JP3222660B2 - Substrate surface treatment method - Google Patents

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】この発明は、基材表面を粗化する
工程を含む基材表面の処理方法、あるいは、基材表面を
粗化する工程と粗化された基材表面に膜を形成する工程
を含む基材表面の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of treating a substrate surface including a step of roughening the surface of a substrate, or a step of roughening the surface of a substrate and forming a film on the surface of the roughened substrate. The present invention relates to a method for treating the surface of a base material, the method including:

【０００２】[0002]

【従来の技術】従来のプリント配線板の製造方法では、
基材表面を粗化した後、粗化された基材表面に導電膜を
形成している。この従来のプリント配線板の製造方法
を、図２４を参照しながら説明する。まず、図２４の最
上段に示す基材２００の表面全面を湿式粗化した後、洗
浄してから、核付けに続いて無電解めっきを施して無電
解めっき膜２０１を形成し、その後、電気めっきを施し
て電気めっき膜２０２を形成する。ついで、レジスト塗
布によりレジスト層２０３を形成してから、露光と現像
によりレジスト層２０３の不要部分を除去して所定パタ
ーンと反対のパターンのレジストマスク２０４を形成し
た後、エッチング処理により非マスク域の無電解めっき
膜２０１および電気めっき膜２０２を選択的に除去し、
ついで、レジストマスク２０４を除去すれば、無電解め
っき膜と電気めっき膜の２層構成の所定パターンの導電
膜２０５が基材２００の表面に形成されたプリント配線
板２０６が得られる（特開昭６１−６８９２号公報）。2. Description of the Related Art In a conventional method of manufacturing a printed wiring board,
After roughening the substrate surface, a conductive film is formed on the roughened substrate surface. This conventional method for manufacturing a printed wiring board will be described with reference to FIG. First, after wet roughening the entire surface of the base material 200 shown in the uppermost stage in FIG. 24, and then cleaning, electroless plating is performed following nucleation to form an electroless plating film 201. The electroplating film 202 is formed by plating. Next, after forming a resist layer 203 by applying a resist, an unnecessary portion of the resist layer 203 is removed by exposure and development to form a resist mask 204 having a pattern opposite to a predetermined pattern. Selectively removing the electroless plating film 201 and the electroplating film 202,
Then, if the resist mask 204 is removed, a printed wiring board 206 in which a conductive film 205 having a predetermined pattern of a two-layer structure of an electroless plating film and an electroplating film is formed on the surface of the base material 200 is obtained. 61-6892).

【０００３】しかしながら、上の場合、絶縁基材２００
の表面粗化は、いわゆる薬液処理による湿式粗化である
ため、下記の問題がある。湿式粗化は、アルカリ等の薬
液処理管理の困難さや残留薬液の洗浄処理および環境上
有害な薬液を含む洗浄液の排水に伴う汚染の問題があ
る。湿式粗化の他にホーニングやブラスト処理による機
械的粗化もあるが、従来の機械的粗化では、粗化面の凹
みが浅いことなどから膜密着力を十分に向上させること
は難しく実用性は低い。However, in the above case, the insulating substrate 200
Surface roughening is a wet roughening by a so-called chemical solution treatment, and therefore has the following problems. The wet roughening has problems in that it is difficult to control the treatment of chemicals such as alkali, and there is a problem of contamination due to cleaning treatment of residual chemicals and drainage of cleaning liquids containing environmentally harmful chemicals. In addition to wet roughening, there is mechanical roughening by honing and blasting.However, with conventional mechanical roughening, it is difficult to sufficiently improve the film adhesion force due to the shallow dents in the roughened surface, which makes it practical. Is low.

【０００４】[0004]

【発明が解決しようとする課題】この発明は、上記の事
情に鑑みて、湿式粗化を用いずに膜密着力を十分に向上
させられる粗化が基材表面に施せる方法を提供すること
を第１の課題とし、湿式粗化を用いずに膜密着力の十分
な膜を基材表面に形成することのできる方法を提供する
ことを第２の課題とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide a method of performing roughening on the surface of a substrate which can sufficiently improve film adhesion without using wet roughening. A second object is to provide a method capable of forming a film having sufficient film adhesion on a substrate surface without using wet roughening.

【０００５】[0005]

【課題を解決するための手段】この発明にかかる基材表
面の処理方法は、上記第１の課題を解決するため、基材
表面に紫外レーザを照射して前記基材表面の粗化を行う
工程を含む構成をとるようにしており、第２の課題を解
決するため、基材表面に紫外レーザを照射して前記基材
表面の粗化を行う工程と粗化された基材表面に膜を形成
する工程を含む構成をとっている。According to the present invention, there is provided a method of treating a surface of a substrate, wherein the surface of the substrate is roughened by irradiating the surface with an ultraviolet laser to solve the first problem. In order to solve the second problem, a step of irradiating the surface of the base material with an ultraviolet laser to roughen the surface of the base material and a step of forming a film on the roughened base material surface are performed. Is formed.

【０００６】以下、この発明をより詳しく説明する。こ
の発明では、粗化のために照射する紫外レーザとして、
通常、波長１００〜４００ｎｍ程度、レーザエネルギー
０．１〜１．０Ｊ／cm² 程度の紫外レーザが使われる。
紫外レーザの波長が、１００ｎｍ未満の場合は空気中で
のレーザ光の減衰が大きく使用できる光学材料も少なく
という不都合が見られる傾向があり、波長４００ｎｍを
超す場合、基材表面への熱影響が大き過ぎて表面が粗化
よりも溶融し易くなるという不都合がみられる傾向があ
る。紫外レーザのエネルギーが０．１Ｊ／cm² 未満の場
合は粗化効果が弱く実用上十分な凹凸が得られないとい
う不都合が見られる傾向があり、１．０Ｊ／cm² を超す
場合は粗化と同時に被照射基材の分解蒸発が起こり溝部
が形成され後の膜形成に対して好ましくないという不都
合がみられる傾向がある。Hereinafter, the present invention will be described in more detail. In the present invention, as an ultraviolet laser for irradiation for roughening,
Usually, an ultraviolet laser having a wavelength of about 100 to 400 nm and a laser energy of about 0.1 to 1.0 J / cm ² is used.
When the wavelength of the ultraviolet laser is less than 100 nm, there is a tendency that the laser light is greatly attenuated in the air and there are few optical materials that can be used, and when the wavelength exceeds 400 nm, the thermal effect on the substrate surface is reduced. There is a tendency that the size is too large and the surface is more easily melted than roughened. Tend to energy of the ultraviolet laser is observed disadvantageously 0.1 J / cm in the case of less than ² is not practically sufficient irregularities weak roughening effect obtained, roughened if more than 1.0 J / cm ² At the same time, the substrate to be irradiated tends to decompose and evaporate to form a groove, which is unfavorable for the subsequent film formation.

【０００７】この発明の基材表面の処理方法の場合、基
材表面への膜形成方法は、限定される訳ではないが、例
えば、無電解めっきや、電気めっき、ＣＶＤなどによる
金属膜の形成法が挙げられるし、さらに、膜自体も無機
膜や有機膜であってもよい。紫外レーザの照射は、基材
表面の全面でなく、特定域（例えば、後形成または同時
形成で所定パターンの膜を設ける膜形成用域）だけに行
うようにしてもよい。In the method of treating the surface of a substrate according to the present invention, the method of forming a film on the surface of the substrate is not limited, but for example, the formation of a metal film by electroless plating, electroplating, CVD or the like. A method may be used, and the film itself may be an inorganic film or an organic film. Irradiation with the ultraviolet laser may be performed not on the entire surface of the base material but only on a specific area (for example, a film formation area where a film of a predetermined pattern is formed by post-formation or simultaneous formation).

【０００８】湿式粗化は膜形成用域のみを粗化する選択
的粗化にも適さないが、紫外レーザの照射による粗化は
膜形成用域のみを粗化する選択的粗化にも適する。湿式
粗化で選択的粗化を行う場合は、非粗化面だけにマスキ
ングテープを貼り付け薬液に浸漬するのであるが、マス
キングテープは余り細くできないため微細（ファイン）
パターン化が難しい上、テープ剥離後に残る接着剤を除
去するためにフロンなどの有機溶剤を使う必要もあるの
に対し、紫外レーザ照射による粗化は、照射を膜形成用
域に限る程度で済むからである。Although wet roughening is not suitable for selective roughening in which only the film forming region is roughened, roughening by irradiation with ultraviolet laser is also suitable for selective roughening in which only the film forming region is roughened. . In the case of selective roughening by wet roughening, a masking tape is applied only to the non-roughened surface and immersed in a chemical solution. However, the masking tape cannot be made very thin, so it is fine.
Patterning is difficult and it is necessary to use an organic solvent such as chlorofluorocarbon to remove the adhesive remaining after the tape is peeled off, whereas roughening by ultraviolet laser irradiation only requires irradiation to be limited to the film formation area. Because.

