JP4485570B2 - Barrier film for flexible copper substrate and sputtering target for barrier film formation - Google Patents

Barrier film for flexible copper substrate and sputtering target for barrier film formation Download PDF

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JP4485570B2
JP4485570B2 JP2007503590A JP2007503590A JP4485570B2 JP 4485570 B2 JP4485570 B2 JP 4485570B2 JP 2007503590 A JP2007503590 A JP 2007503590A JP 2007503590 A JP2007503590 A JP 2007503590A JP 4485570 B2 JP4485570 B2 JP 4485570B2
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修一 入間田
康廣 山越
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Nippon Mining Holdings Inc
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • 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
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Parts Printed On Printed Circuit Boards (AREA)
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Description

本発明は、ポリイミド等の樹脂フィルムへの銅の拡散を効果的に抑制することのできるフレキシブル銅基板用バリア膜及びバリア膜形成用スパッタリングターゲットに関する。   The present invention relates to a barrier film for a flexible copper substrate and a sputtering target for forming a barrier film that can effectively suppress the diffusion of copper into a resin film such as polyimide.

従来、フレキシブル銅基板の製造に際し、ベースフィルムとなるポリイミド等の樹脂フィルム上に銅層を形成することが行なわれている。具体的には、ポリイミドフィルムにスパッタリング法や無電解めっき法により銅のシード層を形成し、さらにこの上に銅の厚めっき層を形成することが行われている。この後、銅のエッチング工程を経て、銅配線回路パターンが形成される。
こうして形成したフレキシブル基板を使用する際に、前記ポリイミドフィルム上に形成した銅が化学的に活発な金属であるために、ポリイミドフィルム中で容易に拡散し（マイグレーション）、回路基板の相互が短絡するという問題が発生した。Conventionally, in the production of a flexible copper substrate, a copper layer is formed on a resin film such as polyimide as a base film. Specifically, a copper seed layer is formed on a polyimide film by a sputtering method or an electroless plating method, and a thick copper plating layer is further formed thereon. Thereafter, a copper wiring circuit pattern is formed through a copper etching process.
When using the flexible substrate thus formed, since the copper formed on the polyimide film is a chemically active metal, it easily diffuses in the polyimide film (migration) and the circuit boards are short-circuited. The problem that occurred.

このようなＣｕのポリイミドフィルムへの拡散を抑制するために、ポリイミドフィルム上に予めＣｕの拡散を防止するためのバリア層を形成し、その上にＣｕのシード層及びＣｕの厚付けめっき層を形成することが提案されている。
その代表的なものとして、Ｎｉ−Ｃｒ合金のバリア層を形成したものがある（特許文献１参照）。しかし、このＮｉ−Ｃｒ合金のバリア層を形成したものでは、２００〜３００°Ｃ程度の温度上昇があると、依然としてＣｕのポリイミドフィルムへの拡散が認められる。また、特に配線ピッチが３０μｍより狭くなると、従来のバリア層ではポリイミド層への拡散を防ぐことができず、必ずしも効果的でないことが分かった。In order to suppress such diffusion of Cu into the polyimide film, a barrier layer for preventing diffusion of Cu is previously formed on the polyimide film, and a Cu seed layer and a Cu thick plating layer are formed thereon. It has been proposed to form.
A typical example is a Ni-Cr alloy barrier layer formed (see Patent Document 1). However, in the case where this Ni—Cr alloy barrier layer is formed, if there is a temperature rise of about 200 to 300 ° C., diffusion of Cu into the polyimide film is still recognized. Further, it has been found that when the wiring pitch is narrower than 30 μm, the conventional barrier layer cannot prevent diffusion to the polyimide layer and is not necessarily effective.

これを防ぐ手段として、従来のバリア層の厚さを厚くすることで、バリア特性を向上させることも考えられる。しかし、一定値以上に厚さを厚くすると、膜が剥がれてしまうという問題が発生した。したがって、これも根本的な解決手段とは言えなかった。
その他の提案として、熱硬化性ポリイミドベースフィルムに熱可塑性ポリイミド層を形成し、さらにＮｉ、Ｃｒ、Ｃｏ、Ｍｏから選んだ少なくとも１種の金属からなるバリアメタルを被覆し、熱可塑性樹脂を加熱して流動化させ、熱可塑性ポリイミドとバリアメタルとの結合力を増加させるという提案もある（特許文献２参照）。
しかし、この場合は、バリアメタルの拡散というものの根本的なものを解決するものではないので、依然として問題は残っている。
このようなことから、本発明者らはＣｏをベースにＣｒを添加するものを提案した（特許文献３）。この材料は特性的には優れているが、Ｃｏの価格がＮｉの２〜３倍となり、コストの上昇を招くという問題がある。
特開２００２−２５２２５７号公報 特開２００２−２８０６８４号公報 特願２００４−２３２８７２号公報 As a means for preventing this, it is conceivable to improve the barrier characteristics by increasing the thickness of the conventional barrier layer. However, when the thickness is increased beyond a certain value, there is a problem that the film is peeled off. Therefore, this was not a fundamental solution.
As another proposal, a thermoplastic polyimide layer is formed on a thermosetting polyimide base film, and a barrier metal composed of at least one metal selected from Ni, Cr, Co, and Mo is coated, and the thermoplastic resin is heated. There is also a proposal to increase the bonding force between the thermoplastic polyimide and the barrier metal (see Patent Document 2).
However, in this case, the problem remains because it does not solve the fundamental barrier metal diffusion.
In view of the above, the present inventors have proposed the addition of Cr based on Co (Patent Document 3). Although this material is excellent in characteristics, there is a problem that the price of Co is two to three times that of Ni, which causes an increase in cost.
JP 2002-252257 A JP 2002-280684 A Japanese Patent Application No. 2004-2322872

以上の従来技術の問題点から、ポリイミド等の樹脂フィルムへの銅の拡散を抑制するに際し、膜剥離を生じさせない程度の薄い膜厚で、また細かい配線ピッチでも十分なバリア効果を得ることができ、さらに熱処理等により温度上昇があっても、バリア特性に変化がないフレキシブル銅基板用バリア膜及びバリア膜形成用スパッタリングターゲット得ることを課題とする。   Due to the above-mentioned problems of the prior art, a sufficient barrier effect can be obtained with a thin film thickness that does not cause film peeling and a fine wiring pitch when suppressing the diffusion of copper into a resin film such as polyimide. Another object of the present invention is to obtain a barrier film for a flexible copper substrate and a sputtering target for forming a barrier film that do not change in barrier characteristics even when the temperature is increased by heat treatment or the like.

