JPH0718421A - Substrate of high molecular material coated with electric conductive metallic film and its production - Google Patents
Substrate of high molecular material coated with electric conductive metallic film and its productionInfo
- Publication number
- JPH0718421A JPH0718421A JP16765593A JP16765593A JPH0718421A JP H0718421 A JPH0718421 A JP H0718421A JP 16765593 A JP16765593 A JP 16765593A JP 16765593 A JP16765593 A JP 16765593A JP H0718421 A JPH0718421 A JP H0718421A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- film
- metal film
- conductive metal
- metallic film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、集積回路（ＩＣ）等の
電子部品を実装したいわゆるタブ（ＴＡＢ）パッケージ
を製造するための基体となるフィルムや、フレキシブル
プリント回路（ＦＰＣ）を製造するための基体となるフ
ィルムのような、通常合成樹脂の如き高分子材料からな
る基体であって、導電性金属膜で被覆されたもの及びそ
れを製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is for producing a film as a base for producing a so-called tab (TAB) package on which electronic parts such as an integrated circuit (IC) are mounted, and a flexible printed circuit (FPC). The present invention relates to a substrate, which is usually made of a polymer material such as a synthetic resin, such as a film to be the substrate, coated with a conductive metal film, and a method for producing the same.
【０００２】[0002]
【従来の技術】集積回路（ＩＣ）や大規模集積回路（Ｌ
ＳＩ）の実用化と共に、それらを実装するために各種の
高分子材料からなる基体上に配線する技術が確立されて
きた。かかる配線の方法としては様々な方法が試みられ
ているが、現在主流となっているのは以下に示す方法で
ある。即ち、配線基体として、例えば絶縁性、耐熱性等
に優れたポリエチレンテレフタレートやポリイミド系樹
脂からなる高分子材料フィルムを用い、該基体上に配線
前駆体である導電性金属膜、例えば銅（Ｃｕ）膜やアル
ミニウム（Ａｌ）膜を真空蒸着又はスパッタリング等に
より形成する。さらに、該膜で被覆された基体上に例え
ば所望の配線パターンをレジストで形成し、その後エッ
チングにより不要な導電性金属膜部分を除去した後、該
レジストを溶剤等で除去する。2. Description of the Related Art Integrated circuits (IC) and large scale integrated circuits (L)
Along with the practical application of (SI), a technique for wiring on a substrate made of various polymer materials has been established for mounting them. Although various methods have been tried as the wiring method, the following method is the most popular at present. That is, as the wiring substrate, for example, a polymer material film made of polyethylene terephthalate or a polyimide resin having excellent insulation and heat resistance is used, and a conductive metal film which is a wiring precursor, for example, copper (Cu), is formed on the substrate. A film or an aluminum (Al) film is formed by vacuum vapor deposition, sputtering, or the like. Further, for example, a desired wiring pattern is formed on the substrate covered with the film with a resist, and then unnecessary conductive metal film portions are removed by etching, and then the resist is removed with a solvent or the like.
【０００３】[0003]
【発明が解決しようとする課題】しかし、このように配
線前駆体としての導電性金属膜を高分子材料基体上に形
成すると、該基体とその上に形成された導電性金属膜と
の密着力が弱く、例えば成膜後、該基体が高温あるいは
低温に曝されると該膜が剥がれることもある。また、基
体に対する膜密着力が経時的に低下するという問題もあ
る。However, when the conductive metal film as the wiring precursor is formed on the polymer material substrate as described above, the adhesion between the substrate and the conductive metal film formed thereon is high. However, the film may peel off when the substrate is exposed to a high temperature or a low temperature after the film formation. There is also a problem that the film adhesion to the substrate decreases with time.
【０００４】このような問題を解決する手段として、配
線前駆体である導電性金属膜と基体との密着力をより向
上させるために、基体上にまずニッケル（Ｎｉ）、チタ
ン（Ｔｉ）、クロム（Ｃｒ）等の金属から成る中間膜を
形成し、その外側に導電性金属膜を被覆することも行わ
れているが、このような手法により形成された導電性金
属膜であっても、成膜直後の密着力は強いものの、その
密着力は経時的に著しく低下する。As a means for solving such a problem, nickel (Ni), titanium (Ti), and chromium are first formed on the substrate in order to improve the adhesion between the conductive metal film, which is a wiring precursor, and the substrate. It is also practiced to form an intermediate film made of a metal such as (Cr) and cover the outside with a conductive metal film. However, even a conductive metal film formed by such a method can be formed. Although the adhesive strength immediately after the film is strong, the adhesive strength significantly decreases with time.
【０００５】そこで本発明は、導電性金属膜で被覆され
た高分子材料基体であって、該導電性金属膜と基体との
密着力が成膜後も経時的に変化、低下し難いもの及びそ
の製造方法を提供することを課題とする。Therefore, the present invention relates to a polymer material substrate coated with a conductive metal film, in which the adhesive force between the conductive metal film and the substrate is unlikely to change or decrease with time even after film formation. It is an object to provide a manufacturing method thereof.