【０００９】基材表面の特定域のみに紫外レーザの照射
を行う場合は、図１の（ａ）にみるように、基材１の前
面に膜形成用域に対応する個所が窓となって開いている
マスクを配しておいて、紫外レーザを全面的に当てる
か、図１の（ｂ）にみるように、ビーム状の紫外レーザ
をマスクの上から走査させるか、あるいは、図１の
（ｃ）にみるように、絶縁基材１の前にガルバノミラー
等のスキャンニング機構を設けてビーム状の紫外レーザ
を走査させるか、さらには、図１の（ｄ）にみるよう
に、基材１の表面にビーム状の紫外レーザを当てた状態
で基材１の方をＸ−Ｙテーブル等で移動させ相対的に紫
外レーザを走査させるなどすればよい。When the ultraviolet laser is applied only to a specific area on the surface of the base material, as shown in FIG. 1A, a window corresponding to the area for film formation is formed on the front surface of the base material 1 as a window. An open mask is arranged, and an ultraviolet laser is applied to the entire surface. As shown in FIG. 1B, a beam-shaped ultraviolet laser is scanned from above the mask. As shown in (c), a scanning mechanism such as a galvanometer mirror is provided in front of the insulating base material 1 to scan with a beam-shaped ultraviolet laser, or further, as shown in (d) of FIG. The substrate 1 may be moved with an XY table or the like while the beam-shaped ultraviolet laser is applied to the surface of the material 1 to relatively scan the ultraviolet laser.

【００１０】この発明の場合、加えて、紫外レーザの照
射により、粗化された基材表面を光照射により加熱する
こともある。この光照射は、粗化表面に膜を形成する
前、膜形成中、膜形成後の３つのいずれの場合でもよ
い。光照射する粗化面は、基材表面の全面に施されてい
てもよいし、基材表面の特定域だけに施されていてもよ
い。光照射は、例えば、赤外レーザや可視光ビームなど
の熱作用の強い光を粗化表面に照射することで行える。
光照射を伴う加熱により、粗化面の凸部の先端が溶融な
いし軟化して球状化し先端のみが太くなってアンカー効
果を発揮するようになったり、膜形成後の場合は、基板
材料と膜形成材料との間で混合ないし拡散などが起こり
混合域を形成し密着力を強化したりする。In the case of the present invention, in addition, the surface of the substrate which has been roughened by irradiation with an ultraviolet laser may be heated by light irradiation. This light irradiation may be any of the three cases before, during, and after formation of the film on the roughened surface. The roughened surface to be irradiated with light may be applied to the entire surface of the substrate, or may be applied only to a specific region of the surface of the substrate. Light irradiation can be performed by irradiating the roughened surface with light having a strong thermal effect, such as an infrared laser or a visible light beam.
By heating with light irradiation, the tip of the convex part of the roughened surface is melted or softened and becomes spherical, and only the tip becomes thicker to exhibit the anchor effect. Mixing or diffusion occurs with the forming material to form a mixed region to enhance adhesion.

【００１１】この発明の場合、基材表面への紫外レーザ
照射を、反応ガスの導入と同反応ガスへのレーザ照射を
伴うレーザＣＶＤの前記反応ガスへのレーザ照射として
も用い、基材表面に対し粗化と同時にレーザＣＶＤによ
る膜の形成を行うようにしてもよい。つまり、この発明
の場合、粗化工程と膜形成工程が同時に行われることも
あるのである。この場合も、基材表面への紫外レーザの
照射は、基材表面の全面でもよいし、特定域だけでもよ
い。In the case of the present invention, ultraviolet laser irradiation on the surface of the substrate is also used as laser irradiation on the reaction gas by laser CVD accompanied by introduction of the reaction gas and laser irradiation on the reaction gas. On the other hand, a film may be formed by laser CVD simultaneously with the roughening. That is, in the case of the present invention, the roughening step and the film forming step may be performed simultaneously. Also in this case, the irradiation of the ultraviolet laser to the surface of the base material may be performed on the entire surface of the base material surface or may be performed only on a specific region.

【００１２】上に説明した、この発明の様々な態様にお
いて使われる基材は、特定の基材に限られる訳ではな
く、たとえば、樹脂基材、セラミック基材などの絶縁基
材、金属基材などの導電基材が挙げられる。さらに、下
記のような基材Ａ〜Ｆを用いることも有用である。樹脂
基材Ａは、紫外レーザの照射によっても除去されにくい
粒子が表面部分に分散されている樹脂基材である。この
粒子は、必ずしも樹脂基材全体に含まれている必要はな
く、少なくとも粗化を行う領域（例えば、膜形成用域）
に含まれていればよく、普通、樹脂基材全体１００重量
％のうち粒子は１０〜９０重量％を占める。この紫外レ
ーザの照射によっても除去されにくい粒子としては、具
体的に、無機粉末や非粒子部分の樹脂より硬質の樹脂粉
末が挙げられる。The substrate used in the various embodiments of the present invention described above is not limited to a specific substrate. For example, a resin substrate, an insulating substrate such as a ceramic substrate, a metal substrate, and the like. And the like. Further, it is also useful to use the following substrates A to F. The resin base material A is a resin base material in which particles that are difficult to be removed even by irradiation with an ultraviolet laser are dispersed in a surface portion. These particles do not necessarily need to be contained in the entire resin base material, and at least a region to be roughened (for example, a film forming region)
In general, the particles account for 10 to 90% by weight of 100% by weight of the entire resin base material. Specific examples of the particles that are not easily removed by the irradiation of the ultraviolet laser include inorganic powder and resin powder harder than the resin in the non-particle portion.

【００１３】樹脂基材Ｂは、紫外レーザの照射により除
去され易い粒子が表面部分に分散されている樹脂基材で
ある。この粒子は、必ずしも樹脂基材全体に含まれてい
る必要はなく、少なくとも粗化を行う領域（例えば、膜
形成用域）に含まれていればよく、普通、樹脂基材全体
１００重量％のうち粒子は１０〜９０重量％を占める。
この紫外レーザの照射により除去され易い粒子として
は、非粒子部分の樹脂より柔らかい軟質の樹脂粉末が挙
げられる。The resin base material B is a resin base material in which particles which are easily removed by irradiation with an ultraviolet laser are dispersed in a surface portion. The particles do not necessarily need to be contained in the entire resin base material, but may be contained at least in a region to be roughened (for example, a film formation region). The particles account for 10 to 90% by weight.
Examples of the particles that can be easily removed by irradiation with the ultraviolet laser include soft resin powder that is softer than the resin in the non-particle portion.

【００１４】樹脂基材Ｃは、紫外レーザの照射によって
も除去されにくい粒子と紫外レーザの照射により除去さ
れ易い粒子の両方の粒子が表面部分に分散されている樹
脂基材である。これらの粒子は、必ずしも樹脂基材全体
に含まれている必要はなく、少なくとも粗化を行う領域
（例えば、膜形成用域）に含まれていればよく、普通、
樹脂基材全体１００重量％のうち粒子は１０〜９０重量
％を占める。この場合、紫外レーザの照射に対する除去
性は、紫外レーザの照射により除去され易い粒子が一番
良く、紫外レーザの照射によっても除去され難い粒子が
一番悪く、非粒子部分の樹脂が両粒子の間となる。The resin base material C is a resin base material in which both particles that are hardly removed by irradiation with ultraviolet laser and particles that are easily removed by irradiation with ultraviolet laser are dispersed on the surface. These particles do not necessarily need to be contained in the entire resin base material, but may be contained at least in a region to be roughened (for example, a film forming region).
Particles account for 10 to 90% by weight of 100% by weight of the whole resin base material. In this case, the particles that can be easily removed by the ultraviolet laser irradiation are the best, and the particles that are not easily removed by the ultraviolet laser irradiation are the worst, and the resin in the non-particle portion is the resin of both particles. Between.

【００１５】樹脂基材Ｄは、一部表面部分を紫外レーザ
の照射により粗化されやすい樹脂材料で形成した樹脂基
材である。他の部分は紫外レーザによっても粗化され難
い樹脂材料からなる。基材表面の粗化を行う部分のみを
紫外レーザの照射により粗化されやすい樹脂材料で形成
しておくのである。樹脂基材Ｄは、粗化容易な樹脂材料
と粗化困難な樹脂材料を二色成形法などを用いて成形す
ることで簡単に作れる。The resin substrate D is a resin substrate whose surface is partially formed of a resin material which is easily roughened by irradiation with an ultraviolet laser. Other portions are made of a resin material that is hardly roughened even by an ultraviolet laser. Only the part where the surface of the base material is to be roughened is formed of a resin material which is easily roughened by irradiation with an ultraviolet laser. The resin base material D can be easily formed by molding a resin material that is easily roughened and a resin material that is hardly roughened using a two-color molding method or the like.

【００１６】樹脂基材Ｅは、基材表面に金属材料を分散
付着させた樹脂基材である。金属材料は粗化を行う領域
だけに分散付着させてもよいし全面に付着させてもよ
い。基材表面に対する金属材料の分散付着は、特定の方
法に限らないが、例えば、反射率の高い金属材料を無電
解めっきなどで部分的に分散析出させたり、粒径の小さ
な金属粒子（粉体）と有機溶剤との混合物（ペーストな
ど）を塗布し有機溶剤だけを飛ばして金属粒子を表面に
分散残留させたり、金属材料を蒸着（例えば、真空蒸
着）で部分的に分散付着させたりすることで行える。The resin substrate E is a resin substrate in which a metal material is dispersed and adhered to the surface of the substrate. The metal material may be dispersed and attached only to the region to be roughened, or may be attached to the entire surface. The dispersion adhesion of the metal material to the substrate surface is not limited to a specific method. For example, a metal material having a high reflectance is partially dispersed and deposited by electroless plating or the like, or a metal particle having a small particle diameter (powder) is used. ) And an organic solvent (paste, etc.) and apply only the organic solvent to disperse and leave metal particles on the surface, or to partially disperse and adhere the metal material by vapor deposition (for example, vacuum vapor deposition). Can be done with

【００１７】樹脂基材Ｆは、表面部分に膜形成物質と結
合し易い物質が含まれている（通常は分散含有してい
る）樹脂基材である。この場合の表面部分には、事実
上、表面にのみに分散している形態を含む。樹脂基材Ａ
〜Ｆの粒子や物質は、表面付近の必要域に含まれていれ
ばよいが、基材全体に含まれていてもよい。また、上記
樹脂基材Ａ〜Ｅ中に膜形成物質と結合し易い物質を含ま
せる形態もある。膜形成物質と結合し易い物質として
は、めっき触媒、カップリング剤、膜形成物質と同じ物
質又は類似の物質（金属膜であれば同一の金属または類
似の金属に結合し易いのである）などが挙げられる。The resin base material F is a resin base material containing (usually dispersed and contained) a substance which easily binds to the film-forming substance in the surface portion. The surface portion in this case includes a form that is practically dispersed only on the surface. Resin base material A
The particles and substances F to F need only be contained in a necessary area near the surface, but may be contained in the entire substrate. Further, there is also a mode in which a substance which easily binds to the film-forming substance is contained in the resin base materials A to E. Examples of the substance that easily binds to the film-forming substance include a plating catalyst, a coupling agent, and the same substance or a similar substance as the film-forming substance (a metal film is likely to bind to the same metal or a similar metal). No.