本発明者らは鋭意研究を行った結果、効果的なバリア特性を有する合金を使用し、バリア膜をできる限り薄くして剥離を防止すると共に、成膜した膜の均一性を高めることにより、上記の課題を解決することができるとの知見を得た。   As a result of diligent research, the present inventors have used an alloy having effective barrier properties, made the barrier film as thin as possible to prevent peeling, and by improving the uniformity of the film formed, The knowledge that said subject can be solved was acquired.

本発明はこの知見に基づき、
（１）Ｃｒ：５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金膜からなり、膜厚が３〜１５０ｎｍ、膜厚均一性が１σで１０％以下であることを特徴とするフレキシブル銅基板用バリア膜
（２）Ｃｒ：５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金であって、スパッタ面の面内方向の比透磁率が１００以下であることを特徴とするバリア膜形成用スパッタリングターゲット
を提供する。The present invention is based on this finding,
(1) Cr: 5 to 30 wt%, Ti and / or Zr: 1 to 10 wt%, the balance is made of an Ni—Cr alloy film made of inevitable impurities and Ni, the film thickness is 3 to 150 nm, the film thickness Uniformity is 1σ at 10% or less barrier film for flexible copper substrate (2) Cr: 5 to 30 wt%, Ti and / or Zr: 1 to 10 wt%, the balance being inevitable impurities and There is provided a sputtering target for forming a barrier film, which is a Ni—Cr alloy made of Ni and has a relative magnetic permeability of 100 or less in the in-plane direction of the sputtering surface.

本発明のフレキシブル銅基板用バリア膜は、膜剥離を生じさせない程度の薄い膜厚とし、また細かい配線ピッチでも十分なバリア効果を得ることができ、さらに熱処理等により温度上昇があっても、バリア特性に変化がないという優れた特徴を有している。本発明は、ポリイミド等の樹脂フィルムへの銅の拡散を効果的に抑制する著しい特性を有する。  The barrier film for a flexible copper substrate of the present invention has a thin film thickness that does not cause film peeling, and a sufficient barrier effect can be obtained even with a fine wiring pitch. It has an excellent feature that there is no change in characteristics. The present invention has remarkable characteristics that effectively suppress the diffusion of copper into a resin film such as polyimide.

実施例１のＮｉ−２０ｗｔ％Ｃｒ−４．９ｗｔ％Ｔｉ合金のバリア膜を使用した場合の、Ｃｕ拡散の分析（ＡＥＳ）結果を示す図である。It is a figure which shows the analysis (AES) result of Cu diffusion at the time of using the barrier film | membrane of the Ni-20 wt% Cr-4.9 wt% Ti alloy of Example 1. FIG. 実施例９のＮｉ−１９．６ｗｔ％Ｃｒ−５．１ｗｔ％Ｚｒ合金のバリア膜を使用した場合の、Ｃｕ拡散の分析（ＡＥＳ）結果を示す図である。It is a figure which shows the analysis (AES) result of Cu diffusion at the time of using the barrier film of the Ni-19.6wt% Cr-5.1wt% Zr alloy of Example 9. FIG. 比較例１のＮｉ−１９．７ｗｔ％Ｃｒ合金のバリア膜を使用した場合の、Ｃｕ拡散の分析（ＡＥＳ）結果を示す図である。It is a figure which shows the analysis (AES) result of Cu diffusion at the time of using the barrier film of the Ni-19.7 wt% Cr alloy of the comparative example 1.

本発明のフレキシブル銅基板用バリア膜は、Ｃｒ：５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金膜である。
膜組成において、Ｃｒが５ｗｔ％に満たない場合はバリア性が十分でなく、従来のバリア膜に比べ優位性が無い。また、Ｃｒが３０ｗｔ％を超えるとＣｕ層をエッチングして回路を形成する際に、このバリア膜がエッチングを阻害するので、除去するのに非常に時間がかかり過ぎ、実用に向かない。したがって、上記のＣｒの範囲とする。
また、Ｔｉ及び／又はＺｒの添加は、後述する実施例に示すように、バリア特性を著しく向上させて膜の耐久性を上げ、膜の均一性を確保するのに有効である。その添加量は１〜１０ｗｔ％とするのが良い。Ｔｉ及び／又はＺｒの含有量が１ｗｔ％未満であると、膜の耐久性向上の効果が少なく、膜均一性の向上が期待できない。逆に、Ｔｉ及び／又はＺｒの含有量が１０ｗｔ％を超えると、膜の剥離を発生し易くなるので、上記の範囲とする。The barrier film for a flexible copper substrate of the present invention is a Ni—Cr-based alloy film containing Cr: 5 to 30 wt%, Ti and / or Zr: 1 to 10 wt%, with the balance being inevitable impurities and Ni.
In the film composition, when Cr is less than 5 wt%, the barrier property is not sufficient, and there is no advantage over the conventional barrier film. On the other hand, if Cr exceeds 30 wt%, this barrier film hinders etching when the Cu layer is etched to form a circuit, so that it takes too much time to remove and is not suitable for practical use. Therefore, the Cr range is set.
Further, the addition of Ti and / or Zr is effective for significantly improving the barrier characteristics and increasing the durability of the film and ensuring the uniformity of the film, as shown in the examples described later. The addition amount is preferably 1 to 10 wt%. When the content of Ti and / or Zr is less than 1 wt%, the effect of improving the durability of the film is small, and improvement in film uniformity cannot be expected. On the other hand, if the content of Ti and / or Zr exceeds 10 wt%, film peeling is likely to occur, so the above range is set.