【０００６】[0006]
【課題を解決するための手段】本発明者は前記課題を解
決すべく研究を重ね、以下の知見を得た。即ち、先ず、
このような導電性金属膜と高分子材料基体との密着力の
低下は、基体内部に存在する水（Ｈ2 Ｏ）に由来する酸
素（Ｏ）により、前記導電性金属膜や該膜と基体との界
面に両者の密着力を強化する目的で形成された中間金属
膜が酸化され、劣化することに起因すると推測するに至
った。そこで、導電性金属膜或いは中間金属膜の形成に
先立って、基体表面部分に水素イオン注入層を形成して
みたところ、導電性金属膜或いは中間金属膜の基体に対
する密着力が長期に亘り保持されることを見出した。Means for Solving the Problems The present inventor has conducted extensive studies to solve the above problems and has obtained the following findings. That is, first,
The decrease in the adhesive force between the conductive metal film and the polymer material substrate is caused by oxygen (O) derived from water (H 2 O) existing inside the substrate, the conductive metal film or the film and the substrate. It has been speculated that this is due to the oxidation and deterioration of the intermediate metal film formed at the interface with and for the purpose of strengthening the adhesion between the two. Therefore, when a hydrogen ion-implanted layer was formed on the surface of the substrate prior to the formation of the conductive metal film or the intermediate metal film, the adhesion of the conductive metal film or the intermediate metal film to the substrate was maintained for a long period of time. I found that.
【０００７】以上の知見に基づき、本発明は、導電性金
属膜で被覆された高分子材料基体であって、該基体表面
部分に水素イオン（Ｈ+ ）が注入された層を有し、その
外側に導電性金属膜が被覆されていることを特徴とする
基体およびその製造方法であって、高分子材料基体に水
素イオン（Ｈ+ ）を照射することにより、該基体表面部
分に水素イオン（Ｈ+ ）が注入された層を形成し、その
後該イオン注入層の外側に導電性金属膜を形成すること
を特徴とする方法を提供するものである。Based on the above findings, the present invention is a polymeric material substrate coated with a conductive metal film, which has a layer in which hydrogen ions (H + ) are implanted in the surface portion of the substrate. A substrate characterized by being coated with a conductive metal film on the outside and a method for producing the same, wherein a polymer material substrate is irradiated with hydrogen ions (H + ) so that a hydrogen ion ( H + ) -implanted layer is formed, and then a conductive metal film is formed outside the ion-implanted layer.
【０００８】前記導電性金属膜は、基体のイオン注入層
上に直接形成してもよいが、イオン注入層上に中間金属
膜を形成し、その上に形成してもよい。本発明における
高分子材料基体の材質は特に限定されず、例えば絶縁性
及び耐熱性等に優れたポリエチレンテレフタレート（Ｐ
ＥＴ）、ポリイミド系樹脂等が考えられる。The conductive metal film may be formed directly on the ion-implanted layer of the substrate, but may be formed on the ion-implanted layer by forming an intermediate metal film. The material of the polymeric material substrate in the present invention is not particularly limited, and for example, polyethylene terephthalate (P
ET), polyimide resin, etc. are considered.
【０００９】前記基体において、導電性金属膜の材質と
しては、例えば電気伝導度が大きく、可撓性に優れ、し
かも品質を均一化し易いＣｕ、Ａｌ、銀（Ａｇ）、白金
（Ｐｔ）、金（Ａｕ）等が考えられる。また、該基体と
前記導電性金属膜との界面に形成される中間金属膜の材
質としては、Ｎｉ、Ｔｉ、Ｃｒ等が考えられる。In the substrate, the material of the conductive metal film is, for example, Cu, Al, silver (Ag), platinum (Pt), gold, which has high electric conductivity, excellent flexibility, and easy quality uniformity. (Au) and the like are possible. The material of the intermediate metal film formed at the interface between the substrate and the conductive metal film may be Ni, Ti, Cr or the like.
【００１０】前記Ｈ+ 照射において用いるイオン源の方
式は特に限定はなく、例えば非質量分離型の高周波型、
カウフマン型、バケット型等のものが考えられる。ま
た、Ｈ+ を生成させるための原料ガスとしては、水素ガ
ス（Ｈ2 ）等が考えられる。前記Ｈ+ 照射における照射
エネルギ及び照射量は、基体、中間金属膜及び導電性金
属膜の材質によって異なるが、照射エネルギは５００ｅ
Ｖ〜１０ＫｅＶ程度、照射量は１×１０15〜１×１０20
ｉｏｎｓ／ｃｍ2 程度とするのが望ましい。照射エネル
ギが５００ｅＶより小さいと、Ｈ+ が基体内部に注入さ
れず、１０ＫｅＶより大きいと、基体に与えるダメージ
が大きくなり、導電性金属膜と基体との密着力が逆に低
下する。また、照射量が１×１０15ｉｏｎｓ／ｃｍ2 よ
り小さいと、Ｈ+ を注入することによる効果が不十分に
なり、１×１０20ｉｏｎｓ／ｃｍ2 より大きいと、基体
に与えるダメージが大きくなり、導電性金属膜と基体と
の密着力が逆に低下する。The method of the ion source used in the H + irradiation is not particularly limited, and for example, a non-mass separation type high frequency type,
Kauffman type, bucket type, etc. are conceivable. Further, hydrogen gas (H 2 ) or the like can be considered as a source gas for generating H + . The irradiation energy and the irradiation amount in the H + irradiation differ depending on the materials of the substrate, the intermediate metal film and the conductive metal film, but the irradiation energy is 500e.
V to 10 KeV, irradiation dose is 1 × 10 15 to 1 × 10 20
Ions / cm 2 is preferable. When the irradiation energy is less than 500 eV, H + is not injected into the inside of the substrate, and when it is more than 10 KeV, the damage given to the substrate increases, and the adhesive force between the conductive metal film and the substrate decreases conversely. If the dose is less than 1 × 10 15 ions / cm 2 , the effect of H + implantation is insufficient, and if it is greater than 1 × 10 20 ions / cm 2 , the damage to the substrate increases. However, the adhesive force between the conductive metal film and the substrate is decreased.
