JP2008130585A - Copper-coated polyimide substrate and manufacturing method thereof - Google Patents
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本発明は、銅被覆ポリイミド基板とその製造方法に関し、さらに詳しくは、チップオンフィルム(COF)の折り曲げ実装時に求められる耐屈曲性において、MIT耐折性試験(JIS C 5016)により200回以上の折曲げ性が得られ、折曲げに対する耐久性に優れる半導体実装用の銅被覆ポリイミド基板とその製造方法に関する。 The present invention relates to a copper-coated polyimide substrate and a method for producing the same, and more specifically, in the bending resistance required when a chip-on-film (COF) is bent and mounted, the MIT folding resistance test (JIS C 5016) is performed 200 times or more. The present invention relates to a copper-coated polyimide substrate for semiconductor mounting, which can be bent and has excellent durability against bending, and a method for manufacturing the same.
近年、銅被覆ポリイミド基板は、液晶画面に画像を表示するための駆動用半導体を実装するための半導体実装用の基板として汎用されている。ポリイミドフィルムは、優れた耐熱性を有し、しかも機械的、電気的及び化学的特性においても他のプラスティック材料に比べ遜色のないことから、例えば、プリント配線板(PWB)、フレキシブルプリント配線板(FPC)、テープ自動ボンディング用テープ(TAB)、チップオンフィルム(COF)等の電子部品用の絶縁基板材料として多用されている。 In recent years, a copper-coated polyimide substrate has been widely used as a semiconductor mounting substrate for mounting a driving semiconductor for displaying an image on a liquid crystal screen. The polyimide film has excellent heat resistance and is not inferior to other plastic materials in mechanical, electrical and chemical characteristics. For example, a printed wiring board (PWB), a flexible printed wiring board ( It is widely used as an insulating substrate material for electronic components such as FPC), tape automatic bonding tape (TAB), and chip on film (COF).
この中で、液晶画面表示用のドライバICチップを実装する手法として、COF(Chip on Film)が注目されている。COFは、従来の実装法であったTCP(Tape Carrier Package)に比べて、ファインピッチ実装が可能であり、かつドライバICチップの小型化及びコストダウンを図ることが容易な実装法である。
一般的に、COFには、ポリイミドフィルムと導電体である金属層を接合させることによって得られる金属被覆ポリイミド基板が使用されている。ここで、実装においては、金属被覆ポリイミド基板の金属層に、フォトリソグラフィー法によって微細な配線パターンを形成し、さらに所望の箇所にスズめっき及びソルダーレジストを被覆した後に用いられる。
Of these, COF (Chip on Film) has attracted attention as a method for mounting a driver IC chip for displaying a liquid crystal screen. COF is a mounting method that allows fine pitch mounting and facilitates downsizing and cost reduction of the driver IC chip, as compared with TCP (Tape Carrier Package), which is a conventional mounting method.
Generally, a metal-coated polyimide substrate obtained by bonding a polyimide film and a metal layer as a conductor is used for COF. Here, in mounting, a fine wiring pattern is formed on a metal layer of a metal-coated polyimide substrate by a photolithography method, and further, tin plating and a solder resist are coated on a desired portion.
上記金属被覆ポリイミド基板の製造方法としては、一般に、ポリイミドフィルムの表面に、まずスパッタリング法によってニッケル−クロム系合金等の金属層を形成し、引き続き良好な導電性を付与するために同様の方法によって銅等の金属層を形成する。さらに、電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で金属層の厚膜化を行い、所望の金属層を形成する。このような方法により製造される金属被覆ポリイミド基板は、接着剤を用いないためその影響を受けないため、高温安定性をはじめとするポリイミド本来の特徴を利用することができるという利点を有している。 As a method for producing the metal-coated polyimide substrate, generally, a metal layer such as a nickel-chromium alloy is first formed on the surface of the polyimide film by a sputtering method, and then a similar method is used to impart good conductivity. A metal layer such as copper is formed. Further, the metal layer is thickened by an electroplating method or a method using an electroplating method and an electroless plating method in combination to form a desired metal layer. Since the metal-coated polyimide substrate manufactured by such a method is not affected by the use of an adhesive, it has the advantage that the original characteristics of polyimide including high-temperature stability can be used. Yes.
上記金属層として銅を選択する場合、通常、電気めっき法における陽極としては溶解性の含リン銅ボールが用いられている(例えば、特許文献1参照。)。この手法では、陽極である含リン銅ボールが溶解することにより、めっき液中に銅イオンを供給している。その際、含リン銅ボール中の不純物元素が、陽極スライムと呼ばれる残渣としてめっき液中に分散し、めっき液を汚染する。このため、これらの汚染物質がめっき基板に付着し、めっき皮膜の表面に凹凸、すなわち陽極スライムに起因するめっきノジュールの発生を引き起こすという問題があった。 When copper is selected as the metal layer, a soluble phosphorus-containing copper ball is usually used as the anode in the electroplating method (see, for example, Patent Document 1). In this method, copper ions are supplied into the plating solution by dissolving the phosphorus-containing copper balls as the anode. At that time, the impurity element in the phosphorus-containing copper ball is dispersed in the plating solution as a residue called anode slime and contaminates the plating solution. For this reason, there is a problem that these contaminants adhere to the plating substrate and cause the generation of irregularities on the surface of the plating film, that is, plating nodules due to the anode slime.