本発明のフレキシブル銅基板用バリア膜の膜厚は、３〜１５０ｎｍとする。膜厚が３ｎｍ未満の場合：充分なバリア性を持たない。また、膜厚が１５０ｎｍを超えると膜剥がれを生じ易くなるので、上記の範囲とする。
本発明のフレキシブル銅基板用バリア膜の膜厚は、膜厚均一性が１σで１０％以下とする。この膜均一性を適切な値を維持することは均一幅の配線を形成する上で極めて重要である。膜厚均一性（１σ）が、１０％を超えると、パターニングの際のエッチング時に、バリア膜の厚い部分を除去するまでエッチングした場合、バリア膜が薄かった部分では、除去しようとした部分より広くエッチングされ、その部分の配線幅が狭くなり、耐久性が低下するという問題がある。したがって、上記の膜厚均一性（１σ）を１０％以下とする。The film thickness of the barrier film for a flexible copper substrate of the present invention is 3 to 150 nm. When the film thickness is less than 3 nm: it does not have sufficient barrier properties. Moreover, since it will become easy to produce film peeling when a film thickness exceeds 150 nm, it is set as said range.
The film thickness of the barrier film for a flexible copper substrate of the present invention is 10% or less when the film thickness uniformity is 1σ. Maintaining this film uniformity at an appropriate value is extremely important in forming a wiring having a uniform width. When the film thickness uniformity (1σ) exceeds 10%, when etching is performed until the thick part of the barrier film is removed during the patterning, the thin part of the barrier film is wider than the part to be removed. Etching results in a problem that the wiring width of the portion is narrowed and durability is lowered. Therefore, the film thickness uniformity (1σ) is set to 10% or less.

本発明のバリア膜形成用スパッタリングターゲットについては、Ｃｒを５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金ターゲットを用いる。本発明のＮｉ−Ｃｒ系合金ターゲットの組成は、バリア膜の組成に直接反映される。すなわち、ターゲット組成のＣｒが５ｗｔ％に満たない場合、５ｗｔ％Ｃｒ以上のＮｉ−Ｃｒ系合金膜が成膜できない。一方、Ｃｒが３０ｗｔ％を超えると、Ｃｒ量が３０％以下となるＮｉ合金の膜が成膜できない。
同様に、Ｔｉ及び／又はＺｒが１ｗｔ％に満たない含有量では、Ｔｉ及び／又はＺｒが１ｗｔ％以上のＮｉ−Ｃｒ系合金膜が成膜できない。また、Ｔｉ及び／又はＺｒが１０ｗｔ％を超える含有量では、Ｔｉ及び／又はＺｒが１０ｗｔ％以下のＮｉ−Ｃｒ系合金膜が成膜できない。したがって、Ｎｉ−Ｃｒ系合金ターゲットの組成は、上記の範囲とする。
また、本発明のバリア膜形成用スパッタリングターゲットの、スパッタ面の面内方向の比透磁率が１００以下とする。比透磁率が１００を超えると、スパッタ膜の膜厚均一性が１σで１０％を超えてしまうからである。For the sputtering target for forming a barrier film of the present invention, a Ni—Cr based alloy target containing 5 to 30 wt% of Cr, Ti and / or Zr: 1 to 10 wt%, and the balance of inevitable impurities and Ni is used. The composition of the Ni—Cr alloy target of the present invention is directly reflected in the composition of the barrier film. That is, when the target composition Cr is less than 5 wt%, a Ni—Cr alloy film of 5 wt% Cr or more cannot be formed. On the other hand, when Cr exceeds 30 wt%, a Ni alloy film having a Cr content of 30% or less cannot be formed.
Similarly, when the content of Ti and / or Zr is less than 1 wt%, a Ni—Cr alloy film with Ti and / or Zr of 1 wt% or more cannot be formed. Further, when the content of Ti and / or Zr exceeds 10 wt%, a Ni—Cr-based alloy film having Ti and / or Zr of 10 wt% or less cannot be formed. Therefore, the composition of the Ni—Cr-based alloy target is within the above range.
Further, the relative permeability in the in-plane direction of the sputtering surface of the sputtering target for forming a barrier film of the present invention is set to 100 or less. This is because when the relative magnetic permeability exceeds 100, the film thickness uniformity of the sputtered film exceeds 10% at 1σ.

本発明のＮｉ−Ｃｒ系合金ターゲットは、平均結晶粒径が５００μｍ以下、特に１００μｍ以下が望ましい。平均結晶粒径が５００μｍを超えると、パーティクル発生量多くなり、ピンホールと呼ばれる膜欠陥が増加し、製品収率が低下するからである。
また、本発明のＮｉ−Ｃｒ系合金ターゲットは、ターゲット内の平均結晶粒径のバラツキが３０％以内のものが望ましい。平均粒径のばらつきが３０％を超えると、スパッタ成膜した膜の膜厚均一性が１σで１０％を超えるおそれがあるからである。
本発明のターゲットを製造するに際しては、７００〜１２８０°Ｃの熱間における鍛造と、圧延の組み合わせにより、ターゲット板に加工するのが望ましい。
さらに、前記熱間鍛造・圧延後、大気中、真空中又は不活性ガス雰囲気中で、保持温度：３００〜９５０°Ｃの熱処理を行うのが良い。これによって得たターゲットは、スパッタリングされる部分の平均粗さ (Ｒａ) が、０．０１〜５μｍとする。The Ni—Cr-based alloy target of the present invention preferably has an average crystal grain size of 500 μm or less, particularly 100 μm or less. This is because when the average crystal grain size exceeds 500 μm, the amount of particles generated increases, film defects called pinholes increase, and the product yield decreases.
Further, the Ni—Cr alloy target of the present invention desirably has an average crystal grain size variation within 30% within the target. This is because if the variation in average particle diameter exceeds 30%, the film thickness uniformity of the sputtered film may exceed 10% at 1σ.
When manufacturing the target of the present invention, it is desirable to process the target plate by a combination of hot forging at 700 to 1280 ° C. and rolling.
Further, after the hot forging / rolling, heat treatment at a holding temperature of 300 to 950 ° C. may be performed in the air, in a vacuum, or in an inert gas atmosphere. The target thus obtained has an average roughness (Ra) of a portion to be sputtered of 0.01 to 5 μm.