【００１１】前記Ｈ+ 照射において、基体に到達するＨ
+ の数はイオン電流測定器、例えば２次電子抑制電極を
備えたファラデーカップでモニタできる。なお、基体の
Ｈ+入射角度は、目的とするイオン注入層が得られる限
り特に限定されない。前記導電性金属膜及び前記中間金
属膜の形成方法としては、電子ビーム、抵抗、レーザ、
高周波等の手段で目的とする金属元素を含む物質を蒸着
させる真空蒸着、前記物質のイオンビーム、マグネトロ
ン、高周波等の手段によるスパッタリング、前記物質を
蒸着させる際に蒸着粒子を不活性ガスのプラズマ、電子
ビーム等の手段でイオン化させ、前記蒸着に該イオンの
照射を併用するイオンプレーティング等が考えられる。
また、前記物質の蒸着又はスパッタリングと前記物質と
は異なる元素からなるイオン種の照射とを併用するイオ
ンビームミキシング技術により、該基体上に膜形成して
もよい。In the above H + irradiation, H that reaches the substrate
The number of + can be monitored by an ion current measuring device, for example, a Faraday cup equipped with a secondary electron suppressing electrode. The H + incident angle of the substrate is not particularly limited as long as the target ion-implanted layer can be obtained. As the method of forming the conductive metal film and the intermediate metal film, electron beam, resistance, laser,
Vacuum deposition for depositing a substance containing a target metal element by means such as high frequency, ion beam of the substance, magnetron, sputtering by means such as high frequency, plasma of an inert gas vapor deposition particles when depositing the substance, Ion plating or the like is conceivable in which ionization is performed by a means such as an electron beam, and irradiation of the ions is also used in the vapor deposition.
Further, a film may be formed on the substrate by an ion beam mixing technique in which vapor deposition or sputtering of the substance and irradiation of an ion species composed of an element different from the substance are used in combination.
【００１２】前記成膜において蒸着又はスパッタされる
物質の原子数は膜厚モニタ、例えば水晶振動子式膜厚計
を用いた膜厚モニタでモニタでき、イオンビームミキシ
ング技術において基体上に到達するイオンの数は前記Ｈ
+ 照射の場合と同様にイオン電流測定器を用いてモニタ
できる。前記中間金属膜を形成させるために蒸着又はス
パッタ又はイオンプレートさせる物質としては、Ｎｉ単
体、Ｔｉ単体、及びＣｒ単体等が考えられる。The number of atoms of a substance vapor-deposited or sputtered in the above film formation can be monitored by a film thickness monitor, for example, a film thickness monitor using a crystal oscillator type film thickness meter, and ions arriving on the substrate in the ion beam mixing technique. The number of H
As in the case of + irradiation, it can be monitored using an ion current measuring device. As the substance to be vapor-deposited, sputtered or ion-plated to form the intermediate metal film, a simple substance of Ni, a simple substance of Ti, a simple substance of Cr or the like can be considered.
【００１３】本発明の基体は、さらにその外側に湿式め
っき等の手段にて、電極として用いるために、導電性金
属膜の膜厚を任意の膜厚まで増加させることが考えられ
る。Since the substrate of the present invention is used as an electrode on the outside by means such as wet plating, it is conceivable to increase the thickness of the conductive metal film to an arbitrary thickness.
【００１４】[0014]
【作用】本発明方法によると、先ず高分子材料基体にＨ
+ が照射されることで、該基体表面部分にＨ+ が注入さ
れた層が形成され、その上に直接又はその上に中間金属
膜が形成された後その上に、導電性金属膜が形成され
る。これにより形成される本発明の基体によると、導電
性金属膜と高分子材料基体との密着性が良く、且つ、そ
の良好な密着性がその後も維持される。According to the method of the present invention, H is first applied to the polymer material substrate.
By irradiating +, a layer in which H + has been injected is formed on the surface portion of the substrate, and a conductive metal film is formed directly or after an intermediate metal film is formed thereon. To be done. According to the substrate of the present invention thus formed, the adhesion between the conductive metal film and the polymer material substrate is good, and the good adhesion is maintained thereafter.
【００１５】本発明の基体において膜密着性が経時的に
変化、低下し難い理由は、基体表面部分に注入されたＨ
+ が、該基体内部に存在する水（Ｈ2 Ｏ）に由来する酸
素（Ｏ）を、該酸素が該基体外部へ湧き出す過程でトラ
ップすることにより、該酸素が導電性金属膜や中間金属
膜内へ侵入するのを防ぎ、これにより、それらの膜の酸
化による劣化が防がれるからではないかと考えられる。The reason why the film adhesiveness of the substrate of the present invention is less likely to change or decrease with time is because H injected into the surface portion of the substrate.
+ Traps oxygen (O) derived from water (H 2 O) existing inside the substrate in the process of the oxygen flowing out to the outside of the substrate, so that the oxygen can be a conductive metal film or an intermediate metal. It is thought that this is because it is possible to prevent the film from penetrating into the film and thereby prevent the film from being deteriorated due to oxidation.
【００１６】[0016]
【実施例】以下、本発明の実施例を図面を参照して説明
する。図１は本発明の１実施例の導電性金属膜で被覆さ
れた基体の断面図を示し、図２は図１に示す基体の製造
方法に用いる成膜装置の概略構成を示したものである。
図２の成膜装置は成膜真空容器２ａ、２ｂ、２ｃを備え
ている。容器２ａの一側部には補助真空室３ｂ、３ａが
順次接続され、容器２ｃの一側部には補助真空室３ｃ、
３ｄが順次接続されている。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows a sectional view of a substrate coated with a conductive metal film according to one embodiment of the present invention, and FIG. 2 shows a schematic structure of a film forming apparatus used in the method of manufacturing the substrate shown in FIG. .