この解決策として、前記陽極スライムが発生しない手法として、不溶解性陽極を用いる手法が考えられる。この不溶解性陽極を用いる手法は、従来、金属製錬などにおいて余剰の金属や不純物元素を電解採取する工程で用いられている(例えば、特許文献2参照。)ものであるが、近年、電気めっき工程における陽極スライムに起因する問題を解決するため、溶解性の金属陽極の代わりに、イオン交換膜でめっき液から隔てた陽極室内に不溶解性陽極を設けるとともに、酸化銅を充填した銅イオンの供給源専用の槽を設置し、この槽のめっき液をめっき処理を行う槽と循環させ、めっき液中の銅イオン濃度を制御するめっき法が開示されている(例えば、特許文献3参照。)。しかしながら、この方法では、一般的には、電気めっき処理中に陽極上で水の電気分解反応が起こり、それに伴って酸素ガスが発生する。ここで、酸素ガスが発生することによって、めっき液中の添加剤が異常に消耗し、同時にガスが激しく発生することによって陽極そのものが劣化するという問題が発生する。 As a solution to this problem, a technique using an insoluble anode can be considered as a technique for preventing the generation of the anode slime. The method using the insoluble anode is conventionally used in a process of electrolytically collecting excess metal or impurity elements in metal smelting or the like (see, for example, Patent Document 2). In order to solve the problem caused by the anode slime in the plating process, instead of the soluble metal anode, an insoluble anode is provided in the anode chamber separated from the plating solution by an ion exchange membrane, and copper ions filled with copper oxide are provided. A plating method is disclosed in which a tank dedicated to the supply source is installed, the plating solution in this tank is circulated with a bath for plating, and the copper ion concentration in the plating solution is controlled (see, for example, Patent Document 3). ). However, in this method, generally, an electrolysis reaction of water occurs on the anode during the electroplating process, and oxygen gas is generated accordingly. Here, when oxygen gas is generated, the additive in the plating solution is abnormally consumed, and at the same time, the gas is vigorously generated, so that the anode itself deteriorates.
ところで、実装技術の発展、及び銅被覆ポリイミド基板の用途拡大に伴い、銅被覆ポリイミド基板の特性として、耐屈曲性などにおいて、従来技術で得られる以上に向上させることが求められている。すなわち、これらの特性を向上させることは、COFの折り曲げ実装時にリードが断線しにくくなるため、銅被覆ポリイミド基板の信頼性を高めることに繋がる。 By the way, with the development of the mounting technology and the expansion of the use of the copper-coated polyimide substrate, it is required that the characteristics of the copper-coated polyimide substrate be improved in bending resistance and the like beyond those obtained by the conventional technology. That is, improving these characteristics leads to an increase in the reliability of the copper-coated polyimide substrate because the leads are less likely to be disconnected when the COF is bent and mounted.
本発明の目的は、上記の従来技術の問題点に鑑み、チップオンフィルム(COF)の折り曲げ実装時に求められる耐屈曲性において、MIT耐折性試験(JIS C 5016)により200回以上の折曲げ性が得られ、折曲げに対する耐久性に優れる半導体実装用の銅被覆ポリイミド基板とその製造方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art by bending 200 times or more by the MIT folding resistance test (JIS C 5016) in bending resistance required at the time of bending mounting of a chip-on-film (COF). The object is to provide a copper-coated polyimide substrate for semiconductor mounting and a method for producing the same, which are excellent in durability against bending.
本発明者らは、上記目的を達成するために、スパッタリング法によってニッケル−クロム系合金層及び銅層を形成し、さらにその上に電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で銅皮膜を形成してなる銅被覆ポリイミド基板について、鋭意研究を重ねた結果、前記銅皮膜中に形成された結晶の平均結晶粒径(以下、銅皮膜の平均結晶粒径と呼称する場合がある。)を特定の条件に制御したところ、折曲げに対する耐久性が向上し、MIT耐折性試験(JIS C 5016)により200回以上の折曲げ性が得られること、また、その製造方法として、前記銅皮膜を形成する工程で用いる電気めっき法において、不溶解性陽極を用い、かつ鉄イオンを特定の濃度で含有する銅めっき液を用いたところ、前記銅皮膜の平均結晶粒径を制御することができ、それにより前記折曲げ性を有する半導体実装用の銅被覆ポリイミド基板が得られることを見出し、本発明を完成した。 In order to achieve the above object, the inventors of the present invention form a nickel-chromium alloy layer and a copper layer by a sputtering method, and further use an electroplating method or an electroplating method and an electroless plating method in combination thereon. As a result of intensive research on a copper-coated polyimide substrate formed with a copper film by the method, the average crystal grain size of crystals formed in the copper film (hereinafter referred to as the average crystal grain size of the copper film) Is controlled to a specific condition, the durability against bending is improved, and the bending performance of 200 times or more is obtained by the MIT folding resistance test (JIS C 5016), and the manufacturing method thereof In the electroplating method used in the step of forming the copper film, an insoluble anode is used and a copper plating solution containing iron ions at a specific concentration is used. It is possible to control the crystal grain size, thereby it found that the copper-coated polyimide substrate for semiconductor mounting having the bending resistance can be obtained, and have completed the present invention.
