusion of the powder.
(Example 2)
Ｃｕめっきに替えて、黄銅めっきを４μｍとした以外は、実施例１と同様にして製造した。
黄銅のめっきは：
浴組成：
シアン化銅 ：２７ｇ／Ｌ
シアン化亜鉛 ： ９ｇ／Ｌ
シアン化ナトリウム ：５５ｇ／Ｌ
炭酸ナトリウム ：３０ｇ／Ｌ
めっき条件：
温度 ：３０℃
電流密度 ：０．５Ａ／ｄｍ２
（実施例３）
This was manufactured in the same manner as in Example 1 except that the copper plating was changed to 4 μm instead of the Cu plating.
Brass plating is:
Bath composition:
Copper cyanide: 27 g / L
Zinc cyanide: 9g / L
Sodium cyanide: 55 g / L
Sodium carbonate: 30 g / L
Plating conditions:
Temperature: 30 ° C
Current density: 0.5 A / dm 2
(Example 3)
Ｎｉ電気めっきに替えて、Ｎｉ−Ｃｏ−Ｐ合金を無電解めっき形成した以外は、実施例１と同様に製造した。
Ｎｉ−Ｃｏ―Ｐ合金のめっきは：
浴組成：
硫酸ニッケル ：０．０５モル／Ｌ
硫酸コバルト ：０．０５モル／Ｌ
クエン酸ナトリウム ：０．２モル／Ｌ
硫酸アンモニウム ：０．５モル／Ｌ
次亜リン酸ナトリウム ：０．２モル／Ｌ
めっき条件：
ＰＨ ：９
温度 ：９０℃
（実施例４）
It manufactured like Example 1 except having replaced with Ni electroplating and electroless-plating and forming Ni-Co-P alloy.
Ni-Co-P alloy plating:
Bath composition:
Nickel sulfate: 0.05 mol / L
Cobalt sulfate: 0.05 mol / L
Sodium citrate: 0.2 mol / L
Ammonium sulfate: 0.5 mol / L
Sodium hypophosphite: 0.2 mol / L
Plating conditions:
PH: 9
Temperature: 90 ° C
Example 4
実施例１にて、バンプ形成用金属箔として使用した圧延銅箔に替えて、１１０μｍ厚さの電解銅箔を用いてクラッドし、さらに、圧延で全体の厚みが１００μｍとなるように圧延した。
（実施例５）
In Example 1, instead of the rolled copper foil used as the bump-forming metal foil, the electrolytic copper foil having a thickness of 110 μm was clad, and further rolled to a total thickness of 100 μm by rolling.
(Example 5)
実施例１にて、バンプ形成用金属箔として使用した圧延銅箔に替えて、圧延銅合金箔（Ｃｕ−０．２％Ｓｎ−０．０３％Ｐ）を用いた以外は、実施例１と同様に製造した。
（比較例１）
Example 1 and Example 1 except that a rolled copper alloy foil (Cu-0.2% Sn-0.03% P) was used instead of the rolled copper foil used as the bump forming metal foil. Produced similarly.
(Comparative Example 1)
Ｃｕ３μｍの電解めっきを省略した以外は、実施例１と同様に製造した。
（評価）
It was manufactured in the same manner as in Example 1 except that the electrolytic plating of Cu 3 μm was omitted.
(Evaluation)
上記実施例および比較例で製造した各積層金属箔のバンプ形成用金属箔上にレジスト形成し、エッチング後レジストを剥離して、先端径８０μｍのバンプを形成し、バンプ付き複合箔とした。次いで、バンプ先端が露出するように樹脂ラミネートを行い、相手側となる樹脂付き銅箔とホットプレスを行い、層間接続した。
この材料につき、バンプ付き複合箔側に対し９０°引き剥がし試験を行い、剥がれの形態をＮ＝１００にて観察した。
Resist was formed on the metal foil for bump formation of each laminated metal foil manufactured in the above Examples and Comparative Examples, and the resist was peeled off after etching to form a bump having a tip diameter of 80 μm to obtain a composite foil with bump. Next, resin lamination was performed so that the bump tip was exposed, and hot pressing was performed with a copper foil with resin on the other side, and interlayer connection was performed.
About this material, 90 degree peeling test was done with respect to the composite foil side with a bump, and the form of peeling was observed by N = 100.
これらの結果を下記表１に示す。
表１
Ａ：相手側銅箔／バンプの間
Ｂ：バンプ／密着性向上層の間
Ｃ：密着性向上層／エッチングバリア−層の間
Ｄ：バンプ／エッチングバリア−層の間
These results are shown in Table 1 below.
Table 1
A: Between mating copper foil / bump B: Between bump / adhesion improving layer C: Between adhesion improving layer / etching barrier-layer D: Between bump / etching barrier layer
表1から明らかなように、実施例では、いずれも剥がし強度が大きく、一番弱い部分であるタイプＡ部での剥がれが多いのに対して、比較例では、引き剥がし強度が弱く、８０％もがタイプＤで剥がれていた。実施例では比較例に相当する部分であるタイプＢ，Ｃでの剥がれは、４％以下と安定していた。
〔００３５〕
また、各実施例で製造した積層金属箔のバンプ−密着性向上層間の剥がれ、即ち、回路形成側金属箔とバンプ形成用金属箔間の剥がれはバンプ形成（後工程）後でもほとんどなく、優れた多層基板用の積層金属箔であった。これに対し、比較例では密着性向上層が施されていないため、回路形成用金属箔とバンプ形成用金属箔間の剥がれが８０％と、大部分が不良品であった。
As can be seen from Table 1, in the examples, the peeling strength is large and the peeling at the weakest part, Type A, is large, whereas in the comparative example, the peeling strength is weak, 80%. The thigh was peeled off with Type D. In the examples, the peeling in types B and C, which are parts corresponding to the comparative examples, was stable at 4% or less.
[0035]
In addition, the peeling between the bump-adhesion improving layers of the laminated metal foil produced in each example, that is, the peeling between the circuit forming side metal foil and the bump forming metal foil is hardly present even after the bump formation (post-process), and is excellent. It was a laminated metal foil for a multilayer substrate. On the other hand, in the comparative example, since the adhesion improving layer was not applied, the peeling between the metal foil for circuit formation and the metal foil for bump formation was 80%, and most of them were defective products.
Claims (12)
A multilayer substrate using the laminated metal foil according to any one of claims 1 to 6, or the laminated metal foil produced by the production method according to any one of claims 7 to 11.
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