JP5775684B2 - Conductive metal pattern forming method and electronic / electric element - Google Patents
Conductive metal pattern forming method and electronic / electric element Download PDFInfo
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- JP5775684B2 JP5775684B2 JP2010251886A JP2010251886A JP5775684B2 JP 5775684 B2 JP5775684 B2 JP 5775684B2 JP 2010251886 A JP2010251886 A JP 2010251886A JP 2010251886 A JP2010251886 A JP 2010251886A JP 5775684 B2 JP5775684 B2 JP 5775684B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Printing Methods (AREA)
Description
本発明は、昨今盛んに研究が進められている基体表面上に選択的な機能性紋様を直接に形成する方法に関し、特に樹脂基体のデザイン性に優れた修飾や、鍍金によって形成される実装基板などに応用される電子電気素子、化学素子やダイレクトプリンティング技術に関しており、益々微細化し高度化する機能性紋様の形成や、電子電気素子、プリンテッドエレクトロニクスやバイオ素子などの製造に新たな手段を提供し、併せてその品質や信頼性を向上し、更にコスト低減を実現する。 The present invention relates to a method for directly forming a selective functional pattern on the surface of a substrate, which has been actively researched recently, and in particular, a mounting substrate formed by modification or plating with excellent design of a resin substrate. For electronic and electronic devices, chemical devices, and direct printing technology applied to the market, it provides new means for the formation of increasingly sophisticated and sophisticated functional patterns, and the manufacture of electronic and electrical devices, printed electronics, bio devices, etc. At the same time, the quality and reliability are improved and the cost is further reduced.
樹脂基体上に金属を鍍金して機能を形成する製品は多く、種々の鍍金法や下地処理法が提案され、また、使用されている。特に、樹脂基体表面上に選択的な導電性金属紋様を形成してデザイン性に優れた修飾した製品や電子電気デバイスの実装基板には、実に様々な鍍金技術が使われている。一般的な鍍金製品では溶液中での鍍金が多い。直接に樹脂基体上に鍍金出来ないので、先ず、下地処理を行い樹脂全表面を軽く粗面化して、次いでその粗面にPdなどの金属触媒を析出させてから無電解鍍金で銅などの金属を薄く鍍金して、さらに電気メッキなどで厚く金属を成長させる。粗面化することで金属パターンの接着強度も向上する。まお、無電解鍍金で厚くする場合も有る。次いで、パターン形成を行う。先端的な実装基板では、一般的に真空蒸着や金属膜を接合するなどで、先ず樹脂基体表面全面に強固な金属薄膜を付け、次に感光性レジストなどを使ってパターンを形成し、最後に金属を浸蝕除去して所望の導電性金属パターンを形成する。いずれも基体全面の金属層を蝕刻し、パターンを形成している。
以下本発明では、先端的な実装基板を代表例として詳細な説明を行う。
There are many products that form a function by plating a metal on a resin substrate, and various plating methods and ground treatment methods have been proposed and used. In particular, various plating techniques are used for a modified product and a mounting substrate of an electronic / electrical device that are excellent in design by forming a selective conductive metal pattern on the surface of a resin substrate. Common plating products are often plated in solution. Since plating cannot be performed directly on the resin substrate, first, the entire surface of the resin is lightly roughened by performing a surface treatment, and then a metal catalyst such as Pd is deposited on the rough surface, and then a metal such as copper is electrolessly plated. The metal is grown thinly by electroplating. The adhesion strength of the metal pattern is also improved by roughening the surface. It may be thickened with electroless plating. Next, pattern formation is performed. For advanced mounting boards, generally by vacuum deposition or bonding metal films, first a strong metal thin film is applied to the entire surface of the resin substrate, and then a pattern is formed using a photosensitive resist. The metal is eroded and removed to form a desired conductive metal pattern. In either case, the metal layer on the entire surface of the substrate is etched to form a pattern.
Hereinafter, the present invention will be described in detail using a leading mounting board as a representative example.
近年、応用が拡がる実装基板などの製造に関しては、新しい色々な技術が報告されている。例えば特許公報平2−18399に開示され、また、該公報に引用されているような腐蝕浴槽中の界面処理液に浸漬する水平処理法や垂直処理法などがある。また、様々な界面処理液や処理剤が広く一般に汎用されている。新たな表面修飾剤として、金属錯体を活用した国際公開番号WO 2007/066460のような提案も為されている。いずれも全面に鍍金して、パターンを蝕刻により形成しているので、金属腐蝕の際に界面沿ってアンダーエッチが生じて、信頼性の低下などの深刻な課題が微細化に伴って浮上してきているだけで無く、鍍金した銅などの金属の大部分を除去する為にエネルギーや資源の無駄遣いになっている。 In recent years, various new technologies have been reported for manufacturing mounting substrates and the like whose applications are expanding. For example, there are a horizontal processing method and a vertical processing method which are disclosed in Japanese Patent Laid-Open No. 2-18399 and dipped in an interfacial treatment liquid in a corrosion bath as cited in the publication. Moreover, various interface treatment liquids and treatment agents are widely used in general. As a new surface modifier, a proposal such as International Publication No. WO 2007/066460 utilizing a metal complex has been made. In both cases, the entire surface is plated and the pattern is formed by etching, so that under-etching occurs along the interface during metal corrosion, and serious problems such as reduced reliability have emerged along with miniaturization. In addition, it is a waste of energy and resources to remove most of the plated copper and other metals.