すなわち、本発明の第1の発明によれば、ポリイミドフィルムの少なくとも片面に、スパッタリング法によってニッケル−クロム系合金層及び銅層を形成し、さらにその上に電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で銅皮膜を形成してなる銅被覆ポリイミド基板において、
前記銅皮膜の平均結晶粒径は、160〜700nmであることを特徴とする銅被覆ポリイミド基板が提供される。
That is, according to the first invention of the present invention, a nickel-chromium alloy layer and a copper layer are formed on at least one surface of a polyimide film by a sputtering method, and then an electroplating method or an electroplating method is used. In a copper-coated polyimide substrate formed by forming a copper film by a method using an electroplating method in combination,
An average crystal grain size of the copper film is 160 to 700 nm. A copper-coated polyimide substrate is provided.
また、本発明の第2の発明によれば、ポリイミドフィルムの少なくとも片面に、スパッタリング法によってニッケル−クロム系合金層及び銅層を形成する工程、及びさらにその上に電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で銅皮膜を形成する工程を含む、第1の発明の銅被覆ポリイミド基板の製造方法であって、
前記電気めっき法において、不溶解性陽極を用い、かつ鉄イオンを全量に対し0.1〜10g/Lの濃度で含有する銅めっき液を用いることを特徴とする銅被覆ポリイミド基板の製造方法が提供される。
According to the second invention of the present invention, a step of forming a nickel-chromium alloy layer and a copper layer by sputtering on at least one surface of the polyimide film, and further an electroplating method or electroplating method thereon A method for producing a copper-coated polyimide substrate of the first invention, comprising a step of forming a copper film by a method using a combination of an electroless plating method and
In the electroplating method, there is provided a method for producing a copper-coated polyimide substrate, wherein a copper plating solution containing an insoluble anode and containing iron ions at a concentration of 0.1 to 10 g / L is used. Provided.
また、本発明の第3の発明によれば、第2の発明において、前記不溶解性陽極は、金属陽極又はセラミックス系陽極であることを特徴とする銅被覆ポリイミド基板の製造方法が提供される。 According to a third aspect of the present invention, there is provided the method for producing a copper-coated polyimide substrate according to the second aspect, wherein the insoluble anode is a metal anode or a ceramic anode. .
また、本発明の第4の発明によれば、第2の発明において、前記銅めっき液は、銅イオンと鉄イオンを含有する硫酸酸性めっき液であることを特徴とする銅被覆ポリイミド基板の製造方法が提供される。 According to a fourth aspect of the present invention, in the second aspect, the copper plating solution is a sulfuric acid acidic plating solution containing copper ions and iron ions. A method is provided.
また、本発明の第5の発明によれば、第4の発明において、前記銅めっき液の銅イオンは、銅めっき液の排液に無酸素銅を溶解することにより供給することを特徴とする銅被覆ポリイミド基板の製造方法が提供される。 According to a fifth aspect of the present invention, in the fourth aspect, the copper ions of the copper plating solution are supplied by dissolving oxygen-free copper in the drainage of the copper plating solution. A method for producing a copper-coated polyimide substrate is provided.
また、本発明の第6の発明によれば、第4の発明において、前記銅めっき液の鉄イオンは、銅めっき液の排液に硫酸鉄を添加することにより供給することを特徴とする銅被覆ポリイミド基板の製造方法が提供される。 According to a sixth invention of the present invention, in the fourth invention, the iron ions of the copper plating solution are supplied by adding iron sulfate to the drainage of the copper plating solution. A method of manufacturing a coated polyimide substrate is provided.
本発明の銅被覆ポリイミド基板は、MIT耐折性試験(JIS C 5016)において200回以上の折曲げ性を有する銅被覆ポリイミド基板であり、チップオンフィルム(COF)の折り曲げ実装時に求められる耐屈曲性を達成することができ、その製造方法は、該銅被覆ポリイミド基板を安定して製造することができるので、その工業的価値は極めて大きい。これにより、30μmピッチ以下のファインピッチのCOFを折り曲げて実装する際にも、リードが断線しにくい、折曲げに対する耐久性に優れた半導体実装用の銅被覆ポリイミド基板を得ることができる。 The copper-coated polyimide substrate of the present invention is a copper-coated polyimide substrate having a bending property of 200 times or more in the MIT folding resistance test (JIS C 5016), and is required to bend when the chip-on-film (COF) is bent and mounted. The production method can stably produce the copper-coated polyimide substrate, and thus the industrial value thereof is extremely large. As a result, even when a fine pitch COF with a pitch of 30 μm or less is folded and mounted, a copper-coated polyimide substrate for semiconductor mounting excellent in durability against bending, in which leads are hard to break, can be obtained.
1.銅被覆ポリイミド基板
本発明の銅被覆ポリイミド基板は、ポリイミドフィルムの少なくとも片面に、スパッタリング法によってニッケル−クロム系合金層及び銅層を形成し、さらにその上に電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で銅皮膜を形成してなる銅被覆ポリイミド基板において、前記銅皮膜の平均結晶粒径は、160〜700nmであることを特徴とする。
1. Copper-coated polyimide substrate The copper-coated polyimide substrate of the present invention is formed by forming a nickel-chromium alloy layer and a copper layer on at least one surface of a polyimide film by a sputtering method, and further performing an electroplating method or an electroplating method. In the copper-coated polyimide substrate formed by forming a copper film by the combined use of an electrolytic plating method, the average crystal grain size of the copper film is 160 to 700 nm.