【００１８】そして、上記の方法で粗化された基材表面
に対する膜の形成方法は、前述の如く、特定の方法に限
らない。紫外レーザの照射により基材表面の特定域であ
る膜形成用域だけを選択的に粗化しておき、膜の形成を
基材表面の特定域に選択的に行ったり、あるいは、膜を
基材表面の全面に施したあと、基材表面の特定域以外の
膜だけを除去するようにしたり、さらには、加えて、膜
の形成を反応性ガスの導入と同反応ガスへの光照射を伴
うＣＶＤにより膜形成を行うとともに、前記光照射によ
り基材表面の粗化面の加熱をも行うようにしたりしても
よい。The method of forming a film on the substrate surface roughened by the above method is not limited to a specific method as described above. Only the film forming area, which is a specific area on the substrate surface, is selectively roughened by irradiation with an ultraviolet laser, and the film is selectively formed on a specific area on the substrate surface. After applying to the entire surface, it is necessary to remove only the film other than the specific area of the substrate surface, and in addition, the formation of the film involves the introduction of a reactive gas and the irradiation of the reactive gas with light. The film may be formed by CVD, and the roughened surface of the substrate may be heated by the light irradiation.

【００１９】膜形成用域の選択的粗化は、所定パターン
化のために基材表面の全面に形成しためっき膜の不要部
分の選択的除去に好都合である。めっき膜における粗化
域以外の除去する部分の下が粗化されておらず密着力が
弱く剥がれ易く残留しないからである。除去するめっき
膜の下も粗化される全面粗化では、絶縁低下の原因とな
る残留めっき膜が残り易くなる。残留めっき膜が残らな
いように過剰な条件でエッチングを行うと、残るめっき
膜部分にサイドエッチが起こり易くなる。The selective roughening of the film forming area is convenient for selectively removing unnecessary portions of the plating film formed on the entire surface of the base material for forming a predetermined pattern. This is because the portion under the portion to be removed other than the roughened region in the plating film is not roughened, the adhesion is weak, the film is easily peeled off, and does not remain. In the roughening of the entire surface in which the portion under the plating film to be removed is roughened, a residual plating film which causes a decrease in insulation tends to remain. If etching is performed under excessive conditions so that the residual plating film does not remain, side etching tends to occur in the remaining plating film portion.

【００２０】さらに、この発明の基材表面の粗化から膜
の形成までの具体的な処理例を、図２〜７を参照しなが
ら説明する。図２〜７では、最終的に特定パターンの導
電膜２を有するプリント配線板を得ている。図２の処理
例では、紫外レーザによる粗化は基材１の表面全面に行
い、無電解めっき、電気めっきを基材表面の全面に施
し、レジストマスクを設け、選択的エッチングで不要部
分を除去し、特定パターンの導電膜２を基材１の表面に
形成する。核付けの前に、粗化された基材１の表面を光
照射により加熱し、粗化面の凸部の先端を球状化し太く
するのもよい。湿式粗化を用いずとも、導電膜２の密着
力が向上する。Further, a specific processing example from the roughening of the substrate surface to the formation of a film according to the present invention will be described with reference to FIGS. 2 to 7, a printed wiring board having a conductive film 2 having a specific pattern is finally obtained. In the processing example of FIG. 2, roughening by the ultraviolet laser is performed on the entire surface of the substrate 1, electroless plating and electroplating are performed on the entire surface of the substrate, a resist mask is provided, and unnecessary portions are removed by selective etching. Then, a conductive film 2 having a specific pattern is formed on the surface of the substrate 1. Before the nucleation, the roughened surface of the base material 1 may be heated by light irradiation to make the tip of the convex portion of the roughened surface spherical and thick. The adhesion of the conductive film 2 is improved without using wet roughening.

【００２１】図３の処理例では、紫外レーザによる粗化
は基材１の全面ではなく特定パターンの導電膜を設ける
膜形成用域のみに行い、無電解めっきを膜形成用域のみ
に選択的に析出形成した後、基材表面を光照射により加
熱し、粗化面の凸部の先端を球状化し先端のみを太くし
てアンカー効果を発揮させられるようになったり、ある
いは、無電解めっき膜と基材１の混合域を形成させるよ
うにして無電解めっき膜と基材１の密着力を高め、その
後、無電解めっき膜の上に電気めっき膜を積層し、特定
パターンの導電膜２を基材１の表面に形成する。湿式粗
化を用いずとも、レジストマスク形成や選択的エッチン
グの省略が出来、導電膜２の密着力も向上する。In the processing example shown in FIG. 3, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming region where the conductive film of a specific pattern is provided, and the electroless plating is selectively performed only on the film forming region. After depositing on the substrate, the surface of the base material is heated by light irradiation, and the tip of the convex part of the roughened surface is made spherical to make only the tip thicker, so that the anchor effect can be exhibited, or the electroless plating film The adhesion between the electroless plating film and the base material 1 is increased by forming a mixed region of the base material 1 and the electroless plating film. Thereafter, the electroplating film is laminated on the electroless plating film, and the conductive film 2 having a specific pattern is formed. It is formed on the surface of the substrate 1. Even without using wet roughening, formation of a resist mask and selective etching can be omitted, and the adhesion of the conductive film 2 can be improved.

【００２２】図４の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行うが、粗化
用の紫外レーザを、反応ガスの導入と同反応ガスへのレ
ーザ照射を伴うレーザＣＶＤの前記反応ガスへの照射レ
ーザとしても用い、基材表面に対し粗化と同時にレーザ
ＣＶＤにより金属膜の形成を膜形成用域のみに行う。そ
して、金属膜の上に電気めっき膜を積層し、特定パター
ンの導電膜２を基材１の表面に形成している。湿式粗化
を用いず、レジストマスク形成や選択的エッチングの省
略が出来、導電膜２の密着力も向上する。In the processing example of FIG. 4, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only in the film forming region. A metal film is formed only in the film formation region by laser CVD while simultaneously roughening the surface of the base material and using the laser as an irradiation laser for the reaction gas in laser CVD accompanied by laser irradiation. Then, an electroplating film is laminated on the metal film, and a conductive film 2 having a specific pattern is formed on the surface of the substrate 1. The formation of a resist mask and selective etching can be omitted without using wet roughening, and the adhesion of the conductive film 2 is also improved.

【００２３】図５の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、無電解
めっき、電気めっきを基材表面の全面に施し、レジスト
マスクを設け、選択的エッチングで不要部分を除去し、
特定パターンの導電膜２を基材１の表面に形成してい
る。核付けの前に、粗化された基材１の表面を光照射に
より加熱し、粗化面の凸部の先端を球状化し先端のみを
太くしてアンカー効果を発揮させられるようにしておく
のもよい。湿式粗化を用いず、選択的エッチングは、非
粗化面の上の膜を除去するのであるから容易であり、導
電膜２の密着力も向上する。In the processing example shown in FIG. 5, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming area, and electroless plating and electroplating are performed on the entire surface of the substrate 1 and a resist mask is provided. , Remove unnecessary parts by selective etching,
A conductive film 2 having a specific pattern is formed on the surface of the substrate 1. Before nucleation, the surface of the roughened substrate 1 is heated by light irradiation, and the tip of the convex portion of the roughened surface is made spherical so that only the tip is thickened so that the anchor effect can be exhibited. Is also good. The selective etching is easy because the film on the non-roughened surface is removed without using wet roughening, and the adhesion of the conductive film 2 is also improved.

【００２４】図６の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、核付け
を行ったのち、洗浄等で非粗化域の核剤を除去してか
ら、無電解めっきを行い、膜形成用域のみにめっき膜を
析出形成した後、無電解めっき膜の上に電気めっき膜を
積層し、特定パターンの導電膜２を基材１の表面に形成
している。湿式粗化を用いずとも、レジストマスク形成
や選択的エッチングの省略が出来、導電膜２の密着力も
向上する。In the processing example shown in FIG. 6, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming area, and after nucleation, the nucleating agent in the non-roughened area is removed by washing or the like. After that, electroless plating is performed to deposit and form a plating film only in the film forming area. Then, an electroplating film is laminated on the electroless plating film, and a conductive film 2 having a specific pattern is formed on the surface of the substrate 1. Is formed. Even without using wet roughening, formation of a resist mask and selective etching can be omitted, and the adhesion of the conductive film 2 can be improved.