The film forming apparatus in FIG. 2 includes film forming vacuum containers 2a, 2b, and 2c. The auxiliary vacuum chambers 3b and 3a are sequentially connected to one side of the container 2a, and the auxiliary vacuum chamber 3c is connected to one side of the container 2c.
3d are sequentially connected.
【００１７】端部の補助真空室３ａ、３ｄと外部との各
隔壁、補助真空室（３ａと３ｂ）及び（３ｃと３ｄ）間
の各隔壁、補助真空室３ｂと真空容器２ａ及び補助真空
室３ｃと真空容器２ｃとの各隔壁、真空容器（２ａと２
ｂ）及び（２ｂと２ｃ）間の各隔壁のそれぞれには、フ
ィルム状の基体１を通過させ得るできるだけ小さい通孔
４ａ、４ｈ、４ｂ、４ｇ、４ｃ、４ｆ、４ｄ、４ｅが設
けてある。Partition walls between the auxiliary vacuum chambers 3a and 3d at the end and the outside, partition walls between the auxiliary vacuum chambers (3a and 3b) and (3c and 3d), the auxiliary vacuum chamber 3b, the vacuum container 2a and the auxiliary vacuum chamber. 3c and each of the partition walls of the vacuum container 2c, the vacuum containers (2a and 2
Each of the partition walls between b) and (2b and 2c) is provided with through holes 4a, 4h, 4b, 4g, 4c, 4f, 4d, and 4e which are as small as possible and through which the film-shaped substrate 1 can pass.
【００１８】真空容器２ａ、２ｂ、２ｃ、補助真空室３
ａ、３ｂ、３ｃ、３ｄにはそれぞれ真空ポンプ接続部２
ａ１、２ｂ１、２ｃ１、３ａ１、３ｂ１、３ｃ１、３ｄ
１が設けられ、これらに図示しない真空ポンプを接続し
てあり、これにより各容器内及び各室内を真空引きして
真空容器２ａ、２ｂ、２ｃ内を所定の成膜真空度に維持
できる。Vacuum containers 2a, 2b, 2c, auxiliary vacuum chamber 3
Vacuum pump connection 2 is provided on each of a, 3b, 3c and 3d.
a1, 2b1, 2c1, 3a1, 3b1, 3c1, 3d
1 is provided, and a vacuum pump (not shown) is connected to these, so that the inside of each container and each chamber can be evacuated and the inside of the vacuum containers 2a, 2b, 2c can be maintained at a predetermined film forming vacuum degree.
【００１９】補助真空室３ａの外部側には基体繰出しリ
ール５が配置され、補助真空室３ｄの外部側には基体巻
取りリール５が配置されている。リール５は回転自在で
あり、リール６は継手装置６１を介して、モータ６２に
連結され、このモータをオンすることで図上時計方向回
りに回転駆動可能である。容器２ａ、２ｂ、２ｃ中央部
にはそれぞれ回転自在の基体案内ドラム７ａ、７ｂ、７
ｃが架設してあり、リール５からリール６に巻き取られ
るフィルム状の基体１をその周囲で支持して案内するこ
とができる。また、図中１４ａ、１４ｂ、１４ｃ、１４
ｄは基体を支持し案内する基体案内ローラである。A substrate feeding reel 5 is arranged outside the auxiliary vacuum chamber 3a, and a substrate winding reel 5 is arranged outside the auxiliary vacuum chamber 3d. The reel 5 is rotatable, and the reel 6 is connected to a motor 62 via a joint device 61. By turning on the motor 62, the reel 6 can be rotationally driven clockwise in the drawing. At the center of the containers 2a, 2b, 2c, rotatable body guide drums 7a, 7b, 7 are provided.
c is installed, and it is possible to support and guide the film-shaped substrate 1 wound around the reel 5 from the reel 6 around the reel. Also, in the figure, 14a, 14b, 14c, 14
Reference numeral d denotes a substrate guide roller that supports and guides the substrate.
【００２０】容器２ａ内下部にはドラム７ａの真下にイ
オン源８が配置してあり、容器２ｂ、２ｃ内下部には、
ドラム７ｂ、７ｃの真下にそれぞれスパッタ装置９、１
０が配置してある。イオン源８はそれには限定されない
が、ここではバケット型であり、スパッタ装置９、１０
はプレーナ型高周波マグネトロンスパッタ装置である。
前記スパッタ装置９、１０において、９ａ、１０ａはス
パッタされるターゲット、９ｂ、１０ｂは永久磁石、９
ｃ、１０ｃは高周波電源である。An ion source 8 is arranged below the drum 7a in the lower part of the container 2a, and in the lower part of the container 2b, 2c,
Directly below the drums 7b and 7c are sputter devices 9 and 1, respectively.
0 is arranged. The ion source 8 is, but not limited to, a bucket type here, and the sputtering apparatus 9, 10
Is a planar type high frequency magnetron sputtering apparatus.
In the sputtering devices 9 and 10, 9a and 10a are targets to be sputtered, 9b and 10b are permanent magnets, and 9
c and 10c are high frequency power supplies.