このような課題もあって、最近ではダイレクトライティング技術が注目され、ナノ銀ペーストを印刷後、焼成して導電性パターンを画く技術、インクジェットプリンターで直接パターンを描画形成する技術などが広く研究されている。しかし、電気抵抗が高く、接着強度やパターン形状に課題が多く残っており、非常に高コストである。未だに研究開発段階から脱していない。 Due to these problems, the direct writing technology has recently attracted attention, and after printing nano silver paste, the technology of baking and drawing conductive patterns, the technology of drawing and forming patterns directly with inkjet printers, etc. have been widely studied. Yes. However, the electrical resistance is high, and many problems remain in the adhesive strength and pattern shape, which is very expensive. I haven't left the R & D stage yet.
バイオ素子へ向けて、マイクロプリンティング技術がA. Kumarらの報告を機に発展し、幅広く研究されている。特開2009−90673や特開2009−28947に記されているように種々の工夫がなされてきているが、元来単分子膜のような薄膜を対象としており、応用展開には大きな制約が伴い、非常にコストも掛かる。 Microprinting technology has been developed and studied extensively for biodevices following the report of A. Kumar et al. Various devices have been devised as described in JP2009-90673A and JP2009-28947A, but they are originally intended for thin films such as monomolecular films, and there are significant restrictions on application development. It is very expensive.
樹脂基体表面上への紋様形成では、背景技術に示されるように、全面に金属層を形成した後に、フォトリソ過程などで作成した開口部を腐食して所望の紋様を得ている。この時、腐食液によって金属と樹脂の接合界面が浸蝕されることが知られている。紋様の幅が数十ミクロンと精緻になってくると、このサブ〜数ミクロンの界面浸蝕は無視できない大きさとなり、接合強度の低下を招き剥離の原因になっているだけで無く、種々の不良の原因となっている。更に、この浸蝕部は使用と共に伝播し成長してくるので長期信頼性に無視し得ない影響を及ぼす。特に電気電子素子では、線幅20―30ミクロン以下を目指しており、このような界面浸蝕による初期劣化や経年劣化、特性変化は大きな課題となっている。昨今のダイレクトライティング研究開発に力が入っている一大要因である。 In forming a pattern on the surface of a resin substrate, as shown in the background art, after forming a metal layer on the entire surface, an opening created by a photolithography process or the like is corroded to obtain a desired pattern. At this time, it is known that the joint interface between the metal and the resin is eroded by the corrosive liquid. If the width of the pattern becomes as fine as several tens of microns, this sub- to several-micron interface erosion becomes a non-negligible size, leading to a decrease in bonding strength and causing peeling, as well as various defects. Cause. Furthermore, this eroded portion propagates and grows with use, and thus has a non-negligible effect on long-term reliability. In particular, electrical and electronic devices are aimed at line widths of 20-30 microns or less, and such initial deterioration, aging deterioration, and characteristic change due to such interface erosion are major issues. This is one of the major factors that have put emphasis on recent direct writing research and development.
真空蒸着やスパッタ−法等の物理的な鍍金法では基体との密着強度は非常に強いとされているが、線幅が狭くなってくるとやはり上述の界面浸蝕が問題となっている。数百ミクロン台のパターン蒸着は可能であるが、微細な紋様や細線は全く期待出来ない。 In physical plating methods such as vacuum deposition and sputtering, the adhesion strength to the substrate is considered to be very strong, but the above-mentioned interface erosion is also a problem as the line width becomes narrower. Pattern deposition on the order of several hundred microns is possible, but fine patterns and fine lines cannot be expected at all.
一方、低廉で大量生産向きの液中での銅鍍金法では、鍍金下地処理の仕方によって大幅に密着強度が異なる。一般的には、強度の表面腐蝕処理などに依って界面を粗面化して密着強度を上げているが、一般的には強度不足である。また、基体の全面が荒れるという別の課題や紋様形成時での腐蝕と重畳して界面劣化が大きく生じ、特に実装基板などでは銅細線などの初期剥離、強度の低下や長期信頼性の悪化を招いており、微細化への大きな障害となっている。また、パターン形成において、上述の説明のように界面浸蝕を生じ、これまた初期剥離強度の低下や長期信頼性のさらなる悪化を招いている。 On the other hand, in the copper plating method in a liquid that is inexpensive and suitable for mass production, the adhesion strength varies greatly depending on the method of plating plating. In general, the interface is roughened by surface corrosion treatment or the like to increase the adhesion strength, but generally the strength is insufficient. In addition, there is another problem that the entire surface of the substrate becomes rough, and the deterioration of the interface occurs greatly due to the corrosion at the time of pattern formation. Has been a major obstacle to miniaturization. Further, in pattern formation, interfacial erosion occurs as described above, which causes a decrease in initial peel strength and further deterioration in long-term reliability.