【００２５】図７の処理例では、紫外レーザによる粗化
は基材１の全面ではなく膜形成用域のみに行い、その
後、反応性ガスの導入と同反応ガスへの光照射を伴うＣ
ＶＤ（レーザ熱ＣＶＤなど）により行うとともに前記光
照射により基材表面の粗化面の加熱を行うようにして、
膜形成用域のみに金属膜を形成する。光照射の加熱によ
り金属膜は、基材と混合域を形成したり、粗化面の凸部
先端が球状化したりするため、基板に強く密着する。そ
して、この金属膜の上に電気めっき膜を積層し、特定パ
ターンの導電膜２を基材１の表面に形成する。湿式粗化
を用いずとも、無電解めっきやレジストマスク形成や選
択的エッチングの省略が出来、導電膜２の密着力も向上
する。In the processing example shown in FIG. 7, the roughening by the ultraviolet laser is performed not on the entire surface of the substrate 1 but only on the film forming region, and thereafter, the reaction gas is introduced together with the introduction of the reactive gas and the irradiation of the reactive gas with light.
By performing VD (laser thermal CVD etc.) and heating the roughened surface of the substrate surface by the light irradiation,
A metal film is formed only in the film formation area. The metal film forms a mixed region with the base material by heating with light irradiation, or the tip of the convex portion of the roughened surface becomes spherical, so that the metal film strongly adheres to the substrate. Then, an electroplating film is laminated on the metal film, and a conductive film 2 having a specific pattern is formed on the surface of the substrate 1. Even without using wet roughening, electroless plating, formation of a resist mask, and selective etching can be omitted, and the adhesion of the conductive film 2 is also improved.

【００２６】[0026]

【作用】この発明のパターン膜形成方法の場合、基材表
面に対し紫外レーザの照射により粗化を行うため、湿式
粗化を用いずに基材表面の粗化が実現できる。紫外レー
ザは十分なエネルギーを有するため、粗化面での凹みが
膜形成用域に機械的な粗化方法の場合よりも深くなり、
粗化された基材表面に形成される膜は密着力の十分なも
のとなる。In the pattern film forming method of the present invention, the surface of the substrate is roughened by irradiating an ultraviolet laser, so that the surface of the substrate can be roughened without using wet roughening. Since the UV laser has enough energy, the dent on the roughened surface becomes deeper in the film formation area than in the case of the mechanical roughening method,
The film formed on the roughened substrate surface has sufficient adhesion.

【００２７】粗化された基材表面を光照射により加熱す
る場合、粗化面の凸部の先端のみが太くアンカー効果が
備わったり、膜と基材の混在域が出来るなど膜の密着力
はより十分なものとなる。紫外レーザの照射を特定域に
選択的に行う場合は、特定域以外の領域に粗化面が形成
されないため、特定域への選択的膜形成が容易に行える
だけでなく、また、全面的に膜を形成してから膜形成域
以外の領域の膜を選択的に除く場合にも、除去する膜の
下が粗化されていないため容易に除去でき、特定域以外
の領域に膜が残ったり、特定域に残る膜のサイドエッチ
が防止できる。When the roughened surface of the substrate is heated by light irradiation, the adhesion of the film is poor, for example, only the tip of the convex portion of the roughened surface is thick and has an anchor effect, or a mixed region of the film and the substrate is formed. It will be more sufficient. When the ultraviolet laser irradiation is selectively performed in a specific region, a roughened surface is not formed in a region other than the specific region, so that not only the selective film formation in the specific region can be easily performed, but also the entire surface is formed. Even when the film is selectively removed from the area other than the film formation area after forming the film, it can be easily removed because the area under the film to be removed is not roughened, and the film remains in the area other than the specific area. In addition, side etching of a film remaining in a specific area can be prevented.

【００２８】基材表面への紫外レーザを、反応ガスの導
入と同反応ガスへのレーザ照射を伴うレーザＣＶＤの前
記反応ガスへのレーザ照射として用い、基材表面に対し
粗化と同時にレーザＣＶＤによる膜形成をも行うと、粗
化と膜形成が同時に行える利点がある。紫外レーザの照
射によっても除去されにくい粒子が表面部分に分散され
ている樹脂基材に対し紫外レーザ照射を行うと、除去さ
れにくい粒子が突出残留した状態で粗化が行われる。粒
子の大きさや混合量の調節により深い凹みのある粗化が
できる。An ultraviolet laser on the surface of the base material is used as laser irradiation for the reaction gas in laser CVD involving the introduction of a reaction gas and the irradiation of the reaction gas with laser, and the surface of the base material is roughened and the laser CVD is performed simultaneously. When film formation is also performed by the method described above, there is an advantage that roughening and film formation can be performed simultaneously. When ultraviolet laser irradiation is performed on a resin substrate in which particles that are difficult to be removed even by irradiation with ultraviolet laser are dispersed in the surface portion, roughening is performed in a state in which the particles that are hard to be removed protrude and remain. By adjusting the size and mixing amount of the particles, roughening with a deep dent can be achieved.

【００２９】紫外レーザの照射により除去され易い粒子
が表面部分に分散されている樹脂基材に対し紫外レーザ
照射を行うと、紫外レーザで除去され易い粒子が除かれ
凹みが表面に分散現出した状態となる。粒子の大きさや
混合量の調節により深い凹みの粗化ができる。紫外レー
ザの照射によっても除去されにくい粒子と、紫外レーザ
の照射により除去され易い粒子の両方の粒子が表面部分
に分散されている樹脂基材に対し紫外レーザ照射を行う
と、除去され難い粒子は突出残留するとともに除去され
易い粒子が除かれ凹みが表面に分散現出し、粗化が出来
る。やはり、粒子の大きさや混合量の調節により深い凹
みのある粗化ができる。When the resin substrate in which the particles which are easily removed by the irradiation of the ultraviolet laser are dispersed on the surface is irradiated with the ultraviolet laser, the particles which are easily removed by the ultraviolet laser are removed and the dents appear on the surface. State. By adjusting the size and mixing amount of the particles, deep dents can be roughened. Particles that are not easily removed by irradiation with ultraviolet laser and particles that are easily removed by irradiation with ultraviolet laser are subjected to ultraviolet laser irradiation on the resin base material in which both particles are dispersed on the surface portion. Particles that remain protruding and are easily removed are removed, and dents appear on the surface and can be roughened. Again, roughening with a deep dent can be achieved by adjusting the size and mixing amount of the particles.

【００３０】表面部分の一部を紫外レーザの照射により
粗化されやすい樹脂材料で形成した樹脂基材に対し、紫
外レーザ照射を行うと、紫外レーザ照射で粗化されやす
い樹脂材料の部分だけが選択的に粗化される。他の部分
が紫外レーザによっても粗化され難い樹脂材料で出来て
いる樹脂基材でも、基材表面の必要部分の選択的粗化が
可能となる。When ultraviolet laser irradiation is performed on a resin base material having a part of the surface portion formed of a resin material that is easily roughened by ultraviolet laser irradiation, only the resin material portion that is easily roughened by ultraviolet laser irradiation is exposed. It is selectively roughened. Even in a resin base material whose other portion is made of a resin material that is hardly roughened even by an ultraviolet laser, it is possible to selectively roughen a required portion of the base material surface.

【００３１】膜形成物質と結合し易い物質を表面部分に
含有する樹脂基材を用いると、粗化面で膜形成物質と結
合し易い物質が結合して膜の密着力がより高まる。金属
材料を表面に分散付着させた樹脂基材に対し紫外レーザ
を照射すると、金属材料の非付着域が選択的に除かれ深
い凹みが分散現出し十分な深さの粗化が出来る。When a resin base material containing a substance which easily binds to the film-forming substance is used in the surface portion, a substance which easily binds to the film-forming substance on the roughened surface is bonded to further increase the adhesion of the film. When an ultraviolet laser is applied to the resin substrate having the metal material dispersed and adhered to the surface, the non-adhered area of the metal material is selectively removed, and a deep dent is dispersed and the surface is roughened to a sufficient depth.

【００３２】この発明の表面粗化方法により基材表面の
特定域が選択的に粗化された基材を用いる場合、特定域
以外の領域が粗化されていないため、特定域への選択的
な膜形成や、膜形成用域以外の領域上の膜の除去が容易
に行え、特定域だけへサイドエッチのない膜を設けるこ
とが容易に行える。加えて、膜形成を、反応性ガスの導
入と同反応性ガスに対する光照射を伴うＣＶＤにより行
うと同時に光照射により基材表面の粗化面の加熱をも行
う場合、粗化面の凸部の先端が太くなったり、膜と基材
の混在域が出来るなど膜の密着力はより十分なものとな
る。In the case of using a substrate whose specific area on the substrate surface is selectively roughened by the surface roughening method of the present invention, the area other than the specific area is not roughened. It is possible to easily form a film and to remove a film on a region other than the film forming region, and to provide a film without side etching only in a specific region. In addition, when the film is formed by CVD involving the introduction of a reactive gas and light irradiation on the reactive gas, and at the same time heating the roughened surface of the base material surface by light irradiation, the projections on the roughened surface The adhesion of the film becomes more sufficient, for example, the end of the film becomes thicker or a mixed region of the film and the substrate is formed.