本発明において、電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で形成される銅皮膜の平均結晶粒径を、160〜700nmの大きさに制御することが重要である。これによって、チップオンフィルム(COF)の折り曲げ実装時に求められる耐屈曲性において、MIT耐折性試験(JIS C 5016)により200回以上の折曲げ性が得られ、折曲げに対する耐久性に優れる半導体実装用の銅被覆ポリイミド基板が達成される。 In the present invention, it is important to control the average crystal grain size of the copper film formed by the electroplating method or the method using the electroplating method and the electroless plating method to 160 to 700 nm. As a result, in the bending resistance required when the chip-on-film (COF) is bent and mounted, the MIT bending resistance test (JIS C 5016) provides a folding performance of 200 times or more, and the semiconductor has excellent durability against bending. A copper-coated polyimide substrate for mounting is achieved.
上記銅被覆ポリイミド基板の構造を、図面を用いて説明する。図1は、本発明の銅被覆ポリイミド基板の概略断面図の一例を表す。図1において、銅被覆ポリイミド基板の断面は、ポリイミドフィルム1の表面上に、スパッタリング法により形成された金属シード層2と銅層3、及びめっき法による銅層4が順次積層された構造になっている。
The structure of the copper-coated polyimide substrate will be described with reference to the drawings. FIG. 1 shows an example of a schematic cross-sectional view of a copper-coated polyimide substrate of the present invention. In FIG. 1, the cross section of a copper-coated polyimide substrate has a structure in which a
上記銅被覆ポリイミド基板を構成する銅皮膜の平均結晶粒径としては、160nm以上であり、より大きなほど望ましい。すなわち、銅皮膜の平均結晶粒径が大きいほど、銅被覆ポリイミド基板の耐屈曲性が向上する。しかしながら、平均結晶粒径の上限としては、銅皮膜の形成方法により制限され、また、十分な耐屈曲性が得られる700nmで十分である。
なお、折り曲げ時のリードの破断は、銅めっき皮膜中の結晶粒界を起点として起こる場合が多く、結晶粒径を大きくすることで結晶粒界の面積を小さくすることができれば、破断が起こる可能性を低くすることができる。したがって、銅皮膜の平均結晶粒径が160nm以上である銅被覆ポリイミド基板では、MIT耐折性試験(JIS C 5016)において200回以上の特性を得ることができる。
The average crystal grain size of the copper film constituting the copper-coated polyimide substrate is 160 nm or more, and the larger the crystal grain size, the more desirable. That is, as the average crystal grain size of the copper film is larger, the bending resistance of the copper-coated polyimide substrate is improved. However, the upper limit of the average crystal grain size is limited by the method of forming the copper film, and 700 nm is sufficient to obtain sufficient bending resistance.
In addition, the breakage of the lead at the time of bending often occurs from the crystal grain boundary in the copper plating film, and if the crystal grain boundary area can be reduced by increasing the crystal grain size, the breakage may occur. Can be lowered. Therefore, a copper-coated polyimide substrate having an average crystal grain size of the copper film of 160 nm or more can obtain characteristics of 200 times or more in the MIT folding resistance test (JIS C 5016).
2.銅被覆ポリイミド基板の製造方法
本発明の製造方法は、ポリイミドフィルムの少なくとも片面に、スパッタリング法によってニッケル−クロム系合金層及び銅層を形成する工程、及びさらにその上に電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法で銅皮膜を形成する工程を含む、請求項1に記載の銅被覆ポリイミド基板の製造方法であって、前記電気めっき法において、不溶解性陽極を用い、かつ鉄イオンを全量に対し0.1〜10g/Lの濃度で含有する銅めっき液を用いることを特徴とする。
2. Method for Producing Copper-Coated Polyimide Substrate The production method of the present invention comprises a step of forming a nickel-chromium alloy layer and a copper layer by sputtering on at least one surface of a polyimide film, and an electroplating method or electroplating thereon. A method for producing a copper-coated polyimide substrate according to
まず、本発明の製造方法を図面を用いて説明する。図2は、上記銅被覆ポリイミド基板の製造工程を示す。図2において、銅被覆ポリイミド基板8は、原料であるポリイミドフィルム5上に、スパッタリング工程6及び電気メッキ工程7により、スパッタリング処理及び電気めっき処理を施し、所望の金属皮膜を形成することによって製造される。この方法によって製造された銅被覆ポリイミド基板は、接着剤を必要としないため、高耐熱性、高絶縁性などのポリイミド本来の特性を利用することができる。以下に、各工程の詳細な条件を説明する。 First, the manufacturing method of this invention is demonstrated using drawing. FIG. 2 shows a manufacturing process of the copper-coated polyimide substrate. In FIG. 2, a copper-coated polyimide substrate 8 is manufactured by performing sputtering and electroplating processes on a polyimide film 5 as a raw material by a sputtering process 6 and an electroplating process 7 to form a desired metal film. The Since the copper-coated polyimide substrate produced by this method does not require an adhesive, it can utilize the inherent characteristics of polyimide such as high heat resistance and high insulation. Below, the detailed conditions of each process are demonstrated.
上記スパッタリング工程において、ポリイミドフィルムの少なくとも片面の表面上に所望の銅導体層を形成する。
この工程においては、まず、スパッタリング法によって、ニッケル−クロム系合金等の金属シード層を形成する。前記金属シード層としては、特に限定されるものではなく、ポリイミドフィルムと金属層の密着力、及び基板の耐熱、耐湿度環境下での安定性等の特性を確保する役割を果たすことができるものが用いられるが、この中で、スパッタリング法により形成されたニッケル層、クロム層、又はニッケル、クロム及び銅のいずれか2種以上を含む合金層から選ばれる少なくとも1種が好ましく、特に、ニッケル層、クロム層、又はニッケル−クロム合金層がより好ましく、ニッケルクロム合金層がさらに好ましい。この金属シード層の厚さは、特に限定されるものではないが、5〜50nmが好ましい。また、ニッケル−クロム合金層の合金組成としては、特に限定されるものではないが、前記合金層中のクロム品位は5〜30重量%が好ましい。
続いて、良好な導電性を付与するためにスパッタリング法によって銅層を形成する。この工程によって形成される銅層の厚さは50〜500nmが好ましい。なお、この工程においては、スパッタリング法の代わりに蒸着法を用いることもできる。
In the sputtering step, a desired copper conductor layer is formed on at least one surface of the polyimide film.