また、ターゲットの側面やバッキングフレートなどの非スパッタ面、すなわちスパッタされた物質が付着する部分を、サンドブラスト処理、エッチング処理又は溶射被膜層の形成等によって、表面の平均粗さ (Ｒａ)を１〜５０μｍに表面粗化して、付着した被膜が再剥離するのを防止することが望ましい。再剥離してスパッタ雰囲気中に浮遊する物質は、基板へのパーティクル発生の原因となるからである。
本発明のターゲットは、Ａｌ合金、Ｃｕ、 Ｃｕ合金、Ｔｉ、Ｔｉ合金などのバッキングプレートへロウ付け若しくは高出力スパッタに耐えられるように、拡散接合法の金属結合によってボンディングしたり、バッキングプレート部をターゲット材と同じ材料を使用して一体成形して用いられる。
また、ターゲットに含有される不純物として、Ｎａ、Ｋの濃度がそれぞれ５ｐｐｍ以下（以降ｐｐｍは、ｗｔｐｐｍを示す）、Ｕ、Ｔｈの濃度がそれぞれ０．０５ｐｐｍ以下、さらには主元素、添加元素以外の金属元素の総計が０．５ｗｔ％以下、かつ酸素濃度が０．５％以下であることが望ましい。Further, the average roughness (Ra) of the surface of the non-sputtered surface such as the side surface of the target or the backing freight, that is, the portion to which the sputtered material adheres is reduced by sandblasting, etching, or formation of a sprayed coating layer. It is desirable to roughen the surface to 50 μm to prevent the attached film from peeling again. This is because the substance that re-peels and floats in the sputtering atmosphere causes generation of particles on the substrate.
The target of the present invention can be bonded to the backing plate of Al alloy, Cu, Cu alloy, Ti, Ti alloy or the like by brazing or metal bonding of the diffusion bonding method so that it can withstand high power sputtering, or the backing plate portion can be The same material as the target material is used for integral molding.
Further, as impurities contained in the target, the concentrations of Na and K are each 5 ppm or less (hereinafter, ppm indicates wtppm), the concentrations of U and Th are each 0.05 ppm or less, and other than the main elements and additive elements It is desirable that the total amount of metal elements is 0.5 wt% or less and the oxygen concentration is 0.5% or less.

次に、実施例に基づいて本発明を説明する。以下に示す実施例は、理解を容易にするためのものであり、これらの実施例によって本発明を制限するものではない。すなわち、本発明の技術思想に基づく変形及び他の実施例は、当然本発明に含まれる。  Next, the present invention will be described based on examples. The following examples are for ease of understanding, and the present invention is not limited by these examples. That is, modifications and other embodiments based on the technical idea of the present invention are naturally included in the present invention.

（実施例１−９）
表１に示すターゲットを製造するために、Ｎｉ、Ｃｒ、Ｔｉ及び／又はＺｒの組成を溶解・鋳造し、各種Ｎｉ−Ｃｒ系インゴットを作製した。これを、１１００°Ｃで熱間鍛造・熱間圧延し、冷却後５００°Ｃで２時間熱処理を行い、ターゲットに加工した。このターゲットの結晶粒径はターゲットにより８０〜２５０μｍの範囲であった。これを、さらに表面粗さＲａ０．１４μｍに仕上げた。
ターゲット中のＣｒ濃度は１０．２〜２９．５ｗｔ％の範囲、Ｔｉの濃度は１．５〜９．５ｗｔ％の範囲、Ｚｒの濃度は５．３ｗｔ％であった。なお、実施例でＺｒを添加した例は少ないが、ＺｒはＴｉと実質的に同効の材料であり、煩雑になるので省略した。
その他、不純物成分は、Ｎａ：０．２ｐｐｍ、Ｋ：０．１ｗｔｐｐｍ、Ｕ：０．０２ｐｐｍ、Ｔｈ：０．０３ｐｐｍ、 金属成分の総計が２５０〜４７０ｐｐｍ、 酸素が１０〜２０ｐｐｍであった。
このターゲットをバッキングプレートにインジウムをロウ材としてボンディングして、ターゲットの側面とターゲット近傍のバッキングプレート部をサンドブラストで、Ｒａ＝７．５μｍに粗化した。(Example 1-9)
In order to manufacture the target shown in Table 1, the composition of Ni, Cr, Ti and / or Zr was melted and cast to prepare various Ni—Cr ingots. This was hot forged and hot rolled at 1100 ° C., and after cooling, heat-treated at 500 ° C. for 2 hours to be processed into a target. The crystal grain size of this target was in the range of 80 to 250 μm depending on the target. This was further finished to a surface roughness Ra of 0.14 μm.
The Cr concentration in the target was in the range of 10.2 to 29.5 wt%, the Ti concentration was in the range of 1.5 to 9.5 wt%, and the Zr concentration was 5.3 wt%. In addition, although there are few examples which added Zr in the Example, since Zr is a material substantially the same effect as Ti and becomes complicated, it was omitted.
In addition, the impurity components were Na: 0.2 ppm, K: 0.1 wtppm, U: 0.02 ppm, Th: 0.03 ppm, the total of metal components was 250 to 470 ppm, and oxygen was 10 to 20 ppm.
This target was bonded to a backing plate using indium as a brazing material, and the side surface of the target and the backing plate near the target were roughened to Ra = 7.5 μm by sandblasting.