【００３３】[0033]

【実施例】以下、この発明の実施例について説明する。
この発明は、下記の実施例に限らない。 −実施例１− 実施例１では、図８にみるように、基材１の表面の膜形
成用域のみに紫外レーザを照射して選択的に粗化し、図
６の処理例に従って、無電解めっき、電気めっきを施
し、特定パターンの導電膜２を基材１の表面に形成す
る。勿論、粗化のあと、図５の処理例に従って、無電解
めっき、電気めっきを施し、選択エッチングし、特定パ
ターンの導電膜２を基材１の表面に形成してもよい。無
電解めっきは銅めっき、ニッケルめっき、金めっき等が
あり、電気めっきにも、銅めっき、ニッケルめっき、金
めっき等がある。Embodiments of the present invention will be described below.
The present invention is not limited to the following embodiments. -Example 1-In Example 1, as shown in Fig. 8, only the film forming area on the surface of the substrate 1 was irradiated with an ultraviolet laser to selectively roughen the film, and according to the processing example of Fig. 6, Plating and electroplating are performed to form a conductive film 2 having a specific pattern on the surface of the substrate 1. Of course, after the roughening, electroless plating and electroplating may be performed according to the processing example of FIG. 5 and selective etching may be performed to form a conductive film 2 having a specific pattern on the surface of the substrate 1. Electroless plating includes copper plating, nickel plating, gold plating, and the like, and electroplating also includes copper plating, nickel plating, gold plating, and the like.

【００３４】基材１には、ポリイミド、エポキシなどの
樹脂基材、金属基材、アルミナなどのセラミック基材な
ど何でもよい。紫外レーザの波長は１９３〜４００ｎｍ
程度、エネルギーは０．１〜１．０Ｊ／ｃｍ² 程度でよ
い。例えば、基材１が液晶ポリマー基材であれば、約
０．５〜０．７ｋｇ／ｃｍのピール強度がある。粗化し
ない場合の約０．０８ｋｇ／ｃｍのピール強度に比べて
格段の向上である。The substrate 1 may be anything such as a resin substrate such as polyimide or epoxy, a metal substrate, or a ceramic substrate such as alumina. The wavelength of the ultraviolet laser is 193 to 400 nm
Degree and energy may be about 0.1 to 1.0 J / cm ² . For example, if the substrate 1 is a liquid crystal polymer substrate, it has a peel strength of about 0.5 to 0.7 kg / cm. This is a remarkable improvement as compared with the peel strength of about 0.08 kg / cm when the surface is not roughened.

【００３５】具体的に、厚み１．６ｍｍのＡＢＳ樹脂
（アクリロニトリル・ブタジエン・スチレン共重合体系
樹脂）製基材１に波長２４８ｎｍ、エネルギー０．３Ｊ
／ｃｍ ² の紫外レーザを照射し、粗化した後、無電解銅
めっき、ついで、電気銅めっきを行いプリント配線板を
得た。実施例１の場合、湿式粗化不要により問題の薬液
洗浄などがなくなり、基材表面の選択粗化が可能なため
特定パターンの導電膜２のサイドエッチの心配もなく、
導電膜２の密着力も高い。Specifically, an ABS resin having a thickness of 1.6 mm
(Acrylonitrile-butadiene-styrene copolymer system
Resin) base material 1 has a wavelength of 248 nm and energy of 0.3 J
/ Cm ^TwoIrradiated with UV laser and roughened, electroless copper
Plating and then electro copper plating to make the printed wiring board
Obtained. In the case of Embodiment 1, the chemical solution in question is unnecessary because wet roughening is unnecessary.
Eliminates cleaning, etc. and allows selective roughening of the substrate surface
There is no need to worry about side etching of the conductive film 2 with a specific pattern.
The adhesion of the conductive film 2 is also high.

【００３６】−実施例２− この発明では、図９の（ａ）にみるように、基材１全面
に紫外レーザを照射して粗化し、そのまま、図９の
（ｂ）にみるように、膜３を形成してもよいのである
が、図９の（ｃ）にみるように、基材１から膜３が剥が
れるのを十分に防ぐには、以下のようにするのがよい。
すなわち、図１０の（ａ）にみるように、基材１全面に
紫外レーザを照射して粗化し、ついで、図１０の（ｂ）
にみるように、粗化面に光照射による熱処理をし、粗化
面の細い凸部の先端のみを球状化し太くしてから、図１
０の（ｃ）にみるように、膜３を形成する。この後、図
２の処理例に準じて、特定パターンの例えば銅などの導
電膜２を基材１の表面に形成してもよい。Embodiment 2 In the present invention, as shown in FIG. 9A, the entire surface of the base material 1 is irradiated with an ultraviolet laser to roughen it, and as it is, as shown in FIG. The film 3 may be formed. However, as shown in FIG. 9C, the following is preferable in order to sufficiently prevent the film 3 from peeling off from the base material 1.
That is, as shown in FIG. 10A, the entire surface of the substrate 1 is roughened by irradiating an ultraviolet laser, and then, as shown in FIG.
As shown in FIG. 1, the roughened surface is subjected to a heat treatment by light irradiation, and only the tip of the thin convex portion of the roughened surface is made spherical and thick, and then, as shown in FIG.
The film 3 is formed as shown in FIG. Thereafter, a conductive film 2 of a specific pattern such as copper may be formed on the surface of the base material 1 according to the processing example of FIG.

【００３７】基材１には、ＡＢＳ、ポリカーボネイト、
液晶ポリマー等の有機樹脂基材、Ａｌ₂ Ｏ₃ 、ＳｉＯ₂
等の酸化物系セラミックス基材、Ｃｕ、Ａｌ、Ｆｅ、Ｎ
ｉ、Ａｕ、Ａｇ等の金属基材など粗化後の光照射で凸部
の先端が溶ける又は軟化する材料の基材が適当である。
光照射は、ＣＯ₂ レーザ、ＹＡＧレーザなどの赤外レー
ザや光ビーム（例えば、ＹＡＧレーザ第２高調波など）
等が挙げられる。The substrate 1 is made of ABS, polycarbonate,
Organic resin substrate such as liquid crystal polymer, Al ₂ O ₃ , SiO ₂
Oxide ceramic base such as Cu, Al, Fe, N
A substrate made of a material such as a metal substrate such as i, Au, or Ag that melts or softens the tip of the convex portion by light irradiation after roughening is suitable.
Light irradiation is performed using an infrared laser such as a CO ₂ laser or a YAG laser or a light beam (eg, a second harmonic of a YAG laser).
And the like.

【００３８】具体的に、厚み１．６ｍｍのＡＢＳ樹脂製
基材に波長２４８ｎｍ、エネルギー０．３Ｊ／ｃｍ² の
紫外レーザを照射し、粗化した後、波長１０６４ｎｍ、
エネルギー０．１Ｊ／ｃｍ² のＹＡＧレーザを照射し、
図２の処理例に従って、プリント配線板を得た。実施例
２の場合、湿式粗化不要で薬液洗浄などがなくなり、粗
化面の細い凸部の先端のみが太くてアンカー効果を発揮
するため、膜の密着力が非常によくなる。Specifically, a 1.6 mm-thick ABS resin base material is irradiated with an ultraviolet laser having a wavelength of 248 nm and an energy of 0.3 J / cm ^{2 to} roughen the substrate.
Irradiate a YAG laser with energy of 0.1 J / cm ² ,
According to the processing example of FIG. 2, a printed wiring board was obtained. In the case of the second embodiment, the wet roughening is unnecessary, and the cleaning with a chemical solution is eliminated, and only the tip of the thin convex portion having a roughened surface is thicker to exhibit an anchor effect. Therefore, the adhesion of the film becomes very good.

【００３９】−実施例３− 実施例３では、実施例２において、基材１に対する紫外
レーザを、図１１にみるように、膜形成用域のみに照射
し選択的に粗化し、粗化面に光照射を行い熱処理をし、
粗化面の細い凸部の先端のみを球状化して太くし、図５
の処理例に従って、プリント配線板を得た。Example 3 In Example 3, in Example 2, an ultraviolet laser beam for the substrate 1 was applied to only the film forming region to selectively roughen the substrate 1 as shown in FIG. Irradiates light and heat-treats
Only the tip of the thin convex part of the roughened surface is made spherical and thick, and FIG.
A printed wiring board was obtained according to the processing example of (1).

【００４０】膜形成用域以外の領域は非粗化であるた
め、無電解銅めっき膜と電気銅めっき膜の選択エッチン
グが容易であり、めっき膜の残留やサイドエッチも防止
できる。 −実施例４− 実施例４では、図１２にみるように、樹脂基材やセラミ
ック基材などの基材１を紫外レーザの照射により粗化し
てから、無電解めっき等により金属膜５を形成した後、
光照射による熱処理により、粗化面の凸部の先端に基材
と金属膜層の混合域を形成し金属膜の密着力を上げてい
る。Since the regions other than the film formation region are non-roughened, the selective etching of the electroless copper plating film and the electrolytic copper plating film is easy, and the residual plating film and side etching can be prevented. Example 4 In Example 4, as shown in FIG. 12, after a substrate 1 such as a resin substrate or a ceramic substrate is roughened by irradiation with an ultraviolet laser, a metal film 5 is formed by electroless plating or the like. After doing
By the heat treatment by light irradiation, a mixed region of the base material and the metal film layer is formed at the tip of the convex portion of the roughened surface to increase the adhesion of the metal film.

【００４１】粗化は、基材表面の全面に行ってもよい
し、膜形成用域のみに行ってもよい。膜形成用域のみを
粗化する場合は図３の処理例に従ってプリント配線板を
得ることが出来るし、全面を粗化する場合は、光照射に
よる熱処理のあと従来のパターンニング方式によりプリ
ント配線板を得ることができる。金属膜５としては、
銅、金、ニッケル等の単一膜、あるいは、それらの積層
膜が挙げられる。単一膜としては無電解めっきによる金
属膜が挙げられ、積層膜としては、無電解めっきによる
金属膜に電気めっきによる金属膜を積層したものが挙げ
られる。熱処理用の光としては、ＹＡＧレーザ、ＣＯ₂
レーザ、赤外線などが挙げられる。The roughening may be performed on the entire surface of the substrate, or may be performed only on the film forming area. When only the film formation area is roughened, a printed wiring board can be obtained according to the processing example of FIG. 3. When the entire surface is roughened, the printed wiring board can be obtained by a conventional patterning method after heat treatment by light irradiation. Can be obtained. As the metal film 5,
A single film of copper, gold, nickel, or the like, or a laminated film thereof is used. A single film includes a metal film formed by electroless plating, and a laminated film includes a metal film formed by electroless plating and a metal film formed by electroplating. As the light for the heat treatment, a YAG laser, CO ₂
Laser, infrared rays and the like.