【００２１】また、容器２ｂ、２ｃにはスパッタリング
ガス供給部１１ａ、１１ｂが設けられている。さらに容
器２ａ内にはイオン照射量をモニタするイオン電流測定
器１２、ここでは２次電子抑制電極を備えたファラデー
カップが配置され、容器２ｂ、２ｃ内には基体に到達す
る蒸着物質の原子数及び膜厚をモニタする膜厚モニタ１
３ａ、１３ｂ、ここでは水晶振動子を用いた膜厚モニタ
が配置されている。Further, the containers 2b and 2c are provided with sputtering gas supply units 11a and 11b. Further, in the container 2a, an ion current measuring device 12 for monitoring the amount of ion irradiation, here, a Faraday cup equipped with a secondary electron suppressing electrode is arranged, and in the containers 2b, 2c, the number of atoms of the vapor deposition substance reaching the substrate is reached. And film thickness monitor 1 for monitoring film thickness
3a, 13b, here a film thickness monitor using a crystal oscillator is arranged.
【００２２】以上説明した成膜装置によると、本発明方
法は次のように実施される。リール５には成膜すべきフ
ィルム状の高分子材料基体１を予め巻き納めておき、こ
の基体のリード端を通孔４ａ、４ｂ、４ｃ、４ｄ、４
ｅ、４ｆ、４ｇ、４ｈを通してもう１つのリール６に連
結する。この状態で継手装置６１を係合させておく。こ
のようにして、補助真空室３ａ、３ｂ、３ｃ、３ｄ及び
真空容器２ａ、２ｂ、２ｃ内を図示しない真空ポンプに
て真空引きし、真空容器２ａ内を約１×１０-6〜１×１
０-4Ｔｏｒｒ、真空容器２ｂ、２ｃ内を約１×１０-6〜
１×１０ -4 Ｔｏｒｒの真空度とする。According to the film forming apparatus described above, the present invention
The law is implemented as follows. The film to be formed on the reel 5
The film-shaped polymer material substrate 1 is wound in advance and
Through holes 4a, 4b, 4c, 4d, 4
Connect to another reel 6 through e, 4f, 4g, and 4h.
Tie. In this state, the joint device 61 is engaged. This
And the auxiliary vacuum chambers 3a, 3b, 3c, 3d and
The inside of the vacuum containers 2a, 2b, 2c is replaced by a vacuum pump (not shown).
To evacuate the inside of the vacuum container 2a to about 1 x 10-6~ 1 x 1
0-FourAbout 1 × 10 in the Torr and vacuum containers 2b and 2c-6~
1 x 10 -FourThe degree of vacuum is Torr.
【００２３】容器２ａ内では、ドラム７ａに添った基体
１に対してイオン源８から水素イオン（Ｈ+ ）８ａを照
射する。Ｈ+ の照射エネルギは５００ｅＶ〜１０ＫｅＶ
程度とするのが望ましく、照射量は１×１０15〜１×１
０20ｉｏｎｓ／ｃｍ2 程度とするのが望ましい。イオン
照射量はイオン電流測定器１２、ここでは２次電子抑制
電極を備えたファラデーカップによりモニタする。In the container 2a, the hydrogen ion (H + ) 8a is irradiated from the ion source 8 to the substrate 1 along the drum 7a. The irradiation energy of H + is 500 eV to 10 KeV
It is desirable to set the dose to about 1 × 10 15 to 1 × 1
It is desirable to set it to about 0 20 ions / cm 2 . The amount of ion irradiation is monitored by an ion current measuring device 12, here, a Faraday cup equipped with a secondary electron suppressing electrode.
【００２４】次に容器２ｂ内では、水素イオンが注入さ
れた基体１に対して、スパッタ装置９から目的とする中
間金属膜の構成元素を含む原子、分子、又はイオンを蒸
着させることにより、中間金属膜を形成させる。即ち、
まず容器２ｂ内にスパッタリングガスとして不活性ガ
ス、ここではアルゴン（Ａｒ）ガスを容器２ｂ内が約１
×１０-4〜１×１０-2Ｔｏｒｒになるまで導入し、それ
と同時に高周波電源９ｃから高周波電力を印加する。こ
の電界と永久磁石９ｂにより生じる磁界の作用でプラズ
マが発生し、これにより目的とする中間金属膜層の構成
元素を含むターゲット９ａがスパッタされ、９ａの構成
元素から成るスパッタ粒子がドラム７ｂに添った基体１
上に蒸着され、中間金属膜が形成される。Next, in the container 2b, atoms, molecules, or ions containing the constituent elements of the intended intermediate metal film are vapor-deposited from the sputtering device 9 onto the substrate 1 into which hydrogen ions have been implanted, thereby forming an intermediate product. A metal film is formed. That is,
First, an inert gas, here an argon (Ar) gas, is used as a sputtering gas in the container 2b, and the amount of the inert gas is about 1 in the container 2b.
It is introduced until it reaches a value of × 10 -4 to 1 × 10 -2 Torr, and at the same time, high frequency power is applied from the high frequency power supply 9c. Plasma is generated by the action of this electric field and the magnetic field generated by the permanent magnet 9b, whereby the target 9a containing the constituent elements of the target intermediate metal film layer is sputtered, and the sputtered particles consisting of the constituent elements of 9a are attached to the drum 7b. Base 1
An intermediate metal film is formed by vapor deposition.
【００２５】さらに容器２ｃ内では、容器２ｂ内でのス
パッタリングと同様にして、スパッタ装置１０の高周波
電源１０ｃから高周波電力印加することにより目的とす
る導電性金属膜の構成元素を含むターゲット１０ａがス
パッタされ、ドラム７ｃに添った基体１上に導電性金属
膜が形成される。その他の条件は前記中間金属膜の形成
の場合と同じである。Further, in the container 2c, high frequency power is applied from the high frequency power source 10c of the sputtering device 10 in the same manner as the sputtering in the container 2b, so that the target 10a containing the constituent elements of the target conductive metal film is sputtered. Then, a conductive metal film is formed on the substrate 1 along the drum 7c. Other conditions are the same as in the case of forming the intermediate metal film.