In this step, first, a metal seed layer such as a nickel-chromium alloy is formed by sputtering. The metal seed layer is not particularly limited, and can play a role of ensuring characteristics such as adhesion between the polyimide film and the metal layer, heat resistance of the substrate, and stability in a humidity resistant environment. Among these, at least one selected from a nickel layer formed by sputtering, a chromium layer, or an alloy layer containing any two or more of nickel, chromium, and copper is preferable. A chromium layer or a nickel-chromium alloy layer is more preferable, and a nickel chromium alloy layer is more preferable. The thickness of the metal seed layer is not particularly limited, but is preferably 5 to 50 nm. The alloy composition of the nickel-chromium alloy layer is not particularly limited, but the chromium quality in the alloy layer is preferably 5 to 30% by weight.
Subsequently, a copper layer is formed by a sputtering method in order to impart good conductivity. The thickness of the copper layer formed by this step is preferably 50 to 500 nm. In this step, a vapor deposition method can be used instead of the sputtering method.
次いで、その上に、電気めっき法、或いは電気めっき法と無電解めっき法を併用する方法によって銅層の厚膜化を行い、所望の厚さの銅層を形成する。
この工程によって形成される銅層の厚さは、例えば、サブトラクティブ法によって回路パターンを形成する場合は5〜18μmが好ましい。
Next, the copper layer is thickened by an electroplating method or a method using an electroplating method and an electroless plating method together to form a copper layer having a desired thickness.
For example, when the circuit pattern is formed by the subtractive method, the thickness of the copper layer formed by this step is preferably 5 to 18 μm.
上記電気めっき法において、不溶解性陽極を用い、かつ鉄イオンを全量に対し0.1〜10g/L含有する銅めっき液を用いることが重要である。これによって、所望の大きさの平均結晶粒径を有する結晶からなる銅皮膜が形成される。
すなわち、不溶解性陽極は、溶解性の陽極に比べて、硫酸銅めっき液中でも比較的安定であり、劣化した場合も再度焼成することによって再生可能であるという利点を有している。その一方で、前述の通り、不溶解性陽極を用いる場合には、一般的には、電気めっき処理中に酸素ガスが発生し、これに伴う問題が発生するとともに、形成される銅皮膜の平均結晶粒径は細かいため、銅被覆ポリイミド基板の耐屈曲性が十分でないという課題があった。
In the electroplating method, it is important to use an insoluble anode and a copper plating solution containing 0.1 to 10 g / L of iron ions with respect to the total amount. As a result, a copper film made of crystals having a desired average grain size is formed.
That is, the insoluble anode has an advantage that it is relatively stable in the copper sulfate plating solution as compared with the soluble anode and can be regenerated by firing again even when it is deteriorated. On the other hand, as described above, when using an insoluble anode, oxygen gas is generally generated during the electroplating process, and problems associated therewith occur, and the average of the copper film to be formed Since the crystal grain size is fine, there is a problem that the bending resistance of the copper-coated polyimide substrate is not sufficient.
これに対して、本発明の方法では、不溶解性陽極を用いた場合においても、さらに銅めっき液中に所定量の鉄イオンを添加することによって酸素ガスの発生の抑制を図るとともに、銅皮膜の平均結晶粒径を大きくすることができる。これにより、耐屈曲性において、溶解性の含リン銅の陽極を用いた場合、及び不溶解性陽極を用いた場合においても、銅めっき液中に鉄イオンを添加しない場合に得られる銅被覆ポリイミド基板と比較して優れた銅被覆ポリイミド基板を得ることができた。これは不溶解性陽極を用い、めっき液中の濃度が0.1〜10g/Lとなるように鉄イオンを添加したことによって、銅めっき皮膜の結晶成長モードが変化し、溶解性陽極を用いた場合、及び所定量の鉄イオンを添加しない場合より銅めっき皮膜中の結晶粒径が大きくなったためであると考えられる。 In contrast, in the method of the present invention, even when an insoluble anode is used, the generation of oxygen gas is further suppressed by adding a predetermined amount of iron ions to the copper plating solution, and the copper film is formed. The average crystal grain size can be increased. This makes it possible to obtain a copper-coated polyimide obtained when no iron ions are added to the copper plating solution, even when a soluble phosphorous copper anode is used in bending resistance and when an insoluble anode is used. A copper-coated polyimide substrate superior to that of the substrate could be obtained. This is because an insoluble anode is used, and by adding iron ions so that the concentration in the plating solution is 0.1 to 10 g / L, the crystal growth mode of the copper plating film changes, and the soluble anode is used. It is thought that this is because the crystal grain size in the copper plating film is larger than that in the case where the predetermined amount of iron ions is not added.