この他に、実際の工程では、多くの処理工程を経る度に進む浸蝕界面劣化を防ぐために、また、処理工程の度に表面を汚したり傷つけたりする恐れが有り、歩留まりや信頼性低下を防ぐために、各種設備、各種機器の維持管理を非常に精緻に行なうなどの維持管理や調整コストが嵩んでいる。この為に工程の簡素化、短縮が強く要望されている。
また、上記のいずれの方法においても、残す紋様部分、回路パターンなどの全面積は小さく、鍍金した金属の殆どを除去しているのが現実である。さらに、大量の腐蝕液などの廃液処理に伴う環境コストや、省資源省エネの観点からも大きな課題となっている。
In addition, in the actual process, there is a risk that the surface of the erosion interface deteriorates every time the treatment process is performed, and the surface may be soiled or damaged each time the treatment process is performed, thereby preventing a decrease in yield and reliability. Therefore, maintenance and adjustment costs such as very precise maintenance and management of various facilities and devices are increasing. For this reason, there is a strong demand for simplification and shortening of the process.
In any of the above-described methods, the entire area of the remaining pattern portion, circuit pattern, etc. is small, and in reality, most of the plated metal is removed. Furthermore, it is a major issue from the viewpoint of environmental costs associated with the treatment of waste liquids such as a large amount of corrosive liquid, and resource saving and energy saving.
最近盛んに研究開発が為されている、ダイレクトライティング技術では、上記の界面浸蝕の課題や廃液処理などの環境問題が低減され理想的な工法と大きな期待が持たれているが、一般的に非常に高コストであり、接着強度やパターン形状に課題が多く残っており未だに研究開発段階から脱していない。また、バイオ素子などへ向けてのマイクロプリンティング技術は、元来単分子膜のような薄膜を対象としており、厚膜を伴うような応用展開には大きな制約が伴う。さらに、微細繊細な調整が必要で安定性に欠け、非常に大きなコストが掛かる。 In direct writing technology, which has been actively researched and developed recently, environmental problems such as the above-mentioned interfacial erosion problems and waste liquid treatment have been reduced. The cost is high, and many problems remain in the adhesive strength and pattern shape. In addition, microprinting technology for bio-elements and the like is originally intended for thin films such as monomolecular films, and there are significant restrictions on application development involving thick films. Furthermore, fine and delicate adjustments are necessary and lack of stability, resulting in very high costs.
本発明は、大量生産に向く導電性金属紋様形成方法及び電子電気素子に関する。
その要旨は、鍍金下地調整工程、紋様形成工程、無電解鍍金工程をこの順序で含み、絶縁性樹脂基体表面上に選択的な導電性金属紋様を形成する方法において、前記紋様形成工程が、A.前記絶縁性樹脂基体表面に前記絶縁性樹脂腐蝕性を有する粘度が1000cps以上の高粘性腐蝕液を前記導電性金属紋様状に形成する印刷過程、B.一定時間保持して前記絶縁性樹脂基体表面を僅かに前記導電性金属紋様状に腐蝕する腐蝕過程を経由し、その後前記高粘性腐蝕液を除去する過程を含むことを特徴とした導電性金属紋様形成方法である。以下、電子素子などで広く使われ、良く知られている実装基板を例にとって具体的な説明を行なう。バイオ素子や化学センサーなどにおいても、一見複雑には見えるが類似の工程を経ている。
The present invention relates to a method for forming a conductive metal pattern suitable for mass production and an electronic / electrical element.
The gist thereof includes a plating base preparation step, a pattern formation step, and an electroless plating step in this order, and in the method of forming a selective conductive metal pattern on the surface of the insulating resin substrate, the pattern formation step comprises: . B. a printing process in which a high-viscosity corrosive liquid having a viscosity of 1000 cps or more having the insulating resin corrosivity is formed on the surface of the insulating resin substrate in the conductive metal pattern ; Conductive metal pattern characterized by including a process of holding the insulating resin substrate for a certain period of time through a corrosive process of slightly corroding the surface of the insulating resin substrate to the conductive metal pattern, and then removing the highly viscous corrosive liquid. It is a forming method. Hereinafter, a specific description will be given by taking a well-known mounting board widely used in electronic devices as an example. Bio-elements and chemical sensors also have similar processes, although it seems complicated at first glance.
また本発明の要旨は、前記導電性金属紋様形成方法における前記無電解鍍金工程によって一旦形成された前記導電性金属紋様上に、当該導電性金属紋様の腐蝕液を選択的紋様に印刷して一部の導電性金属紋様を腐蝕除去して前記絶縁性樹脂基体表面上に選択的な導電性金属紋様を形成することを特徴とした、導電性金属紋様形成方法である。そしてこれらの導電性金属紋様形成方法を用いて製造された電子電気素子である。The gist of the present invention is that the conductive metal pattern is temporarily printed on the conductive metal pattern once formed by the electroless plating step in the conductive metal pattern forming method. The conductive metal pattern is formed by selectively removing a portion of the conductive metal pattern on the surface of the insulating resin substrate by corrosion. And it is the electronic electrical element manufactured using these conductive metal pattern formation methods.