【００２６】なお、前記の中間金属膜及び導電性金属膜
は、膜厚モニタ１３ａ、１３ｂ、ここでは水晶振動子を
用いた膜厚モニタにて基体１上に到達する蒸着原子数及
び膜厚をモニタすることにより、所望の膜厚とすること
ができる。以上に述べた成膜操作により、図１に示すよ
うに、基体１の表面部分にＨ+ が注入された層１ａを有
し、その外側に中間金属膜１ｂを有し、さらにその外側
が導電性金属膜１ｃで被覆されている基体１が形成され
る。基体１においては、イオン注入層１ａの存在によ
り、導電性金属膜１ｃと基体１との密着性向上の目的で
形成された中間金属膜１ｂ内と基体１との良好な密着性
が長期に亘り保持され、またそれによって導電性金属膜
１ｃは基体１上に長期に亘り保持される。The above-mentioned intermediate metal film and conductive metal film are the film thickness monitors 13a and 13b, here the film thickness monitor using a crystal oscillator, and the number of vapor-deposited atoms and film thickness reaching the substrate 1 are determined. A desired film thickness can be obtained by monitoring. As a result of the above-described film forming operation, as shown in FIG. 1, the surface portion of the substrate 1 has a layer 1a into which H + has been implanted, the outer side thereof has an intermediate metal film 1b, and the outer side thereof has a conductivity. The base 1 covered with the conductive metal film 1c is formed. In the substrate 1, due to the presence of the ion-implanted layer 1a, good adhesion between the substrate 1 and the inside of the intermediate metal film 1b formed for the purpose of improving the adhesion between the conductive metal film 1c and the substrate 1 is maintained for a long time. The conductive metal film 1c is held on the substrate 1 for a long period of time.
【００２７】次に、図２に示す成膜装置による本発明の
基体の製造方法の具体例と、それによって得られる導電
性金属膜で被覆された基体について説明する。 実施例 基体１として、ポリイミドからなる幅２００ｍｍ×厚さ
５０μｍのフィルム状の基体を用い、以下に示す条件で
成膜を行った。Next, a specific example of the method of manufacturing the substrate of the present invention by the film forming apparatus shown in FIG. 2 and the substrate coated with the conductive metal film obtained by the method will be described. Example As the substrate 1, a film-shaped substrate made of polyimide having a width of 200 mm and a thickness of 50 μm was used, and film formation was performed under the following conditions.
【００２８】Ｈ+ 注入層形成工程： 真空容器２ａ内を
７×１０-6Ｔｏｒｒの真空度とした。その後、イオン源
８に純度６Ｎ（９９．９９９９％）の水素ガス（Ｈ2 ）
を容器２ａ内が５×１０-5Ｔｏｒｒになるまで導入し、
イオン化させ、該イオン８ａを基体１に対して２ＫｅＶ
の照射エネルギで、照射量を１×１０16ｉｏｎｓ／ｃｍ
2 として照射した。H + injection layer forming step: The inside of the vacuum container 2a is set to a vacuum degree of 7 × 10 -6 Torr. After that, hydrogen gas (H 2 ) having a purity of 6N (99.9999%) is applied to the ion source 8.
Is introduced until the inside of the container 2a reaches 5 × 10 −5 Torr,
Ionize the ions 8a to the substrate 1 at 2 KeV
With irradiation energy of 1 × 10 16 ions / cm
Illuminated as 2 .
【００２９】中間金属膜形成工程： 真空容器２ｂ内を
１×１０-5Ｔｏｒｒの真空度とした。その後、ガス源１
１ａからＡｒガスを容器２ａ内が１×１０-3Ｔｏｒｒに
なるまで導入し、それと同時に高周波電源９ｃにより周
波数１３．５６ＭＨｚの高周波電力を印加し、生じたプ
ラズマにより純度３Ｎ（９９．９％）のニッケル（Ｎ
ｉ）ペレットをスパッタさせ、Ｈ+ 注入層１ａを有する
基体１上にＮｉ膜１ｂを形成した。該Ｎｉ膜１ｂの膜厚
は０．０５μｍであった。Intermediate Metal Film Forming Step: The inside of the vacuum container 2b is set to a vacuum degree of 1 × 10 −5 Torr. Then gas source 1
Ar gas was introduced from 1a until the inside of the container 2a reached 1 × 10 −3 Torr, and at the same time, high frequency power having a frequency of 13.56 MHz was applied by the high frequency power source 9c, and the generated plasma generated a purity of 3N (99.9%). Nickel (N
i) The pellets were sputtered to form a Ni film 1b on the base 1 having the H + injection layer 1a. The thickness of the Ni film 1b was 0.05 μm.
【００３０】導電性金属膜形成工程： 真空容器２ｃ内
を１×１０-5Ｔｏｒｒの真空度とした。その後、ガス源
１１ｂからＡｒガスを容器２ｃ内が１×１０-3Ｔｏｒｒ
になるまで導入し、それと同時に高周波電源１０ｃによ
り周波数１３．５６ＭＨｚの高周波電力を印加し、生じ
たプラズマにより純度４Ｎ（９９．９９％）の銅（Ｃ
ｕ）ペレットをスパッタさせ、前記のＮｉ膜１ｂを有す
る基体１上にＣｕ膜１ｃを形成した。該Ｃｕ膜１ｃの膜
厚は０．３μｍであった。Conductive metal film forming step: The inside of the vacuum container 2c was set to a vacuum degree of 1 × 10 −5 Torr. After that, Ar gas from the gas source 11b is introduced into the container 2c at 1 × 10 −3 Torr.