【００４２】実施例２の条件に準じて、図３の処理例に
したがってプリント配線板を得た。金属膜５の一部が、
いわば基材１中に埋め込まれた形となるため、密着強度
は大きい。 −実施例５− 実施例５では、図１３の（ａ）にみるように、基材１
を、チャンバ内に入れ、基材１の表面に対しウインドウ
より紫外レーザを照射しつつ紫外レーザＣＶＤによる粗
化と同時に膜の形成を行っている。紫外レーザＣＶＤ
は、基材１表面に反応性ガスの導入と同反応性ガスに対
する紫外レーザの照射を行い膜形成する方法であり、反
応ガスへの照射用紫外レーザと粗化用紫外レーザを兼用
している。反応性ガスとしては、Ａｌ（ＣＨ）₃ ，Ｃｕ
（ＨＣＯＯ）₂ ・２Ｈ₂ Ｏ，Ｃｕヘキサフルオロアセチ
ルアセトネート，Ｎｉ（ＣＯ）₄ 等が挙げられる。Under the conditions of Example 2, a printed wiring board was obtained according to the processing example of FIG. Part of the metal film 5
As it were, it is embedded in the base material 1, so that the adhesion strength is high. -Example 5-In Example 5, as shown in FIG.
Is placed in a chamber, and the surface of the substrate 1 is irradiated with an ultraviolet laser from a window to form a film simultaneously with the roughening by the ultraviolet laser CVD. UV laser CVD
Is a method of forming a film by introducing a reactive gas onto the surface of the base material 1 and irradiating the reactive gas with an ultraviolet laser, and using both an ultraviolet laser for irradiating the reactive gas and an ultraviolet laser for roughening. . As the reactive gas, Al (CH) ₃ , Cu
_{(HCOO) 2 · 2H 2 O} , Cu hexafluoroacetylacetonate, Ni (CO) ₄ and the like.

【００４３】紫外レーザの照射は基材１の表面の全面で
も膜形成用域のみでもよい。紫外レーザが照射された領
域が粗化される。紫外レーザが照射される領域では、図
１３の（ｂ）にみるように、粗化と同時に膜形成用金属
粒子が凹部に析出し、膜は凹部内に入り込む形となるた
め、密着強度は十分なものとなる。紫外レーザのエネル
ギーは０．１〜１．０Ｊ／ｃｍ² 程度が適当である。Irradiation of the ultraviolet laser may be performed on the entire surface of the substrate 1 or only on the film forming area. The region irradiated with the ultraviolet laser is roughened. In the region irradiated with the ultraviolet laser, as shown in FIG. 13B, the film-forming metal particles precipitate in the concave portions at the same time as the roughening, and the film enters the concave portions. It becomes something. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm ² .

【００４４】厚み１．６ｍｍのＡＢＳ樹脂製基材に波長
２４８ｎｍ、エネルギー０．３Ｊ／ｃｍ² の紫外レーザ
を用い、反応性ガスとしては、Ｃｕ（ＨＣＯＯ）₂ ・２
Ｈ₂Ｏを用い、図４の処理例に従ってプリント配線板を
得た。粗化と膜形成が同時であり、無電解めっき工程が
不要であり、粗化部分では金属膜と基材が混合した状態
となり、密着強度が高い。An ultraviolet laser having a wavelength of 248 nm and an energy of 0.3 J / cm ² was used on a 1.6 mm thick ABS resin base material, and Cu (HCOO) ₂ .2 was used as a reactive gas.
Using H ₂ O, a printed wiring board was obtained according to the processing example of FIG. Roughening and film formation are simultaneous, no electroless plating step is required, and the metal film and the base material are mixed in the roughened portion, and the adhesion strength is high.

【００４５】−実施例６− 実施例６では、図１４の（ａ）にみるように、紫外レー
ザの照射によっては除去されにくい粒子１１が表面部分
に分散されている樹脂基材Ａを用いる。粒子１１は、セ
ラミック、ガラス、テフロンなどであって０．５〜７０
μｍ程度の粒径のものが例示され、非粒子部分の樹脂と
しては、エポキシ、ポリイミド、ポリカーボネート樹脂
等が挙げられる。樹脂基材全体１００重量％のうち粒子
が１０〜９０重量％を占める。Example 6 In Example 6, as shown in FIG. 14A, a resin base material A in which particles 11 which are difficult to be removed by irradiation with an ultraviolet laser are dispersed on the surface is used. The particles 11 are ceramic, glass, Teflon, etc.
A resin having a particle size of about μm is exemplified, and examples of the resin in the non-particle portion include epoxy, polyimide, and polycarbonate resins. Particles account for 10 to 90% by weight of the entire resin substrate of 100% by weight.

【００４６】そして、樹脂基材Ａに、図１４の（ｂ）に
みるように、紫外レーザを照射すると、粒子１１は突出
残留した状態となって粗化されることになる。紫外レー
ザの照射は、樹脂基材Ａの表面の全面でも膜形成用域の
みでもよい。全面を粗化し、所定パターンの導電膜を形
成する場合は、例えば、図２の処理例に従えばよい。膜
形成用域のみを粗化し、所定パターンの導電膜を形成す
る場合は、例えば、図５の処理例に従えばよい。When the resin substrate A is irradiated with an ultraviolet laser as shown in FIG. 14B, the particles 11 are left in a protruding state and are roughened. Irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate A or only on the film forming region. In the case where the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. In the case where only a film formation region is roughened to form a conductive film having a predetermined pattern, for example, the processing example in FIG. 5 may be followed.

【００４７】具体的には、エポキシ樹脂に０．５〜７０
μｍの粒径（平均粒径１０μｍ）のシリカ（ＳｉＯ₂ ）
粉末を８５重量％混合した成形基材（一般の機器に用い
られる電子機器封止材料）を用い、波長２４８ｎｍの紫
外レーザを膜形成用域のみに照射して粗化し、図５の処
理例に従ってプリント配線板を得た。紫外レーザのエネ
ルギーは０．２〜０．５Ｊ／ｃｍ² であった。More specifically, 0.5 to 70
Silica (SiO ₂ ) with a particle size of μm (average particle size of 10 μm)
Using a molding substrate (an electronic device sealing material used for general equipment) in which powder was mixed at 85% by weight, an ultraviolet laser having a wavelength of 248 nm was irradiated only to a film forming area to roughen the film, and the surface was roughened according to the processing example of FIG. A printed wiring board was obtained. The energy of the ultraviolet laser was 0.2 to 0.5 J / cm ² .

【００４８】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例７− 実施例７では、図１５の上の図にみるように、紫外レー
ザの照射により除去され易い粒子１２が表面部分に分散
されている樹脂基材Ｂを用いる。粒子１２は、ポリイミ
ド等の樹脂粉末などであって０．５〜１００μｍ程度の
粒径のものが例示され、非粒子部分の樹脂としては、テ
フロン樹脂等が挙げられる。樹脂基材全体１００重量％
のうち粒子が１０〜９０重量％を占める。A cleaning step, which is an essential problem in wet roughening, is not required, so that the steps can be simplified and the adhesion of the metal film formed on the surface of the base material is improved. Example 7 In Example 7, as shown in the upper diagram of FIG. 15, a resin base material B in which particles 12 which are easily removed by irradiation with an ultraviolet laser are dispersed in a surface portion is used. The particles 12 are, for example, resin powder such as polyimide and have a particle size of about 0.5 to 100 μm. Examples of the non-particle resin include a Teflon resin. 100% by weight of resin base
Of the particles account for 10 to 90% by weight.

【００４９】非粒子部分の樹脂と粒子１２の具体的な組
み合わせ例は以下の通りである。 組み合わせ 非粒子部分の樹脂：テフロン； 粒子１
２：ポリイミド、ポリカーボネート他、殆どの種類の樹
脂粒子； 組み合わせ 非粒子部分の樹脂：ポリカーボネート；
粒子１２：ポリイミド、ポリサルホンなどの樹脂粒
子； 組み合わせ 非粒子部分の樹脂：ポリサルホン； 粒
子１２：ポリイミドなどの樹脂粒子； そして、樹脂基材Ｂに、図１５の下の図にみるように、
紫外レーザを照射すると、粒子１２は除かれ凹みが表面
に分散現出し状態となって粗化されることになる。粒子
１２と非粒子部分の除去速度（エッチングレート）が異
なるため、エッチングレートの速い粒子１２が優先的に
除去される形で粗化が出来るのである。紫外レーザのエ
ネルギーは０．１〜１．０Ｊ／ｃｍ² 程度が適当であ
る。Specific examples of the combination of the resin and the particles 12 in the non-particle portion are as follows. Combination Non-particle resin: Teflon; Particle 1
2: Most kinds of resin particles such as polyimide and polycarbonate; Combination Non-particle resin: Polycarbonate;
Particles 12: Resin particles such as polyimide and polysulfone; Combination Resin in non-particle portion: Polysulfone; Particles 12: Resin particles such as polyimide;
When an ultraviolet laser is irradiated, the particles 12 are removed, and the dents are dispersed and appear on the surface, and are roughened. Since the removal rates (etching rates) of the particles 12 and the non-particle portions are different, roughening can be performed in such a manner that the particles 12 having a high etching rate are preferentially removed. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm ² .