図1に基づいて、本発明の骨子を説明する。図1―イに示すように、清浄な樹脂基体1上に水溶液2を滴下するとはじいて、接触角3が生じて水玉4になったり、端部がワカメ状の形状になって、上手く正確な紋様を画くことが出来ないことは一般に広く知られている。この為に、基体を粗面化する下地処理は必須とされている。一方で、粗面化すると溶液2が速やかに広がり細かな紋様が出来ないことも一般に広く知られている。この為に全面を粗面化して鍍金後に紋様をフォトリソなどで形成するのが従来法である。しかし、本発明者は基体と反応する腐食性の溶液を刷り込むと全くはじくことが無く、むしろはじき易さや滲み難さを逆用した形で微細な紋様が直接簡便に形成されることを見出して、従来の限界を破る金属紋様形成方法の本発明に至った。
Based on FIG. 1, the gist of the present invention will be described. As shown in FIG. 1A, when the
この界面現象を解析考察した処、以下の所見を得た。基体上の溶液の形状は、化学的物理的な結合力と表面張力で決まる。テフロン(登録商標です。)上に水球ができる所以である。しかし、この現象は無反応の平衡状態での話である。溶液は、一時的に表面に張り付き、次いで、平衡状態に為るように盛り上がり(即ちはじいて)平衡状態に移行する。一方、反応性の溶液では一時的に溶液が張り付いた非平衡な界面での反応により基体の表面状態が変化して結合力が増し、はじかないようになる。すると反応がさらに進み、安定した新たな平衡状態に至る。 After analyzing this interface phenomenon, the following findings were obtained. The shape of the solution on the substrate is determined by the chemical physical bonding force and the surface tension. This is why water polo can be formed on Teflon (registered trademark). However, this phenomenon is a story in an unreacted equilibrium state. The solution temporarily sticks to the surface and then rises (i.e., repels) to reach an equilibrium state so as to be in an equilibrium state. On the other hand, in the case of a reactive solution, the surface state of the substrate changes due to the reaction at the non-equilibrium interface where the solution is temporarily adhered, and the binding force increases and does not repel. The reaction then proceeds further and a new stable equilibrium is reached.
図1−ロは、この観測された現象や考察に基づいた本発明の基本的な概念の一例を示している。樹脂基体1に基体樹脂を腐蝕する反応液2を刷り込むと、基体との結合力は弱いために当然表面張力で丸くなろうとするが、一時的に印刷形状を保つ。この間に反応液2に含まれる腐蝕剤が基体を浸潤して表面を変性し活性化層を形成し始めて、段々と結合力が強まって形状を保持するようになる。一定時間経てば、腐蝕剤が界面に拡散してきて十分な腐蝕面が形成され、安定した紋様6が形成されて印刷版の形状を安定に保つように為る。従って、印刷された反応液2は基体1の表面で殆どはじかれることは無く、印刷版の形状を保った紋様6を形成することができる。
原理的には、印刷された紋様溶液の形状とその変化は、主に表面張力、親和性、粘度、時間で決まる。印刷直後は、表面親和性が低くて紋様溶液の拡がりを防ぎ、次の瞬間には腐蝕が始まり界面の親和性を増してはじきを防いで、印刷された紋様6の形状を保ち、更に腐蝕が進行することで、適切な表面活性化層5が形成される。
FIG. 1B shows an example of the basic concept of the present invention based on this observed phenomenon and consideration. When the
In principle, the shape of a printed pattern solution and its change are mainly determined by surface tension, affinity, viscosity and time. Immediately after printing, the surface affinity is low to prevent the spreading of the pattern solution, and at the next moment, corrosion starts and the interface affinity is increased to prevent repellency, keeping the shape of the printed
なお、超微細な紋様ではこのような印刷時に幾分ハジキが認められる場合が有る。この時には、上記の原理に従い、基体の軽い表面処理や腐蝕溶液の増粘が効果的で有ることも見出した。なお、一般の工程におけるように、基体の表面洗浄、プラズマ処理やオゾン処理などによって事前に清浄な樹脂基体表面を得ておくことは云うまでも無い。 It should be noted that some repelling may be observed when printing such an ultra fine pattern. At this time, it has also been found that light surface treatment of the substrate and thickening of the corrosion solution are effective in accordance with the above principle. Needless to say, as in a general process, a clean resin substrate surface is obtained in advance by cleaning the surface of the substrate, plasma treatment, ozone treatment, or the like.
印刷法には、シルクスクリーン印刷、グラビア印刷、インクジェット印刷や直描などの一般的な手法を使える。 As a printing method, general methods such as silk screen printing, gravure printing, ink jet printing, and direct drawing can be used.
次に、この反応液を洗浄除去した後に、ほぼ通常の鍍金処理法に従って、Pdなどの触媒粒子を腐蝕した粗化面へ析出させ、さらに、無電解処理で導電性金属層を形成し厚くして、必要に応じて電解鍍金処理などで一段と厚く形成することもできる。この結果、印刷した紋様を正確に反映した金属鍍金が実現された。なお、上述のように事前に僅か粗化した場合には、極く希に所望の紋様以外にPdなどが僅かに析出し、金属斑点が成長することが認められた。この時は、軽くエッチバックすることで以上の微小な金属斑点状の析出物を簡単に除去できた。
また、反応液中にPd化合物などの触媒金属塩などを予め添加しておき、活性化層へ沈着させておいて、洗浄後に直ぐに無電解鍍金をすることもできる。
Next, after washing and removing the reaction solution, catalyst particles such as Pd are deposited on the roughened roughened surface in accordance with an ordinary plating method, and a conductive metal layer is formed and thickened by electroless treatment. If necessary, it can be formed thicker by electrolytic plating. As a result, a metal plating that accurately reflects the printed pattern was realized. In addition, when it roughened a little in advance as mentioned above, it was recognized that Pd etc. slightly precipitated in addition to a desired pattern very rarely, and a metal spot grew. At this time, the above minute metal spot-like precipitates could be easily removed by lightly etching back.