表１に示す本発明の範囲にある合金組成及び比透磁率のターゲットを用いて、３８μｍ厚のポリイミドシート上に、膜厚：３〜１４０ｎｍのバリア層を作製した。
さらに、このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、その膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。実施例１〜９のバリア膜の膜組成（ｗｔ％）、膜厚（ｎｍ）、膜厚の均一性（％）はいずれも、本願発明の範囲に入るものである。
なお、ターゲット組成と膜組成に若干の差異が認められるが、その量はわずかであり、ターゲット組成が膜に反映されていることが分かる。
さらに、このバリア層の上にスパッタ法でＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチ（配線幅１５μｍ、配線間距離１５μｍ）で作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。これらの結果を同様に、表１に示す。
以上の結果、実施例１〜９は、いずれも各配線の短絡は見られなかった。耐久試験によると表１に示す通り、いずれの合金膜も耐久時間が１０００時間を越えていた。A barrier layer having a film thickness of 3 to 140 nm was formed on a polyimide sheet having a thickness of 38 μm using a target having an alloy composition and a relative magnetic permeability within the range of the present invention shown in Table 1.
Further, the composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined. The results (time) of the durability test are also shown in Table 1. The film compositions (wt%), film thickness (nm), and film thickness uniformity (%) of the barrier films of Examples 1 to 9 all fall within the scope of the present invention.
Although a slight difference is observed between the target composition and the film composition, the amount is slight and it can be seen that the target composition is reflected in the film.
Further, a Cu seed layer having a thickness of 20 nm was formed on the barrier layer by sputtering, and then an 8 μm Cu layer was formed by electroplating. And about the wiring pattern produced by these with a 30 micrometer pitch (wiring width of 15 micrometers, distance between wirings of 15 micrometers), the voltage of + 60V was applied to this and the endurance test which hold | maintains in an atmosphere of 85 degreeC and a humidity of 85% was done. These results are similarly shown in Table 1.
As a result, in all of Examples 1 to 9, no short circuit of each wiring was observed. According to the durability test, as shown in Table 1, all the alloy films had a durability time exceeding 1000 hours.

このＣｕ／Ｎｉ−Ｃｒ系合金膜について、成膜したままの試料と、真空中で３００°Ｃ×２時間の熱処理を行った試料について、ＡＥＳ（オージェ電子分光法）で深さ方向にプロファイルをとり、Ｃｕのバリア層への拡散を評価した。
図１〜２に、ＡＥＳの結果を示す。本実施例におけるＮｉ−Ｃｒ系合金をバリア膜としたものでは、３００°Ｃで熱処理したものでも、Ｃｕのプロファイルは熱処理を行わなかったものと同様のプロファイルを示しており、バリア層への拡散が認められなかった。下記に示す比較例１と比較すると、Ｔｉ及び／又はＺｒの添加により、バリア特性の著しい向上が確認できた。About this Cu / Ni-Cr-based alloy film, a profile was formed in the depth direction by AES (Auger Electron Spectroscopy) for the as-deposited sample and the sample that was heat-treated in vacuum at 300 ° C for 2 hours. Then, the diffusion of Cu into the barrier layer was evaluated.
1 and 2 show the results of AES. In the case where the Ni—Cr alloy in this example is used as a barrier film, the Cu profile shows the same profile as that without heat treatment even when heat-treated at 300 ° C., and diffusion into the barrier layer Was not recognized. When compared with Comparative Example 1 shown below, it was confirmed that the barrier properties were significantly improved by the addition of Ti and / or Zr.

Figure 0004485570
Figure 0004485570

（比較例１）
従来のバリア材であるＮｉ−１９．８０ｗｔ％Ｃｒの組成を有する材料を、溶解・鋳造し、Ｎｉ−Ｃｒインゴットを作製した。これを、１１００°Ｃで熱間鍛造・熱間圧延し、冷却後５００°Ｃで２時間の熱処理を行い、ターゲットに加工した。
このターゲットの結晶粒径は３００μｍで、表面粗さをＲａで０．１５μｍに仕上げた。ターゲット中のＣｒ濃度は１９．７ｗｔ％、不純物成分は、Ｎａ：０．１ｐｐｍ、Ｋ：０．３ｐｐｍ、Ｕ：０．０２ｐｐｍ、Ｔｈ：０．０４ｐｐｍ、 不純物金属成分の総計が５１０ｐｐｍ、 酸素が１０ｐｐｍであった。(Comparative Example 1)
A material having a composition of Ni-19.80 wt% Cr, which is a conventional barrier material, was melted and cast to prepare a Ni-Cr ingot. This was hot forged and hot rolled at 1100 ° C., and after cooling, heat-treated at 500 ° C. for 2 hours to be processed into a target.
The crystal grain size of this target was 300 μm, and the surface roughness was finished to 0.15 μm with Ra. Cr concentration in the target is 19.7 wt%, impurity components are Na: 0.1 ppm, K: 0.3 ppm, U: 0.02 ppm, Th: 0.04 ppm, total of impurity metal components is 510 ppm, oxygen is 10 ppm Met.

ターゲットをバッキングプレートにインジウムでボンディングして、ターゲットの側面とターゲット近傍のバッキングプレート部をサンドブラストで、Ｒａ＝７．０μｍで粗化した。ターゲットの面内方向の比透磁率は３０であった。
このターゲットを使って、バリア膜が剥離しないようにＳｉＯ２基板を用い、その上に膜厚：１４０ｎｍのバリア層を作製した。
このバリア層の各添加成分の組成を分析したところ、Ｃｒ：１９．７ｗｔ％と、若干Ｃｒが少ない組成となった。このバリア層の膜厚を４９点測定し、その膜厚均一性を調べたところ、１σで６．５％であった。以上の結果を同様に、表１に示す。The target was bonded to the backing plate with indium, and the side surface of the target and the backing plate portion in the vicinity of the target were roughened by sand blasting at Ra = 7.0 μm. The relative permeability in the in-plane direction of the target was 30.
Using this target, a SiO 2 substrate was used so that the barrier film was not peeled off, and a barrier layer having a thickness of 140 nm was formed thereon.
When the composition of each additive component in the barrier layer was analyzed, Cr was 19.7 wt%, and the composition was slightly less Cr. When the film thickness of this barrier layer was measured at 49 points and the film thickness uniformity was examined, it was 6.5% at 1σ. The above results are similarly shown in Table 1.