この理由としては、次のように説明される。銅めっき液中に鉄イオンを添加する場合、銅めっき液中には2価の鉄イオンと3価の鉄イオンが共存する。電気化学的に、陽極上では鉄イオンの酸化反応が水の電気分解反応に優先して起こるため、酸素ガスの発生を抑制することとなる。また、このうち3価の鉄イオンは、陰極上では、銅を溶解し、銅めっき液中に銅イオンを供給する。このとき、3価の鉄イオン自身は還元されて2価の鉄イオンとなる。銅めっき皮膜が成長する場合にも同様の作用が起こり、成長初期の微細な結晶粒の一部は、3価の鉄イオンに溶解される。このため、結晶の核の数が鉄イオンを添加しない場合と比較して減少するので、それぞれの結晶粒が大きく成長することによって結晶粒の粗大化が起こると考えられる。 The reason is explained as follows. When iron ions are added to the copper plating solution, divalent iron ions and trivalent iron ions coexist in the copper plating solution. Electrochemically, the oxidation reaction of iron ions takes precedence over the electrolysis reaction of water on the anode, so that the generation of oxygen gas is suppressed. Of these, trivalent iron ions dissolve copper on the cathode and supply the copper ions into the copper plating solution. At this time, the trivalent iron ions themselves are reduced to become divalent iron ions. A similar action occurs when the copper plating film grows, and a part of the fine crystal grains in the initial stage of growth is dissolved in trivalent iron ions. For this reason, since the number of crystal nuclei is reduced as compared with the case where no iron ion is added, it is considered that each crystal grain grows large and thereby coarsening of the crystal grain occurs.
また、溶解性陽極を用いた場合には、陽極が銅イオンの供給源となっているため、陰極であるめっき基板と銅イオンの供給源までの距離が十分近く、陰極の近傍では銅イオンが常に過飽和状態にあると考えられる。これに対して、不溶解性陽極を用いた場合には、陽極と銅イオンの供給源はそれぞれ独立しており、陰極と銅イオンの供給源との距離が溶解性の陽極を用いた場合より離れているため、銅の過飽和度は溶解性の陽極の場合より低くなっていると考えられる。したがって、銅めっき皮膜中の結晶成長のモードは、核成長モードが支配的になっており、結晶粒が大きく成長すると考えられる。 In addition, when a soluble anode is used, the anode serves as a copper ion supply source, so the distance between the plating substrate, which is the cathode, and the copper ion supply source is sufficiently close. It is always considered supersaturated. On the other hand, when an insoluble anode is used, the anode and the copper ion supply source are independent from each other, and the distance between the cathode and the copper ion supply source is greater than when a soluble anode is used. Because of the separation, the supersaturation degree of copper is considered to be lower than that of the soluble anode. Accordingly, it is considered that the crystal growth mode in the copper plating film is dominated by the nucleus growth mode, and the crystal grains grow greatly.
以上の説明のように、めっき液中に鉄イオンを添加したこと、及び不溶性陽極を用いたことによって陰極への銅イオンの供給方法が変化したことが複合して、相乗効果を生み出し、銅めっき皮膜中の結晶の粒径が大きくなっているものと考えられる。 As described above, a combination of the addition of iron ions to the plating solution and the change in the supply method of copper ions to the cathode due to the use of an insoluble anode has created a synergistic effect, and copper plating. It is considered that the crystal grain size in the film is increased.
上記製造方法で用いる銅めっき液中の鉄イオンの濃度としては、0.1〜10g/Lであり、好ましくは0.5〜10g/Lである。すなわち、鉄イオンの濃度が0.1g/L未満では、酸素ガスの発生低減の効果が十分でなく、かつ、結晶の粗大化と耐屈曲性の向上が不十分である。一方、10g/Lを超えると、電気めっきの際の電流効率が著しく低下するので、経済的でない。 As a density | concentration of the iron ion in the copper plating solution used with the said manufacturing method, it is 0.1-10 g / L, Preferably it is 0.5-10 g / L. That is, when the concentration of iron ions is less than 0.1 g / L, the effect of reducing the generation of oxygen gas is not sufficient, and the coarsening of crystals and the improvement in bending resistance are insufficient. On the other hand, if it exceeds 10 g / L, the current efficiency during electroplating is significantly reduced, which is not economical.
上記製造方法で用いる電気めっき装置としては、特に限定されるものでなく、例えば、イオン交換膜で銅めっき液から隔てた陽極室内に不溶解性陽極を設ける。また、銅イオンの供給源専用の槽を設置し、めっき処理を行う槽からの銅めっき液の排液を循環して、銅源を溶解する。 The electroplating apparatus used in the manufacturing method is not particularly limited. For example, an insoluble anode is provided in an anode chamber separated from a copper plating solution by an ion exchange membrane. Also, a tank dedicated to the copper ion supply source is installed, and the copper source is dissolved by circulating the drainage of the copper plating solution from the tank for performing the plating treatment.
上記不溶解性陽極としては、特に限定されるものではなく、例えば、白金、鉛等の金属陽極、又は,チタン製のフレームに酸化イリジウム、酸化ロジウム、酸化ルテニウム等の導電性を有するセラミックスを焼成してコーティングしたセラミックス系の陽極が好適に使用できるが、この中で、特にチタン製のフレームに酸化イリジウム及び酸化ロジウムをコーティングしたセラミックス系の陽極が好ましい。 The insoluble anode is not particularly limited. For example, a metal anode such as platinum or lead or a ceramic having conductivity such as iridium oxide, rhodium oxide, or ruthenium oxide on a titanium frame is fired. The ceramic-based anode coated in this manner can be suitably used. Among these, a ceramic-based anode in which a titanium frame is coated with iridium oxide and rhodium oxide is particularly preferable.