Alternatively, a catalytic metal salt such as a Pd compound may be added to the reaction solution in advance and deposited on the activated layer, and electroless plating may be performed immediately after washing.
なお、電解鍍金をする場合には、紋様が繋がっていなければならない。連続せずに浮島になった部分があると無電解鍍金はできても、電解鍍金を行なえないことになる。このような時には、一旦連続したダミーの紋様を作成して、電解鍍金で仮の紋様を一旦完成してから、不要となる紋様部分に腐蝕性の高粘性液を選択的に印刷してその部分を除去することで、最終的に望まれた紋様を形成でき、所望の厚膜の電子電気素子などを得ることができる。 In addition, when performing electrolytic plating, the pattern must be connected. If there is a part that is not continuous and becomes floating islands, even if electroless plating is possible, electrolytic plating cannot be performed. In such a case, create a continuous dummy pattern once, complete the temporary pattern with electrolytic plating, and then selectively print the corrosive high-viscosity liquid on the unnecessary pattern part. By removing the film, a desired pattern can be finally formed, and an electronic / electrical element having a desired thick film can be obtained.
本発明により、大量生産に向く低コストの印刷法で微細な紋様を有する機能性商品や微細な回路パターンを有する電子電気素子を提供できる。さらに、電子電気素子に使われる微細な回路パターンにおいては、従来、スパッタ−法などによる優れた接着強度を与える工程を用いても、微細線の形成のために生じる図2に示すようなアンダーカット7や界面の劣化で剥離強度の低下や信頼性の低下が問題となっていたが、本発明によって、このような弊害が解消する。 According to the present invention, a functional product having a fine pattern and an electronic / electric element having a fine circuit pattern can be provided by a low-cost printing method suitable for mass production. Further, in a fine circuit pattern used for an electronic / electrical element, an undercut as shown in FIG. 2 is generated for forming a fine line even if a conventional process for giving excellent adhesive strength by a sputtering method or the like is used. 7 and the deterioration of the interface caused problems such as a decrease in peel strength and a decrease in reliability. However, the present invention eliminates such a problem.
また、従来工程では多くの処理工程を経て、各種設備、各種機器の維持管理や調整コストが嵩み、その上処理工程の度に表面を汚したり傷つけたりする欠点や、歩留まりや信頼性低下が有ったが、本発明では全工程が大幅に簡略化された為に、これらの課題が一挙に解消された。更にプロセス操業度が向上したのみならず、歩留まりの向上など生産性の大幅な向上が図られるなどの副次的な効果も認められた。
さらに本発明では、面積の非常に小さい回路パターンなどの紋様部分だけに鍍金する為に省資源であり、全面鍍金した金属を除去する余計な腐食液なども不要であることから、一層の省資源省エネとなっている。これらによるコスト低減効果も大きい。
なお、同様の手法をバイオ素子や化学センサーなどにも適用でき、上記と同様な優れた特徴が得られることは云うまでも無い。
In addition, the conventional process goes through many processing steps, which increases the maintenance and adjustment costs of various facilities and various equipment, and also has the disadvantages of soiling and scratching the surface each time the processing process is performed, as well as yield and reliability degradation. However, in the present invention, since all the processes are greatly simplified, these problems are solved at once. Furthermore, not only the process operation rate was improved, but also secondary effects such as a significant improvement in productivity such as an increase in yield were recognized.
Furthermore, in the present invention, resources are saved because the plating is applied only to the pattern portion such as a circuit pattern having a very small area, and an extra corrosive solution for removing the metal plated on the entire surface is not required. It is energy saving. The cost reduction effect by these is also great.
Needless to say, the same technique can be applied to bio-elements and chemical sensors, and the same excellent features as described above can be obtained.
本発明の基本的な界面処理法を、代表的な応用例である先端的な実装基板を例にとって以下に詳細な説明を行う。なお、基体や反応液の様々な組み合わせで多用な応用が展開出来ることは云うまでも無い。
絶縁性樹脂基体として38ミクロンのポリイミド膜を用いて、先ず、下地調整工程でその表面を脱脂、清浄化した。次いで、ポリイミド膜表面を加水分解し腐蝕するアルカリ性の腐蝕液をグラビア印刷で所望の紋様を印刷した。数秒から数十秒放置してポリイミド膜表面を適度に粗化した後に腐蝕液を除去し洗浄する界面活性付与過程からなる紋様形成工程を経てポリイミド膜表面に潜在的な紋様を転写作成した。
The basic interface processing method of the present invention will be described in detail below using a leading mounting board as a typical application example. It goes without saying that various applications can be developed with various combinations of substrates and reaction solutions.
Using a 38-micron polyimide film as the insulating resin substrate, the surface was first degreased and cleaned in the base preparation step. Next, a desired pattern was printed by gravure printing with an alkaline corrosion solution that hydrolyzes and corrodes the polyimide film surface. A latent pattern was transferred onto the polyimide film surface through a pattern formation process consisting of a surface activation process in which the surface of the polyimide film was moderately roughened by leaving it for several seconds to several tens of seconds, and then the corrosion solution was removed and washed.