Until a high frequency power source 10c applies a high frequency power having a frequency of 13.56 MHz, and the generated plasma causes a purity of 4N (99.99%) copper (C
u) The pellet was sputtered to form a Cu film 1c on the substrate 1 having the Ni film 1b. The film thickness of the Cu film 1c was 0.3 μm.
【００３１】以上の過程で膜形成された基体１に、さら
にテストのために、湿式めっきの手法により、Ｃｕ膜を
形成し、先のＣｕ膜１ｃとの合計のＣｕ膜の厚みを３０
μｍとした。このＣｕ膜の密着力をテストするため、比
較例として、図２の装置を用いてＨ + 照射を行わず、他
の条件は前記実施例の具体例と同様にしてＮｉ膜１及び
Ｃｕ膜を形成したポリイミドフィルム（比較例１）、及
び図２の装置を用いてＨ+ 照射及びＮｉ膜形成を行わ
ず、他の条件は前記実施例の具体例と同様にしてＣｕ膜
のみを形成したポリイミドフィルム（比較例２）を準備
した。次いでこの３者を１５０℃の温度で加熱し、経時
的にＪＩＳＣ−５０１６による方法に準じてＣｕ膜の引
き剥がし強度テストを行った。被検ピール幅は２ｍｍと
し、角度９０°で５ｃｍ／ｍｉｎの速度で引き剥がし
た。The substrate 1 formed with the film in the above process is further
For testing, the Cu film was formed by the wet plating method.
The total thickness of the Cu film formed and the Cu film 1c is 30
μm. To test the adhesion of this Cu film,
As a comparative example, using the device of FIG. +No irradiation, other
The conditions of are similar to those of the specific example of the above-mentioned embodiment, and the Ni film 1 and
A polyimide film having a Cu film (Comparative Example 1), and
And using the device of FIG.+Irradiation and Ni film formation
The other conditions are the same as in the specific example of the above-described embodiment, and the Cu film is formed.
Prepare a polyimide film (Comparative Example 2) that has only formed
did. Then, heat the three at a temperature of 150 ° C.
Of Cu film according to the method according to JISC-5016.
A peel strength test was performed. The test peel width is 2 mm
Then peeled off at an angle of 90 ° at a speed of 5 cm / min
It was
【００３２】結果を図３に示す。実施例によるＨ+ 注入
層を有する基体では成膜後加熱処理前のＣｕ膜引き剥が
し強度が強く、且つ、約４０ｈｒ加熱処理後にＣｕ膜引
き剥がし強度が２０％低下しているものの、その後もそ
の強度がほぼ維持されていることが分かる。一方、比較
例１によるＨ+ 注入層を有しない基体では、成膜後加熱
処理前のＣｕ引き剥がし強度は実施例による基体と同様
に強いが、約５０ｈｒ加熱処理後にはＣｕ膜引き剥がし
強度が約８０％低下している。The results are shown in FIG. In the substrate having the H + injection layer according to the example, the Cu film peeling strength after film formation and before the heat treatment was strong, and the Cu film peeling strength was reduced by 20% after the heat treatment for about 40 hr, but after that, It can be seen that the strength is almost maintained. On the other hand, in the substrate having no H + injection layer according to Comparative Example 1, the Cu peeling strength after film formation and before the heat treatment is as strong as that of the substrate according to the embodiment, but after the heat treatment for about 50 hr, the Cu film peeling strength is high. It is about 80% lower.
【００３３】さらに比較例２によるＨ+ 注入層及びＮｉ
膜を有しない基体では、加熱処理によっても引き剥がし
強度は低下しないが、引き剥がし強度は当初から実施例
による基体の約１／３と低い。なお、中間Ｎｉ膜を形成
しないで、他は前記実施例と同条件で、基体上に直接Ｃ
ｕ膜を形成し、同様の強度テストを行ったところ、その
強度の経時的低下は前記実施例と同様に少なかった。Furthermore, the H + injection layer and Ni according to Comparative Example 2 were used.
The peel strength of the substrate having no film is not lowered even by the heat treatment, but the peel strength is as low as about 1/3 of that of the substrate according to the example from the beginning. Incidentally, without forming the intermediate Ni film, the C was directly formed on the substrate under the same conditions as in the above-mentioned embodiment.
When a u film was formed and the same strength test was performed, the decrease in the strength with time was small as in the above-mentioned Examples.
【００３４】以上の結果から、Ｃｕ膜と基体との密着力
は、基体表面部にＨ+ 注入層を形成しておくことにより
維持されることが明らかになった。From the above results, it became clear that the adhesion between the Cu film and the substrate is maintained by forming the H + injection layer on the surface of the substrate.
【００３５】[0035]
【発明の効果】本発明によると、導電性金属膜で被覆さ
れた高分子材料基体であって、導電性金属膜と基体との
密着力が成膜後も経時的に変化、低下し難い基体及びそ
の製造方法を提供することができる。According to the present invention, a polymeric material substrate coated with a conductive metal film, in which the adhesion between the conductive metal film and the substrate is unlikely to change or decrease with time even after film formation. And a manufacturing method thereof.
【図１】本発明の１実施例基体の一部の拡大断面図であ
る。FIG. 1 is an enlarged cross-sectional view of a part of a substrate according to an embodiment of the present invention.