上記銅めっき液としては、銅イオンと鉄イオンを含有する硫酸酸性めっき液を用いられ、必要に応じて、平滑性等を確保するため通常のめっき液で用いられる添加物等が添加される。 As said copper plating solution, the sulfuric acid acidic plating solution containing a copper ion and an iron ion is used, and the additive etc. which are used with a normal plating solution in order to ensure smoothness etc. are added as needed.
上記銅源としては、特に限定されるものではなく、例えば、酸化銅、炭酸銅、無酸素銅等が好適に用いられるが、この中で、銅めっき液中に添加した3価の鉄イオンによって容易に溶解される無酸素銅が好ましい。 The copper source is not particularly limited, and for example, copper oxide, copper carbonate, oxygen-free copper, etc. are suitably used. Among these, depending on trivalent iron ions added to the copper plating solution. Oxygen-free copper that is easily dissolved is preferred.
上記銅めっき液へ鉄イオンを添加する方法としては、特に限定されるものではなく、例えば、硫酸系のめっき液であるので硫酸鉄を所定の濃度になるように溶解し、銅めっき液に添加するのが好ましい。なお、銅めっき液中の鉄イオンが全量に対し0.1〜10g/L含有するように調整する。 The method of adding iron ions to the copper plating solution is not particularly limited. For example, since it is a sulfuric acid-based plating solution, iron sulfate is dissolved to a predetermined concentration and added to the copper plating solution. It is preferable to do this. In addition, it adjusts so that the iron ion in a copper plating solution may contain 0.1-10 g / L with respect to the whole quantity.
以下に、本発明の実施例及び比較例によって本発明をさらに詳細に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。なお、実施例及び比較例で用いた評価方法としては、以下の通りである。
(1)平均結晶粒径:X線回折装置X´Pert PRO MPD(PANalytical社製)を用いて、サンプルの半価幅をScherrerの式に代入して結晶子の大きさを算出した。
(2)耐屈曲性の評価方法:JIS C 5016 MIT耐折性試験方法によって、折れ曲げに至るまでの折曲げ回数を求めた
Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, as an evaluation method used by the Example and the comparative example, it is as follows.
(1) Average crystal grain size: Using an X-ray diffractometer X'Pert PRO MPD (manufactured by PANalytical), the half width of the sample was substituted into Scherrer's formula to calculate the crystallite size.
(2) Evaluation method of bending resistance: The number of bending until bending was obtained by the JIS C 5016 MIT folding resistance test method.
(実施例1)
ポリイミドフィルムとして東レ・デュポン製のKapton 150EN(厚さ38μm)を用いた。
まず、このフィルムに、真空度を0.01〜0.1Paに保持したチャンバー内で150℃で1分間の熱処理を施した。引き続き、このフィルム上にスパッタリング法によってクロムを7重量%含有するニッケル−クロム合金層を7nmの厚さで形成し、さらに銅層を100nmの厚さで形成した。その後、電気めっき工程で電気めっき法によって銅層を8μmの厚さで形成した。
ここで用いた銅めっき液の基本的な組成は、硫酸濃度180g/L、硫酸銅濃度80g/L、及び塩素濃度50mg/Lであり、これに銅めっき皮膜の平滑性等を確保する目的で有機系の添加剤を所定量添加した。電気めっき工程における陽極としては、酸化イリジウム系の不溶解性陽極である日本カーリット製のエクセロード・Fタイプ(チタン製のフレームに酸化イリジウムを焼成してコーティングしたセラミックス系の陽極)を採用した。また、銅イオンの供給源としては、無酸素銅ボールを採用した。また、銅めっき液中の鉄イオン濃度は、0.1g/Lとなるように硫酸鉄溶液を添加した。
その後、得られた銅被覆ポリイミド基板の銅皮膜中の平均結晶粒径と耐折性を、上記評価方法にしたがって評価した。結果を表1に示す。
(Example 1)
As the polyimide film, Kapton 150EN (thickness 38 μm) manufactured by Toray DuPont was used.
First, this film was heat-treated at 150 ° C. for 1 minute in a chamber maintained at a vacuum degree of 0.01 to 0.1 Pa. Subsequently, a nickel-chromium alloy layer containing 7% by weight of chromium was formed with a thickness of 7 nm on this film by sputtering, and a copper layer was further formed with a thickness of 100 nm. Thereafter, a copper layer having a thickness of 8 μm was formed by electroplating in the electroplating step.
The basic composition of the copper plating solution used here is a sulfuric acid concentration of 180 g / L, a copper sulfate concentration of 80 g / L, and a chlorine concentration of 50 mg / L, for the purpose of ensuring the smoothness of the copper plating film. A predetermined amount of an organic additive was added. As an anode in the electroplating process, an exotic F type (ceramics type anode made by firing and coating iridium oxide on a titanium frame), which is an insoluble anode based on iridium oxide, was employed. In addition, an oxygen-free copper ball was adopted as a copper ion supply source. Further, an iron sulfate solution was added so that the iron ion concentration in the copper plating solution was 0.1 g / L.
Thereafter, the average crystal grain size and folding resistance in the copper film of the obtained copper-coated polyimide substrate were evaluated according to the above evaluation methods. The results are shown in Table 1.