このバリア層の上にスパッタ法でＣｕ膜を２００ｎｍ成膜した。このＣｕ／Ｎｉ−Ｃｒ膜について、成膜したままの試料と、真空中で３００°Ｃ×２時間の熱処理を行った試料について、ＡＥＳ（オージェ電子分光法）で深さ方向にプロファイルをとり、Ｃｕのバリア層への拡散の評価した。図３に、ＡＥＳの結果を示す。
３００°Ｃで熱処理したもののＣｕのプロファイルが、熱処理していないものよりも、バリア層に入り込んでいる。すなわち、バリア層としての機能が低いことが分かった。A Cu film having a thickness of 200 nm was formed on the barrier layer by sputtering. About this Cu / Ni-Cr film, about the sample as it was formed and the sample which performed heat processing for 300 ° C x 2 hours in a vacuum, take a profile in the depth direction by AES (Auger electron spectroscopy), The diffusion of Cu into the barrier layer was evaluated. FIG. 3 shows the results of AES.
The Cu profile that was heat-treated at 300 ° C. entered the barrier layer more than the one that was not heat-treated. That is, it turned out that the function as a barrier layer is low.

（比較例２）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚２．５ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は３５であった。このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例２のバリア膜の膜厚が２．５ｎｍと薄く、本願発明のターゲットと成分組成は同じであるが、膜厚が異なるものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチで作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。これらの結果を同様に、表１に示す。以上の耐久試験の結果、比較例２は１２０時間持続したが、その後配線の短絡を生じた。(Comparative Example 2)
The target shown in Table 1 was manufactured by the same operation as Comparative Example 1, and a Ni—Cr—Ti alloy barrier layer having a thickness of 2.5 nm shown in Table 1 was formed on a 38 μm-thick polyimide sheet using this target. Formed. The relative permeability in the in-plane direction of the target was 35. The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The film thickness of the barrier film of Comparative Example 2 is as thin as 2.5 nm, and the target composition of the present invention is the same as the component composition, but the film thickness is different. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. And about the wiring pattern which produced these with the 30 micrometer pitch, the durability test which applied the voltage of + 60V to this and hold | maintains in the atmosphere of 85 degreeC and 85% of humidity was done. These results are similarly shown in Table 1. As a result of the above durability test, Comparative Example 2 lasted for 120 hours, but then a short circuit occurred in the wiring.

（比較例３）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１７０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は３２であった。このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例３のバリア膜の膜厚が１７０ｎｍと厚く、本願発明のターゲットと成分組成は同じであるが、膜厚が異なるものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。
そして、これらを３０μｍピッチで作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。
これらの結果を同様に、表１に示す。以上の耐久試験開始直後、比較例３は膜の剥離を生じた。その結果膜の耐久性の試験を続けることができなかった。以上から、バリア層の過剰な膜厚は、適切でないことが分かった。(Comparative Example 3)
A target shown in Table 1 was manufactured in the same manner as in Comparative Example 1, and a 170 nm thick Ni—Cr—Ti alloy barrier layer shown in Table 1 was formed on a 38 μm thick polyimide sheet using this target. did. The relative permeability in the in-plane direction of the target was 32. The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The film thickness of the barrier film of Comparative Example 3 is as thick as 170 nm, and the target composition of the present invention is the same as the component composition, but the film thickness is different. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating.
And about the wiring pattern which produced these with the 30 micrometer pitch, the voltage of + 60V was applied to this, and the durability test hold | maintained at 85 degreeC and 85% of humidity atmosphere was done.
These results are similarly shown in Table 1. Immediately after the start of the above durability test, Comparative Example 3 caused film peeling. As a result, the durability test of the film could not be continued. From the above, it was found that an excessive film thickness of the barrier layer is not appropriate.

（比較例４）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は２５であった。このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例４のバリア膜は、Ｔｉが１２．０と過剰に添加されたものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチで作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。
これらの結果を同様に、表１に示す。以上の耐久試験の結果、比較例４は試験の途中で、膜の剥離を生じた。その結果膜の耐久性の試験を続けることができなかった。以上から、バリア層のＴｉの過剰な添加は、適切でないことが分かった。(Comparative Example 4)
A target shown in Table 1 was manufactured in the same manner as in Comparative Example 1, and a Ni—Cr—Ti alloy barrier layer having a thickness of 10 nm shown in Table 1 was formed on a 38 μm-thick polyimide sheet using this target. did. The relative permeability in the in-plane direction of the target was 25. The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
In the barrier film of Comparative Example 4, Ti is excessively added at 12.0. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. And about the wiring pattern which produced these with the 30 micrometer pitch, the voltage of + 60V was applied to this, and the durability test hold | maintained at 85 degreeC and 85% of humidity atmosphere was done.
These results are similarly shown in Table 1. As a result of the above durability test, Comparative Example 4 caused film peeling during the test. As a result, the durability test of the film could not be continued. From the above, it was found that excessive addition of Ti in the barrier layer is not appropriate.