さらに、腐蝕液で活性化された潜在的な紋様を有する表面に一般的なパラジウム付与処理を行い、続けて一般的な無電解ニッケル鍍金液や無電解銅鍍金液で処理して薄い電導性の金属紋様を顕在化した。この結果、印刷の紋様にほぼ一致する無電解銅の紋様が得られた。このまま厚く無電解銅鍍金を施し、また、純水で洗浄をした後、必要な場合には電解銅鍍金を施して厚い高電導性の銅の紋様を形成し、洗浄して完成品とした。 Further, the surface having a latent pattern activated by the corrosion solution is subjected to a general palladium application treatment, followed by treatment with a general electroless nickel plating solution or an electroless copper plating solution. The metal pattern was revealed. As a result, an electroless copper pattern almost identical to the printed pattern was obtained. A thick electroless copper plating was applied as it was, and after washing with pure water, an electrolytic copper plating was applied if necessary to form a thick highly conductive copper pattern, which was then washed to obtain a finished product.
なお、腐蝕液の濃度が薄いときには、腐蝕よりはじく速度が速く紋様が細くなるので、この時には、腐蝕液の粘性を上げる事によりはじく速度を遅くすることで紋様の形状を保つことが出来た。逆に、濃度が濃いときには紋様が太くなる傾向(図3参照)が認められた。この際には腐蝕液の除去を早めることにより紋様の大きさを保つことが出来た。 When the concentration of the corrosive solution is low, the pattern repels faster and the pattern becomes thinner. At this time, the pattern shape can be maintained by lowering the repelling speed by increasing the viscosity of the corrosive liquid. Conversely, when the density was high, the pattern tended to thicken (see Fig. 3). In this case, the size of the pattern could be maintained by expediting the removal of the corrosion solution.
また、薄い無電解の導電性金属紋様を顕在化した際に、所定外の部分に触媒のPdが付着してこれが核となって形成された微小な金属付着物が生ずることがあった。このような付着物は電解鍍金で成長することは無く、軽いエッチバックで効果的に除去できた。 Further, when a thin electroless conductive metal pattern was made apparent, catalyst Pd adhered to a portion other than a predetermined portion, and a minute metal deposit formed by using this as a nucleus sometimes occurred. Such deposits did not grow by electrolytic plating and could be effectively removed by light etch back.
なお、不連続の浮島状の紋様を電解鍍金で厚くするためには、一旦ダミーの紋様で連続させ電解鍍金を施して後に、鍍金された金属を腐食する粘着性の腐蝕液を印刷ないしはスタンプして、ダミー部を腐蝕除去した。これにより、全て印刷法で一貫して、独立した種々の紋様が形成された。 In order to thicken the discontinuous floating island pattern with electrolytic plating, apply a continuous pattern with a dummy pattern, apply electrolytic plating, and then print or stamp an adhesive corrosion solution that corrodes the plated metal. The dummy part was removed by corrosion. As a result, various independent patterns were formed consistently by the printing method.
基体として、幅50cm、38ミクロン厚を有するポリイミド膜を適切な大きさに切断、その表面の脱脂を行なった。脱脂液としては標準的なモノエタトルアミン44%、ポリオキシエチレンアルキルエーテル1.7%に若干のキレート剤を含む水溶液を用いた。さらに蒸留水で洗浄した後、ポリイミド表面を加水分解し腐蝕するKOH4mol/L液に界面活性剤や増粘剤、チクソ剤を加えた腐蝕液を、スクリーン印刷にて50〜100ミクロン幅3mm長の線状紋様、100ミクロン角の市松模様、10mmX30mmの矩形を印刷した。
As a substrate, a polyimide film having a width of 50 cm and a thickness of 38 microns was cut into an appropriate size, and the surface was degreased. As the degreasing solution, an aqueous solution containing 44% of standard mono-ethanolamine and 1.7% of polyoxyethylene alkyl ether and some chelating agents was used. Furthermore, after washing with distilled water, a
印刷後35秒放置、直ちに純水で洗浄して浸潤液を除去して得られた活性界面へ触媒となるパラジウム付与処理を行なった。市販の薬剤を用い通常の手法でポリイミド界面にパラジウム付与を行なった。ほぼ幅55〜105ミクロン長さ3mmの線状紋様と105ミクロン角の市松模様の痕跡が顕微鏡で認められた。全体として幅が約5−10%太めに紋様が形成された。 35 seconds after printing, and immediately washed with pure water to remove the infiltrating liquid, the active interface obtained by applying palladium as a catalyst was applied. Palladium was imparted to the polyimide interface by a conventional method using a commercially available drug. Traces of a linear pattern having a width of 55 to 105 microns and a length of 3 mm and a checkered pattern of 105 microns square were observed with a microscope. As a whole, a pattern with a width of about 5-10% thick was formed.
この時点で、一連の処理を施したポリイミド膜から試料を切り取り、ESCAにてパラジウムの分布状況を測定した。その結果、所定の幅55―105ミクロンの線状紋様と市松紋様が確認された。また、それ以外の部分には、特異なパラジウムの痕跡は認められなかった。引き続き無電解銅鍍金処理を行なった処、厚さ約1ミクロンでほぼ同じ大きさの紋様が確認された。
形成された銅の紋様は、ほぼ幅55―110ミクロン長さ3mmの線状の紋様と110ミクロン角の市松模様である事が顕微鏡で認められた。全体として幅が約5−10%太めに紋様が形成されたが、ほぼ同じ大きさの紋様と確認された。
At this point, a sample was cut from the polyimide film subjected to a series of treatments, and the distribution of palladium was measured by ESCA. As a result, a linear pattern and a checkered pattern having a predetermined width of 55 to 105 microns were confirmed. In addition, no trace of peculiar palladium was observed in the other portions. Subsequent electroless copper plating treatment revealed a pattern of approximately the same size with a thickness of about 1 micron.