【図２】図１に示す基体の製造に用いる成膜装置の１例
の概略構成を示す図である。FIG. 2 is a diagram showing a schematic configuration of an example of a film forming apparatus used for manufacturing the substrate shown in FIG.
【図３】図１に示す基体の経時的なＣｕ膜引き剥がし強
度の変化を示す図である。FIG. 3 is a diagram showing changes in Cu film peeling strength over time of the substrate shown in FIG.
１ 基体 １ａ 水素イオン（Ｈ+ ）注入層 １ｂ 中間金属膜 １ｃ 導電性金属膜 ２ａ、２ｂ、２ｃ 真空容器 ２ａ１、２ｂ１、２ｃ１、３ａ１、３ｂ１、３ｃ１、３
ｄ１ 真空ポンプ接続部 ３ａ、３ｂ、３ｃ、３ｄ 補助真空室 ４ａ、４ｂ、４ｃ、４ｄ、４ｅ、４ｆ、４ｇ、４ｈ 通
孔 ５ 基体繰出しリール ６ 基体巻取りリール ６１ 継手装置 ６２ モータ ７ａ、７ｂ、７ｃ 基体案内ドラム ８ イオン源 ９、１０ スパッタ装置 ９ａ、１０ａ ターゲット ９ｂ、１０ｂ 永久磁石 ９ｃ、１０ｃ 高周波電源 １１ａ、１１ｂ スパッタリングガス供給部 １２ イオン電流測定器 １３ａ、１３ｂ 膜厚モニタ １４ａ、１４ｂ、１４ｃ、１４ｄ 基体案内ローラ1 Substrate 1a Hydrogen Ion (H + ) Injection Layer 1b Intermediate Metal Film 1c Conductive Metal Film 2a, 2b, 2c Vacuum Container 2a1, 2b1, 2c1, 3a1, 3b1, 3c1, 3
d1 vacuum pump connection part 3a, 3b, 3c, 3d auxiliary vacuum chambers 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h through hole 5 substrate feeding reel 6 substrate winding reel 61 joint device 62 motors 7a, 7b, 7c Substrate guide drum 8 Ion source 9, 10 Sputtering device 9a, 10a Target 9b, 10b Permanent magnet 9c, 10c High frequency power supply 11a, 11b Sputtering gas supply unit 12 Ion current measuring instrument 13a, 13b Film thickness monitor 14a, 14b, 14c, 14d Substrate guide roller
───────────────────────────────────────────────────── フロントページの続き (72)発明者 今井 修 京都市右京区梅津高畝町47番地 日新電機 株式会社内 (72)発明者 緒方 潔 京都市右京区梅津高畝町47番地 日新電機 株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Imai 47 Umezu Takaunemachi, Ukyo-ku, Kyoto City Nissin Electric Co., Ltd. (72) Inventor Kiyoshi Ogata 47 Umezu Takaune-cho, Ukyo-ku, Kyoto City Nissin Electric Co., Ltd.
Claims (6)
体であって、該基体表面部分に水素イオン（Ｈ+ ）が注
入された層を有し、その外側に導電性金属膜が被覆され
ていることを特徴とする導電性金属膜で被覆された高分
子材料基体。1. A polymer material substrate coated with a conductive metal film, which has a layer into which hydrogen ions (H + ) are implanted at a surface portion of the substrate, the outside of which is coated with a conductive metal film. A polymeric material substrate coated with a conductive metal film.
性金属膜との間に中間金属膜が形成されている請求項１
記載の基体。2. An intermediate metal film is formed between the hydrogen ion-implanted layer of the substrate and the conductive metal film.
The substrate described.
はクロムからなる膜である請求項２記載の基体。3. The substrate according to claim 2, wherein the intermediate metal film is a film made of nickel, titanium or chromium.
照射することにより、該基体表面部分に水素イオン（Ｈ
+ ）が注入された層を形成し、その後、該イオン注入層
の外側に導電性金属膜を形成することを特徴とする導電
性金属膜で被覆された高分子材料基体の製造方法。4. A polymer material substrate is irradiated with hydrogen ions (H + ), whereby the hydrogen ion (H
+ ) Is formed, and then a conductive metal film is formed on the outside of the ion-implanted layer, and a method for producing a polymer material substrate covered with a conductive metal film.
記基体のイオン注入層上に中間金属膜を形成し、該中間
金属膜上に前記導電性金属膜を形成する請求項４記載の
基体の製造方法。5. The method according to claim 4, wherein an intermediate metal film is formed on the ion-implanted layer of the substrate and the conductive metal film is formed on the intermediate metal film prior to the formation of the conductive metal film. Substrate manufacturing method.
はクロムで形成する請求項５記載の基体の製造方法。6. The method for manufacturing a substrate according to claim 5, wherein the intermediate metal film is formed of nickel, titanium or chromium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16765593A JPH0718421A (en) | 1993-07-07 | 1993-07-07 | Substrate of high molecular material coated with electric conductive metallic film and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16765593A JPH0718421A (en) | 1993-07-07 | 1993-07-07 | Substrate of high molecular material coated with electric conductive metallic film and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0718421A true JPH0718421A (en) | 1995-01-20 |
Family
ID=15853788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16765593A Withdrawn JPH0718421A (en) | 1993-07-07 | 1993-07-07 | Substrate of high molecular material coated with electric conductive metallic film and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0718421A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD958049S1 (en) | 2020-03-24 | 2022-07-19 | Husqvarna Ab | Wheel for robotic mower |
-
1993
- 1993-07-07 JP JP16765593A patent/JPH0718421A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD958049S1 (en) | 2020-03-24 | 2022-07-19 | Husqvarna Ab | Wheel for robotic mower |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20001003 |