（比較例５）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は６０であった。このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例５のバリア膜は、Ｔｉが０．９と添加量が本発明の規定に達しないものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチで作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。
これらの結果を同様に、表１に示す。以上の耐久試験の結果、比較例５は膜厚の均一性が１５．３％と悪く、耐久試験の結果、２３０時間でバリア効果が低下し、耐久性が悪いという結果になった。したがって、バリア層に十分な量のＴｉがない場合には、耐久性が劣ることが分かった。(Comparative Example 5)
A target shown in Table 1 was manufactured in the same manner as in Comparative Example 1, and a Ni—Cr—Ti alloy barrier layer having a thickness of 10 nm shown in Table 1 was formed on a 38 μm-thick polyimide sheet using this target. did. The relative permeability in the in-plane direction of the target was 60. The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The barrier film of Comparative Example 5 has a Ti content of 0.9 and the amount added does not meet the requirements of the present invention. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. And about the wiring pattern which produced these with the 30 micrometer pitch, the voltage of + 60V was applied to this, and the durability test hold | maintained at 85 degreeC and 85% of humidity atmosphere was done.
These results are similarly shown in Table 1. As a result of the above durability test, the uniformity of the film thickness of Comparative Example 5 was as bad as 15.3%, and as a result of the durability test, the barrier effect was lowered after 230 hours and the durability was poor. Therefore, it was found that the durability is inferior when there is not a sufficient amount of Ti in the barrier layer.

（比較例６）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は３０であった。このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例６のバリア膜は、Ｃｒが３３．２ｗｔ％と添加量が本発明の規定量を超えるものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチで配線パターンを作製しようとしたが、バリア層のエッチングに時間がかかり過ぎ、Ｃｕ部が過剰にエッチングされて配線パターンが形成できなかった。以上から、バリア層のＣｒの過剰な添加は、適切でないことが分かった。(Comparative Example 6)
A target shown in Table 1 was manufactured in the same manner as in Comparative Example 1, and a Ni—Cr—Ti alloy barrier layer having a thickness of 10 nm shown in Table 1 was formed on a 38 μm-thick polyimide sheet using this target. did. The relative permeability in the in-plane direction of the target was 30. The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The barrier film of Comparative Example 6 has a Cr content of 33.2 wt% and an added amount exceeding the specified amount of the present invention. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. Then, although an attempt was made to produce a wiring pattern with a pitch of 30 μm, it took too much time to etch the barrier layer, and the Cu part was excessively etched, so that the wiring pattern could not be formed. From the above, it was found that excessive addition of Cr in the barrier layer is not appropriate.

（比較例７）
比較例１と同様の操作により、表１に示すターゲットを製造し、このターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。ターゲットの面内方向の比透磁率は３０であった。
このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例７のバリア膜は、Ｃｒが９．２ｗｔ％と添加量が本発明の規定量に達しないものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチ（配線幅１５μｍ、配線間距離１５μｍ）で作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。
これらの結果を同様に、表１に示す。以上の耐久試験の結果、比較例７は、耐久試験の結果、１００時間でバリア効果が低下し、耐久性が悪いという結果になった。したがって、バリア層に十分な量のＣｒがない場合には、耐久性が劣ることが分かった。(Comparative Example 7)
A target shown in Table 1 was manufactured in the same manner as in Comparative Example 1, and a Ni—Cr—Ti alloy barrier layer having a thickness of 10 nm shown in Table 1 was formed on a 38 μm-thick polyimide sheet using this target. did. The relative permeability in the in-plane direction of the target was 30.
The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The barrier film of Comparative Example 7 has a Cr content of 9.2 wt% and does not reach the specified amount of the present invention. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. And about the wiring pattern produced by these with a 30 micrometer pitch (wiring width of 15 micrometers, distance between wirings of 15 micrometers), the voltage of + 60V was applied to this and the endurance test which hold | maintains in an atmosphere of 85 degreeC and a humidity of 85% was done.
These results are similarly shown in Table 1. As a result of the above durability test, Comparative Example 7 resulted in the result that the barrier effect was lowered and the durability was poor in 100 hours as a result of the durability test. Therefore, it was found that the durability is poor when there is not a sufficient amount of Cr in the barrier layer.

（比較例８）
比較例１と同様の操作で溶解し、１１００°Ｃで熱間鍛造・圧延して、表１に示すターゲットを製造した。ターゲットの面内方向の比透磁率は１２０であったこのターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。
このバリア層の各添加成分の組成（ｗｔ％）、バリア層の膜厚（ｎｍ）、バリア層の膜厚を４９点測定し、膜厚の均一性（％）を調べた結果、及び耐久試験の結果（時間）を、同様に表１に示す。
比較例８のターゲットは比透磁率は１２０であり、本発明の規定に達しないものである。さらに、このバリア層の上にＣｕシード層を２０ｎｍ成膜後、電気めっきにより８μｍのＣｕ層を形成した。そして、これらを３０μｍピッチ（配線幅１５μｍ、配線間距離１５μｍ）で作製した配線パターンについて、これに＋６０Ｖの電圧をかけて、８５°Ｃ、湿度８５％の雰囲気で保持する耐久試験を行った。
これらの結果を同様に、表１に示す。以上の耐久試験の結果、比較例８は、耐久試験の結果、膜厚の均一性が１３．１％と悪く、６２０時間でバリア効果が低下し、耐久性が悪いという結果になった。したがって、比透磁率が高すぎる場合には、膜厚の均一性が悪く、耐久性が劣ることが分かった。(Comparative Example 8)
It melt | dissolved by the same operation as the comparative example 1, and hot forged and rolled at 1100 degreeC, and produced the target shown in Table 1. Using this target having a relative permeability of 120 in the in-plane direction, a 10 nm thick Ni—Cr—Ti alloy barrier layer shown in Table 1 was formed on a 38 μm thick polyimide sheet.
The composition of each additive component of the barrier layer (wt%), the thickness of the barrier layer (nm), the thickness of the barrier layer was measured at 49 points, and the uniformity of the thickness (%) was examined, and the durability test The results (time) are also shown in Table 1.
The target of Comparative Example 8 has a relative magnetic permeability of 120 and does not meet the definition of the present invention. Further, after forming a Cu seed layer on the barrier layer to a thickness of 20 nm, an 8 μm Cu layer was formed by electroplating. And about the wiring pattern produced by these with a 30 micrometer pitch (wiring width of 15 micrometers, distance between wirings of 15 micrometers), the voltage of + 60V was applied to this and the endurance test which hold | maintains in an atmosphere of 85 degreeC and a humidity of 85% was done.
These results are similarly shown in Table 1. As a result of the above durability test, Comparative Example 8 resulted in a poor uniformity of film thickness of 13.1% as a result of the durability test, and the barrier effect decreased in 620 hours, resulting in poor durability. Therefore, it was found that when the relative permeability is too high, the uniformity of the film thickness is poor and the durability is inferior.