The formed copper pattern was observed to be a linear pattern having a width of 55-110 microns and a length of 3 mm and a checkered pattern having a 110-micron square. As a whole, a pattern with a width of about 5 to 10% thick was formed, but it was confirmed that the pattern had almost the same size.
次いで、10mmX30mmの矩形の紋様から所定の大きさを切り取り150度で熱処理した後に、金属層とポリイミド膜との間の剥離強度試験(JIS C 6471 8.1)を行った。引っ張り強度試験器(TEST STAND MODEL-1310DW及びFORCE ANALYZER EXPLORER2)を用いて、引張速度50mm/分、引張角度90°で金属層の引き剥がし強度を測定した。熱処理後の剥離強度は約0.4N/mm前後と直接鍍金膜としてはかなり高い値を示した。 Next, a predetermined size was cut out from a rectangular pattern of 10 mm × 30 mm and heat-treated at 150 ° C., and then a peel strength test (JIS C 6471 8.1) between the metal layer and the polyimide film was performed. Using a tensile strength tester (TEST STAND MODEL-1310DW and FORCE ANALYZER EXPLORER2), the peel strength of the metal layer was measured at a tensile speed of 50 mm / min and a tensile angle of 90 °. The peel strength after the heat treatment was about 0.4 N / mm, which was a considerably high value as a direct plating film.
実施例1と同様に、脱脂液としては標準的なモノエタトルアミン44%、ポリオキシエチレンアルキルエーテル1.7%に若干のキレート剤を含む水溶液を用いた。さらに蒸留水で洗浄した後、ポリイミド表面を加水分解し浸潤するKOH4mol/L液に、アラビアゴム1%、PVA5%アルギン酸ソーダ3%を含む水溶液を等量合せた水飴状の高粘性浸潤液をスクリーン印刷にて幅50〜100ミクロン長さ3mmの線状紋様と100ミクロン角の市松模様、10mmX30mmの矩形を印刷した。実施例1と同様に処理を行なった処、無電解銅鍍金厚3ミクロンで、幅55〜105ミクロン長さ3mmの線状紋様と105ミクロン角の市松模様が顕微鏡で認められた。全体として幅が約3−10%太めに紋様が形成された。
剥離強度は約0.45N/mm前後と実用に耐える値を得た。
As in Example 1, as the degreasing solution, an aqueous solution containing 44% of standard mono-ethanolamine and 1.7% of polyoxyethylene alkyl ether and some chelating agents was used. Furthermore, after washing with distilled water, a
The peel strength was about 0.45 N / mm, which was a practical value.
ポリイミド表面を加水分解する腐蝕液の増粘剤やチクソ剤の量や種類を変えて、粘度を水のような1cpsから粘土の様な数万cpsまで作成し、印刷後の放置時間を5秒から50秒と変えた。粘性の低い腐食液では5秒と短く、高い腐食液では50秒と長くした。他の条件は実施例1とほぼ同様の実験を行った。幅50〜100ミクロン長さ3mmの線状の巾を計測した結果を表1に示す。なお、固い粘土のような場合は、現実には印刷できなかったので除外している。
なお、良品の紋様の剥離強度は、実施例1と同じように概略0.4〜0.45N/mmと変わらなかった。
The peel strength of the non-defective pattern was not changed from about 0.4 to 0.45 N / mm as in the case of Example 1.
実施例2において、基体のポリイミド表面を軽くプラズマ処理を行い、親水性に変化さ
せた。他の条件は実施例2と全く同じである。その結果を表2に示す。表から判るように親水化処理により、腐蝕液が湿潤して腐食反応が優先的に進んだ結果、低粘度域では紋様が太めになったことが示されており、良好な範囲が広がったことが認められた。
なお、良品の剥離強度は約0.4〜0.5N/mmと、やや改善された。
The peel strength of the non-defective product was slightly improved to about 0.4 to 0.5 N / mm.
上記の実施例1をおいて、先ず、無電解鍍金を硫酸ニッケル、塩化ニッケル、次亜燐酸塩等からなる一般市販の無電解ニッケル液で0.1ミクロン厚のニッケル無電解鍍金で行ない、続けて純水で洗浄を行なった。以降は、実施例1と同様に無電解銅鍍金を行なった。その結果、ほぼ幅55〜110ミクロン長さ3mmの線状紋様と105ミクロン角の市松模様が顕微鏡で認められた。全体として幅が約5−10%太めに紋様が形成された。
同時に紋様を150度で熱処理した後に剥離強度を測定したところ、約0.6〜0,8N/mmと非常に高い値を示した。一般に報告されているスパッタ−法での剥離強度に遜色無く、非常に高強度であることが判明した。これは界面のニッケルの接着強度が高いことに因ると推定される。
また、ニッケルは耐酸化性が有ると共に、酸素や水分の効果的なバリアーにもなる為に、銅界面の安定性が増して長期信頼性の向上が図れる特徴がある。150℃200時間の高温処理後も0.55N/m以上の高い値を保持しており、長期信頼性が確認された。
(比較例1)
In Example 1 described above, first, electroless plating is performed with a nickel electroless plating having a thickness of 0.1 micron with a commercially available electroless nickel solution made of nickel sulfate, nickel chloride, hypophosphite, etc. And washed with pure water. Thereafter, electroless copper plating was performed in the same manner as in Example 1. As a result, a linear pattern having a width of 55 to 110 microns and a length of 3 mm and a checkered pattern of 105 microns square were observed with a microscope. As a whole, a pattern with a width of about 5-10% thick was formed.