【００５０】紫外レーザの照射は、樹脂基材Ｂの表面の
全面でも膜形成用域のみでもよい。全面を粗化し、所定
パターンの導電膜を形成する場合は、例えば、図２の処
理例に従えばよい。膜形成用域のみを粗化し、所定パタ
ーンの導電膜を形成する場合は、例えば、図５の処理例
に従えばよい。具体的には、テフロン（四フッ化エチレ
ン系樹脂）に、粒径５０μｍのポリイミド粉末を３０重
量％混合した成形基材を用い、波長２４８ｎｍの紫外レ
ーザを膜形成用域のみに照射して粗化し、図５の処理例
に従ってプリント配線板を得た。紫外レーザのエネルギ
ーは０．３Ｊ／ｃｍ² であった。Irradiation with the ultraviolet laser may be performed on the entire surface of the resin base material B or only on the film forming area. In the case where the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. In the case where only a film formation region is roughened to form a conductive film having a predetermined pattern, for example, the processing example in FIG. 5 may be followed. Specifically, using a molding substrate in which Teflon (polytetrafluoroethylene-based resin) is mixed with 30% by weight of a polyimide powder having a particle size of 50 μm, an ultraviolet laser having a wavelength of 248 nm is irradiated only to a film forming region to roughly generate the film. And a printed wiring board was obtained according to the processing example of FIG. The energy of the ultraviolet laser was 0.3 J / cm ² .

【００５１】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例８− 実施例８では、図１６の（ａ）にみるように、紫外レー
ザの照射によっても除去されにくい粒子１１と紫外レー
ザの照射により除去され易い粒子１２の両方が表面に分
散されている樹脂基材Ｃを用いる。粒子１１は、セラミ
ック、ガラス、テフロンなどであって０．５〜１００μ
ｍ程度の粒径のものが例示され、粒子１２は、ポリイミ
ド等の樹脂粉末などであって０．５〜１００μｍ程度の
粒径のものが例示される。非粒子部分の樹脂としては、
ポリカーボネート樹脂等が挙げられる。樹脂基材全体１
００重量％のうち粒子１１，１２が１０〜９０重量％を
占める。The cleaning step, which is an essential problem in wet roughening, is not required, so that the process can be simplified and the adhesion of the metal film formed on the surface of the substrate is improved. Example 8 In Example 8, as shown in FIG. 16A, both the particles 11 that are hardly removed by irradiation with ultraviolet laser and the particles 12 that are easily removed by irradiation with ultraviolet laser are dispersed on the surface. Resin substrate C is used. Particles 11 are ceramic, glass, Teflon, etc.
The particle 12 is, for example, a resin powder of polyimide or the like and has a particle size of about 0.5 to 100 μm. As the non-particle resin,
Examples include a polycarbonate resin. Resin base material whole 1
Particles 11 and 12 account for 10 to 90% by weight of the 00% by weight.

【００５２】そして、樹脂基材Ｃに、図１６の（ｂ）に
みるように、紫外レーザを照射すると、粒子１１は表面
に残留突出するとともに粒子１２は除かれ凹みが表面に
分散現出し状態となって粗化されることになる。粒子１
１，１２および非粒子部分の樹脂の材料は、除去速度
（エッチングレート）は粒子１１が最も遅く、粒子１２
が最も速く、非粒子部分の樹脂が両者の中間となるよう
に選定する。エッチングレートの差で粗化が出来るから
である。紫外レーザのエネルギーは０．１〜１．０Ｊ／
ｃｍ² 程度が適当である。When the resin substrate C is irradiated with an ultraviolet laser as shown in FIG. 16B, the particles 11 remain on the surface, the particles 12 are removed, and the dents are dispersed and appear on the surface. Therefore, it is roughened. Particle 1
For the resin materials of the resin particles 1 and 12 and the non-particle portion, the removal rate (etching rate) of the particle 11 is the lowest,
Is fastest, and the resin in the non-particle portion is intermediate between the two. This is because the surface can be roughened by a difference in etching rate. The energy of the ultraviolet laser is 0.1 to 1.0 J /
About ² cm ² is appropriate.

【００５３】紫外レーザの照射は、樹脂基材Ｃの表面の
全面でも膜形成用域のみでもよい。全面を粗化し、所定
パターンの導電膜を形成する場合は、例えば、図２の処
理例に従えばよい。膜形成用域のみを粗化し、所定パタ
ーンの導電膜を形成する場合は、例えば、図５の処理例
に従えばよい。具体的には、実施例６で用いた粒子１１
と実施例７で用いた粒子１２をテフロンに合計で３０重
量％混合した成形基材を用い、波長２４８ｎｍの紫外レ
ーザを膜形成用域のみに照射して粗化し、図５の処理例
に従ってプリント配線板を得た。紫外レーザのエネルギ
ーは０．３Ｊ／ｃｍ² であった。The irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate C or only on the film forming area. In the case where the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. In the case where only a film formation region is roughened to form a conductive film having a predetermined pattern, for example, the processing example in FIG. 5 may be followed. Specifically, the particles 11 used in Example 6
Using a molding base in which the particles 12 used in Example 7 were mixed with Teflon in a total of 30% by weight, an ultraviolet laser having a wavelength of 248 nm was irradiated only to the region for film formation to roughen, and printed according to the processing example of FIG. A wiring board was obtained. The energy of the ultraviolet laser was 0.3 J / cm ² .

【００５４】湿式粗化で必須の問題の洗浄工程が不要で
工程簡略化が行え、基材表面に形成する金属膜の密着力
が向上する。 −実施例９− 実施例９では、図１７の（ａ）にみるように、紫外レー
ザの照射により粗化されやすい樹脂材料１４で表面部分
の一部を形成し他の部分は紫外レーザでも粗化され難い
樹脂材料（基材樹脂）１５で形成した樹脂基材Ｄを用い
る。図１７の（ａ）にみるように、基材表面の粗化を行
う部分のみ樹脂材料１４としておけばよい。樹脂基材Ｄ
は、図１８にみるように、粗化容易な樹脂材料１４と粗
化困難な樹脂材料１５とを二色成形などを用いて複合化
することで簡単に作製することができる。The cleaning step, which is an essential problem in wet roughening, is not required, and the process can be simplified, and the adhesion of the metal film formed on the surface of the base material is improved. Example 9 In Example 9, as shown in FIG. 17A, a part of the surface portion is formed of a resin material 14 which is easily roughened by irradiation with an ultraviolet laser, and the other portions are roughened even with an ultraviolet laser. A resin base material D made of a resin material (base resin) 15 that is difficult to convert is used. As shown in FIG. 17A, only the portion where the surface of the base material is roughened may be set as the resin material 14. Resin substrate D
18, as shown in FIG. 18, the resin material 14 that is easily roughened and the resin material 15 that is hardly roughened can be easily manufactured by compounding using two-color molding or the like.

【００５５】樹脂材料１４としては、ポリイミドなどが
挙げられ、樹脂材料１５としては、液晶ポリマーやテフ
ロンなどが挙げられる。そして、樹脂基材Ｄに、図１７
の（ｂ）にみるように、紫外レーザを照射すると、樹脂
材料１４の表面が選択的に粗化される。つまり、膜形成
用域部分だけを樹脂材料１４で形成しておくと、自動的
に膜形成用域の選択粗化が出来るのである。紫外レーザ
のエネルギーは０．１〜１．０Ｊ／ｃｍ² 程度が適当で
ある。紫外レーザの照射は、樹脂基材Ｄの表面の全面で
も樹脂材料１４の表面のみでもよい。所定パターンの導
電膜を形成する場合は、例えば、図５または図６の処理
例に従えばよい。Examples of the resin material 14 include polyimide and the like, and examples of the resin material 15 include liquid crystal polymer and Teflon. Then, as shown in FIG.
As shown in (b), when the ultraviolet laser is irradiated, the surface of the resin material 14 is selectively roughened. That is, if only the film forming region is formed of the resin material 14, the film forming region can be automatically selected and roughened. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm ² . Irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate D or only on the surface of the resin material 14. When a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 5 or 6 may be followed.

【００５６】具体的には、樹脂材料１４をポリイミドと
し、樹脂材料１５をテフロンとする二色成形基材を用
い、波長２４８ｎｍの紫外レーザを照射して粗化し、図
６の処理例に従ってプリント配線板を得た。紫外レーザ
のエネルギーは０．２Ｊ／ｃｍ ² であった。金型でもっ
て樹脂材料１４を必要域に選択的に配置し粗化するた
め、不要域には粗化が付きにくく、無電解めっき時にめ
っき不要域に膜が付きにくくなる。Specifically, the resin material 14 is made of polyimide.
And a two-color molding base material using Teflon as the resin material 15 is used.
It is roughened by irradiating an ultraviolet laser with a wavelength of 248 nm.
In accordance with the processing example of No. 6, a printed wiring board was obtained. UV laser
Energy is 0.2 J / cm ^TwoMet. With a mold
To place the resin material 14 selectively in the required area and roughen it.
Unnecessary areas are unlikely to be roughened.
The film is less likely to adhere to unnecessary areas.