（比較例９）
比較例１と同様の操作で溶解し、１１００°Ｃで熱間鍛造のみを行い、表１に示すターゲットを製造し、ターゲットの面内方向の比透磁率は１５０であったこのターゲットを用いて、３８μｍ厚のポリイミドシート上に、表１に示す膜厚１０ｎｍのＮｉ−Ｃｒ−Ｔｉ合金バリア層を形成した。
比較例９のターゲットの比透磁率は１５０と、上記比較例８よりもさらに高い比透磁率を示すものであった。これをスパッタリングにより成膜しようとしたが、成膜不能であった。したがって、比透磁率が高すぎる場合には、成膜すら不能であり、適切でないことが分かった。(Comparative Example 9)
It melt | dissolved by the same operation as the comparative example 1, only hot forging was performed at 1100 degreeC, the target shown in Table 1 was manufactured, and the relative permeability of the in-plane direction of the target was 150 using this target A Ni—Cr—Ti alloy barrier layer having a thickness of 10 nm shown in Table 1 was formed on a 38 μm thick polyimide sheet.
The relative magnetic permeability of the target of Comparative Example 9 was 150, which was higher than that of Comparative Example 8 above. An attempt was made to form a film by sputtering, but film formation was impossible. Therefore, it was found that when the relative magnetic permeability is too high, even film formation is impossible and not appropriate.

以上から、本発明のＮｉ−Ｃｒ系合金膜及びターゲットは、適切な量のＣｒ、Ｔｉ及び／又はＺｒを含有することが重要である。特に、Ｔｉ及び／又はＺｒの添加は、バリア特性を著しく向上させて膜の耐久性を上げ、膜の均一性を確保するのに有効である。
また、本発明のフレキシブル銅基板用バリア膜の膜厚は３〜１５０ｎｍとすることが必要である。膜厚が３ｎｍ未満の場合は充分なバリア性を持たない。また、膜厚が１５０ｎｍを超えると膜剥がれを生じ易くなるので、上記の範囲とする。
さらに、本発明のフレキシブル銅基板用バリア膜の膜厚は、膜厚均一性が１σで１０％以下とすることが必要である。この膜均一性を適切な値を維持することは均一幅の配線を形成する上で極めて重要である。
本発明のバリア膜形成用スパッタリングターゲットにおいては、スパッタ面の面内方向の比透磁率が１００以下とすることが必要である。比透磁率が１００を超えると、スパッタ膜の膜厚均一性が１σで１０％を超えてしまい、場合によっては、スパッタリング不能となることがあるからである。From the above, it is important that the Ni—Cr alloy film and the target of the present invention contain an appropriate amount of Cr, Ti and / or Zr. In particular, the addition of Ti and / or Zr is effective in remarkably improving the barrier properties, increasing the durability of the film, and ensuring the uniformity of the film.
Moreover, the film thickness of the barrier film for flexible copper substrates of this invention needs to be 3-150 nm. When the film thickness is less than 3 nm, it does not have sufficient barrier properties. Moreover, since it will become easy to produce film peeling when a film thickness exceeds 150 nm, it is set as said range.
Furthermore, the film thickness of the barrier film for a flexible copper substrate of the present invention needs to have a film thickness uniformity of 10% or less at 1σ. Maintaining this film uniformity at an appropriate value is extremely important in forming a wiring having a uniform width.
In the sputtering target for forming a barrier film of the present invention, the relative permeability in the in-plane direction of the sputtering surface needs to be 100 or less. When the relative magnetic permeability exceeds 100, the film thickness uniformity of the sputtered film exceeds 10% at 1σ, and in some cases, sputtering may not be possible.

本発明は、細かい配線ピッチでも十分なバリア効果を得ることができ、さらに熱処理等により温度上昇があっても、バリア特性に変化がないという優れた特徴を有している。このように、ポリイミド等の樹脂フィルムへの銅の拡散を効果的に抑制する著しい特性を有するので、フレキシブル銅基板用バリア膜として有用である。
The present invention has an excellent feature that a sufficient barrier effect can be obtained even with a fine wiring pitch, and even if the temperature rises due to heat treatment or the like, the barrier characteristics do not change. Thus, since it has the remarkable characteristic which suppresses the spreading | diffusion of copper to resin films, such as a polyimide, it is useful as a barrier film for flexible copper substrates.

Claims (2)

Ｃｒ：５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金膜からなり、膜厚が３〜１５０ｎｍ、膜厚均一性が１σで１０％以下であることを特徴とするフレキシブル銅基板用バリア膜。  Cr: 5 to 30 wt%, Ti and / or Zr: 1 to 10 wt%, the balance is made of an inevitable impurity and Ni—Cr alloy film made of Ni, the film thickness is 3 to 150 nm, and the film thickness uniformity is A barrier film for a flexible copper substrate, which is 10% or less at 1σ. Ｃｒ：５〜３０ｗｔ％、Ｔｉ及び／又はＺｒ：１〜１０ｗｔ％含有し、残部が不可避的不純物及びＮｉからなるＮｉ−Ｃｒ系合金であって、スパッタ面の面内方向の比透磁率が１００以下であることを特徴とするバリア膜形成用スパッタリングターゲット。  Cr: 5 to 30 wt%, Ti and / or Zr: 1 to 10 wt%, the balance being a Ni—Cr alloy composed of unavoidable impurities and Ni, and the relative permeability in the in-plane direction of the sputtering surface is 100 The sputtering target for barrier film formation characterized by the following.
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