At the same time, when the peel strength was measured after heat-treating the pattern at 150 degrees, it showed a very high value of about 0.6 to 0.8 N / mm. It was found that the peel strength by the sputtering method generally reported is not inferior and is very high. This is presumed to be due to the high adhesion strength of nickel at the interface.
Nickel has oxidation resistance and an effective barrier against oxygen and moisture, so that the stability of the copper interface is increased and long-term reliability is improved. Even after high temperature treatment at 150 ° C. for 200 hours, a high value of 0.55 N / m or more was maintained, and long-term reliability was confirmed.
(Comparative Example 1)
実施例1と同様にして、従来の銅鍍金処理を行った。この時、腐食液の粘度はほぼ水の様な1CPで、印刷の変わりに全面を腐食液に浸漬して表面処理を行った。その後、無電解鍍金を1ミクロン厚に形成した。その後、通常のフォトリソ、エッチングを行って、実施例1と同様の幅50〜100ミクロン長さ3mmの線状紋様を作成した。
銅鍍金された50ミクロン線状の試料をTEMで断面観察を行ったところ、サイドエッチの為に、銅と基体のポリイミド界面に腐蝕の食い込み、アンダーエッチが全般に見られ、一部には深く入っているのが見られた。フォトリソ後に強いエッチングを施したところ数ミクロンの食い込み(図2)が見られた。
一方、実施例1の試料では、基体のポリイミドとの界面は、端部から端部まで全く異常が無く整合していることが判明した。製造工程を考えれば当然といえる。
さらに細い線になれば、比較例の試料では、線が浮き上がり剥がれると思われる。
実施例2−3についても、同じ様にTEM観察したところ、いずれも界面の整合性は良好であることが判明した。これも製造工程からして当然といえる結果である。
A conventional copper plating treatment was performed in the same manner as in Example 1. At this time, the viscosity of the corrosive liquid was approximately 1 CP like water, and the surface treatment was performed by immersing the entire surface in the corrosive liquid instead of printing. Thereafter, an electroless plating was formed to a thickness of 1 micron. Thereafter, normal photolithography and etching were performed to produce a linear pattern having a width of 50 to 100 microns and a length of 3 mm, similar to Example 1.
When a cross section of a 50 micron linear sample plated with copper was observed with a TEM, due to side etching, corrosion of the polyimide interface between the copper and the substrate was observed, and under-etching was generally observed. I could see it inside. When strong etching was performed after photolithography, biting of several microns was observed (FIG. 2).
On the other hand, in the sample of Example 1, it was found that the interface between the substrate and the polyimide was aligned from end to end without any abnormality. Naturally considering the manufacturing process.
If the line becomes even thinner, it is likely that the line floats up and peels off in the comparative sample.
Also in Example 2-3, TEM observation was performed in the same manner. As a result, it was found that the interface consistency was good. This is also a natural result from the manufacturing process.
実施例3と同様に、種々の濃度の苛性カリ腐蝕液を使い、Pd付着量を調べた。図3に示すように約0.5Nの苛性カリ腐蝕液でポリイミド膜の粗面化が有る程度進行し、Pdの付着が目立ち始め、概略1N以上のでは十分のPd析出が認められた。濃度が高くなるに従い安定な紋様形成が認められた。 In the same manner as in Example 3, using various concentrations of caustic potash solution, the Pd adhesion amount was examined. As shown in FIG. 3, the caustic potash solution of about 0.5 N progressed to some extent with the roughening of the polyimide film, Pd adhesion started to be noticeable, and sufficient Pd precipitation was observed at about 1 N or more. As the concentration increased, stable pattern formation was observed.
本発明は、昨今盛んに研究が進められている基体表面上に選択的な機能性紋様を直接に形成する方法に関し、特に樹脂基体のデザイン性に優れた修飾や、鍍金によって形成される実装基板などに応用される電子電気素子やマイクロコンタクトプリンティング技術に関しており、益々微細化し高度化する機能性紋様の形成や電子電気素子やバイオ素子などの製造に新たな手段を提供し、併せてその品質や信頼性を大幅に向上すると共に、更なる省資源省エネルギーと特段のコスト低減を実現する。 The present invention relates to a method for directly forming a selective functional pattern on the surface of a substrate, which has been actively researched recently, and in particular, a mounting substrate formed by modification or plating with excellent design of a resin substrate. It provides new means for the formation of functional patterns that are becoming increasingly refined and sophisticated, and the manufacture of electronic and electrical elements and bio-elements. In addition to greatly improving the reliability, further resource saving and energy saving will be realized.
1 基体
2 反応液
3 接触角
4 水玉
5 界面層が変性した活性化層
6 紋様
7 アンダーカット
8 配線
DESCRIPTION OF
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KR1020137011700A KR20140018186A (en) | 2010-11-10 | 2011-11-07 | Method for forming functional pattern, and functional element |
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