(実施例2〜6)
電気めっき工程において、銅めっき液中の鉄イオン濃度を0.5g/L(実施例2)、1g/L(実施例3)、2g/L(実施例4)、5g/L(実施例5)、10g/L(実施例6)としたこと以外は実施例1と同様に行い、得られた銅被覆ポリイミド基板の銅皮膜中の平均結晶粒径と耐折性を、上記評価方法にしたがって評価した。結果を表1に示す。
(Examples 2 to 6)
In the electroplating step, the iron ion concentration in the copper plating solution is 0.5 g / L (Example 2), 1 g / L (Example 3), 2 g / L (Example 4), 5 g / L (Example 5). ) 10 g / L (Example 6), except that it was the same as in Example 1, and the average crystal grain size and folding resistance in the copper film of the obtained copper-coated polyimide substrate were determined according to the above evaluation method. evaluated. The results are shown in Table 1.
(比較例1)
電気めっき工程において、陽極として溶解性の含リン銅の陽極を用いたこと、及び銅めっき液中に鉄イオンを添加しないこと以外は実施例1と同様に行い、得られた銅被覆ポリイミド基板の銅皮膜中の平均結晶粒径と耐折性を、上記評価方法にしたがって評価した。結果を表1に示す。
(Comparative Example 1)
In the electroplating step, the same procedure as in Example 1 was performed except that a soluble phosphorous copper anode was used as the anode and no iron ions were added to the copper plating solution. The average crystal grain size and folding resistance in the copper film were evaluated according to the above evaluation methods. The results are shown in Table 1.
(比較例2)
電気めっき工程において、めっき液中の鉄イオン濃度を0.05g/Lとしたこと以外は実施例1と同様に行い、得られた銅被覆ポリイミド基板の銅皮膜中の平均結晶粒径と耐折性を、上記評価方法にしたがって評価した。結果を表1に示す。
(Comparative Example 2)
In the electroplating step, except that the iron ion concentration in the plating solution was set to 0.05 g / L, it was performed in the same manner as in Example 1, and the average crystal grain size and folding resistance in the copper film of the obtained copper-coated polyimide substrate were obtained. The sex was evaluated according to the above evaluation method. The results are shown in Table 1.
表1より、実施例1〜6では、不溶解性陽極を用い、かつ銅めっき液中の鉄イオン濃度は、0.1〜10g/Lに調整して、本発明の方法に従って行われたので、銅皮膜中の結晶の平均結晶粒径が160〜700nmの銅被覆ポリイミド基板が得られ、そのMIT耐折性は200回以上であることが分かる。
これに対して、比較例1又は2では、陽極の種類又は銅めっき液中の鉄イオン濃度がこれらの条件に合わないので、銅皮膜中の結晶の平均結晶粒径が小さく、かつMIT耐折性で満足すべき結果が得られないことが分かる。
As shown in Table 1, in Examples 1 to 6, the insoluble anode was used, and the iron ion concentration in the copper plating solution was adjusted to 0.1 to 10 g / L. It can be seen that a copper-coated polyimide substrate having an average crystal grain size of crystals in the copper film of 160 to 700 nm is obtained, and the MIT folding resistance is 200 times or more.
On the other hand, in Comparative Example 1 or 2, since the type of anode or the iron ion concentration in the copper plating solution does not meet these conditions, the average crystal grain size of crystals in the copper film is small, and the MIT folding resistance It can be seen that satisfactory results cannot be obtained with sex.
以上より明らかなように、本発明の銅被覆ポリイミド基板とその製造法方法は、折曲げに対する耐久性に優れ、耐折曲げ性を要求される携帯電話等のフレキシブル基板の素材として十分な特性を有しているので、携帯電子機器用のTAB及びCOFの小型化、薄膜化に対応する基板として有用である。 As is clear from the above, the copper-coated polyimide substrate and the method for producing the same of the present invention are excellent in durability against bending and have sufficient characteristics as a material for flexible substrates such as mobile phones that require bending resistance. Therefore, it is useful as a substrate for miniaturization and thinning of TAB and COF for portable electronic devices.
1 ポリイミドフィルム
2 スパッタリング法による金属シード層
3 スパッタリング法による銅層
4 めっき法による銅層
5 原料(ポリイミドフィルム)
6 スパッタリング工程
7 電気メッキ工程
8 銅被覆ポリイミド基板
DESCRIPTION OF
6 Sputtering process 7 Electroplating process 8 Copper coated polyimide substrate
Claims (6)
前記銅皮膜の平均結晶粒径は、160〜700nmであることを特徴とする銅被覆ポリイミド基板。 A nickel-chromium alloy layer and a copper layer are formed on at least one surface of the polyimide film by sputtering, and a copper film is further formed thereon by electroplating or a combination of electroplating and electroless plating. In the copper-coated polyimide substrate
The copper-coated polyimide substrate, wherein the copper film has an average crystal grain size of 160 to 700 nm.
前記電気めっき法において、不溶解性陽極を用い、かつ鉄イオンを全量に対し0.1〜10g/Lの濃度で含有する銅めっき液を用いることを特徴とする銅被覆ポリイミド基板の製造方法。 A step of forming a nickel-chromium alloy layer and a copper layer by sputtering on at least one surface of the polyimide film, and further, an electroplating method or a method using a combination of electroplating and electroless plating on the copper film. It is a manufacturing method of the copper covering polyimide substrate according to claim 1 including the process of forming,
In the said electroplating method, the manufacturing method of the copper coating polyimide board | substrate characterized by using the copper plating liquid which uses an insoluble anode and contains iron ion with the density | concentration of 0.1-10 g / L with respect to the whole quantity.
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