【００５７】−実施例１０− 実施例１０では、図１９の（ａ）にみるように、膜形成
物質と結合（物理的結合ないし化学的結合）し易い物質
１８が表面部分に含まれている（勿論、全体に含まれて
いてもよい）樹脂基材Ｆを用いる。膜形成物質と結合し
易い物質としては、めっき触媒、カップリング剤（γ−
アミノプロピルトリエトキシシラン等）、膜形成物質と
同じ物質又は類似の物質（金属膜であれば同一の金属又
は類似の金属：これであれば結合し易いのである）など
が挙げられる。母材樹脂としては、液晶ポリマー、ＡＢ
Ｓ樹脂、ポリカーボネート樹脂などが挙げられる。Example 10 In Example 10, as shown in FIG. 19A, a material 18 which is easily bonded (physical bonding or chemical bonding) to a film-forming substance is contained in the surface portion. A resin substrate F (of course, may be included in the whole) is used. Substances that easily bind to the film-forming substance include plating catalysts and coupling agents (γ-
Aminopropyltriethoxysilane, etc.) and the same or similar substance as the film-forming substance (the same metal or similar metal in the case of a metal film: in this case, it is easy to bond). Liquid crystal polymer, AB
S resin, polycarbonate resin and the like can be mentioned.

【００５８】実施例１０では、図１９の（ｂ）にみるよ
うに、紫外レーザを照射すると、樹脂基材Ｆの表面が粗
化されるとともに物質１８が露出するため、図１９の
（ｃ）にみるように、無電解めっき等で形成した金や
銅、ニッケル等のめっき膜は物質１８と結合し、粗化と
ともに密着力向上に寄与することになる。紫外レーザの
エネルギーは０．１〜１．０Ｊ／ｃｍ² 程度が適当であ
る。紫外レーザの照射は、樹脂基材Ｆの表面の全面でも
膜形成用域のみでもよい。全面を粗化し、所定パターン
の導電膜を形成する場合は、例えば、図２の処理例に従
えばよい。膜形成用域のみを粗化し、所定パターンの導
電膜を形成する場合は、例えば、図５または図６の処理
例に従えばよい。In the tenth embodiment, as shown in FIG. 19B, when the ultraviolet laser is irradiated, the surface of the resin base material F is roughened and the material 18 is exposed. As shown in the above, a plating film of gold, copper, nickel, or the like formed by electroless plating or the like binds to the substance 18 and contributes to roughening and improvement in adhesion. The energy of the ultraviolet laser is suitably about 0.1 to 1.0 J / cm ² . Irradiation with the ultraviolet laser may be performed on the entire surface of the resin base material F or only on the film formation region. In the case where the entire surface is roughened and a conductive film having a predetermined pattern is formed, for example, the processing example of FIG. 2 may be followed. In the case where only a film forming area is roughened to form a conductive film having a predetermined pattern, for example, the processing example of FIG. 5 or FIG. 6 may be followed.

【００５９】具体的には、母材樹脂用のＡＢＳ樹脂に物
質１８として銅粉末を添加混合した成形基材を用い、波
長２４８ｎｍの紫外レーザを膜形成用域のみに照射して
粗化し、図６の処理例に従ってプリント配線板を得た。
紫外レーザのエネルギーは０．３Ｊ／ｃｍ² であった。
湿式粗化が不要であるとともに、無電解めっきの場合の
核付け工程も省略できるようになる。Specifically, using a molding base material obtained by adding and mixing copper powder as a substance 18 to an ABS resin for a base resin, the surface is roughened by irradiating an ultraviolet laser having a wavelength of 248 nm only to a film forming region. In accordance with the processing example of No. 6, a printed wiring board was obtained.
The energy of the ultraviolet laser was 0.3 J / cm ² .
The wet roughening is not required, and the nucleation step in the case of electroless plating can be omitted.

【００６０】−実施例１１− 実施例１１では、図２０の（ａ）にみるように、基材表
面に金属材料２０を分散付着させた樹脂基材Ｅを用い
る。樹脂の種類はこれまでに例示したものが使える。金
属材料２０としては、銅、ニッケル、金、銀など紫外レ
ーザに対する反射率の高いものが好ましいが、これら例
示のものに限らない。金属材料２０の分散付着は、金属
めっき、金属粉体付着、金属材蒸着などの方法がある。Example 11 In Example 11, as shown in FIG. 20A, a resin base material E having a metal material 20 dispersed and adhered to the base material surface is used. As the type of resin, those exemplified above can be used. The metal material 20 is preferably a material having a high reflectance to an ultraviolet laser, such as copper, nickel, gold, and silver, but is not limited thereto. The dispersion adhesion of the metal material 20 includes methods such as metal plating, metal powder adhesion, and metal material evaporation.

【００６１】金属めっきの場合、無電解めっきのめっき
時間やめっき液の濃度の調整により、全面でなく部分的
めっきの範囲にめっきを止める。各部分めっきの大きさ
が０．５〜５μｍ程度となるようにする。金属粉体付着
の場合、粒径１０〜１００μｍ程度の粉体と、有機溶剤
（例えば、アセトン、アルコール等）の混合物（ペース
ト等）を塗布し、溶剤を飛ばして金属粉体を表面に残
す。混合物の粉体濃度は、塗布した際に粉体が基材表面
を覆い尽さない濃度に設定する。In the case of metal plating, the plating is stopped not in the entire surface but in a partial plating range by adjusting the plating time of the electroless plating and the concentration of the plating solution. The size of each partial plating is about 0.5 to 5 μm. In the case of attaching metal powder, a mixture (paste or the like) of a powder having a particle size of about 10 to 100 μm and an organic solvent (for example, acetone, alcohol, or the like) is applied, and the solvent is removed to leave the metal powder on the surface. The powder concentration of the mixture is set to a concentration at which the powder does not cover the surface of the substrate when applied.

【００６２】金属材蒸着の場合、蒸着初期は金属が点在
した状態となることを利用しており、基材全面が覆われ
る前に蒸着を停止し、全面でなく部分的蒸着の範囲に止
める。各部分蒸着の大きさが０．０１〜１μｍ程度が好
ましい。金属材料２０の分散付着の方法の選択で粗度の
調整が可能となる。実施例１１では、図２０の（ｂ）に
みるように、紫外レーザを照射すると、金属材料２０未
着部分の母材樹脂部分が選択的に除かれ深く掘られて粗
化が出来る。In the case of metal material vapor deposition, the fact that metal is scattered in the initial stage of vapor deposition is utilized, and the vapor deposition is stopped before the entire surface of the base material is covered, and is limited to a partial vapor deposition area instead of the entire surface. . The size of each partial deposition is preferably about 0.01 to 1 μm. The roughness can be adjusted by selecting the method of dispersing and attaching the metal material 20. In the eleventh embodiment, as shown in FIG. 20B, when an ultraviolet laser is irradiated, the base material resin portion where the metal material 20 is not adhered is selectively removed, and can be deeply dug and roughened.

【００６３】紫外レーザのエネルギーは０．１〜１．０
Ｊ／ｃｍ² 程度が適当である。紫外レーザの照射は、樹
脂基材Ｅの表面の全面でも膜形成用域のみでもよい。全
面を粗化し、所定パターンの導電膜を形成する場合は、
例えば、図２の処理例に従えばよい。膜形成用域のみを
粗化し、所定パターンの導電膜を形成する場合は、例え
ば、図５の処理例に従えばよい。The energy of the ultraviolet laser is 0.1 to 1.0.
J / cm ² is appropriate. Irradiation with the ultraviolet laser may be performed on the entire surface of the resin substrate E or only on the film forming region. When roughening the entire surface and forming a conductive film of a predetermined pattern,
For example, what is necessary is just to follow the processing example of FIG. In the case where only a film formation region is roughened to form a conductive film having a predetermined pattern, for example, the processing example in FIG. 5 may be followed.

【００６４】具体的には、ＡＢＳ樹脂基材の表面に金属
粉体付着方法で金属材料２０を分散付着させた樹脂基材
に波長２４８ｎｍの紫外レーザを膜形成用域のみに照射
して粗化し、図５の処理例に従ってプリント配線板を得
た。紫外レーザのエネルギーは０．５Ｊ／ｃｍ² であっ
た。金属材料２０の付着量の調整で表面粗度の調整が可
能である。Specifically, the resin substrate having the metal material 20 dispersed and adhered to the surface of the ABS resin substrate by the metal powder adhesion method is irradiated with an ultraviolet laser having a wavelength of 248 nm only in the film forming region to roughen the surface. A printed wiring board was obtained according to the processing example of FIG. The energy of the ultraviolet laser was 0.5 J / cm ² . The surface roughness can be adjusted by adjusting the amount of the metal material 20 attached.

【００６５】−実施例１２− 実施例１２では、図２１にみるように、基材１の表面の
膜形成用域（回路パターンに相当）のみに紫外レーザを
照射し、基材表面の膜形成用域のみを粗化し、無電解め
っき用の核（Ｐｄ等）付けを全面にしてから洗浄するこ
とにより、粗化面のみに核剤を残留させた後、無電解め
っきおよび電気めっきを行い、所定パターンの導電膜２
を膜形成用域のみに選択的に形成し、プリント配線板を
得る。Example 12 In Example 12, as shown in FIG. 21, only a film forming area (corresponding to a circuit pattern) on the surface of the substrate 1 was irradiated with an ultraviolet laser to form a film on the substrate surface. Roughening only the application area, washing the entire surface with nuclei (such as Pd) for electroless plating, and then leaving the nucleating agent only on the roughened surface, then performing electroless plating and electroplating, Conductive film 2 of predetermined pattern
Is selectively formed only in the film formation area to obtain a printed wiring board.

【００６６】未粗化面に付着した核剤よりも粗化面の凹
部に入った核剤は洗浄で除去され難いことを利用してレ
ジストマスク無しで導電膜の選択形成を行うのである。
基材は、液晶ポリマー、ポリイミド、エポキシ等の樹脂
基材あるいはアルミナ等のセラミック基材など、これま
でに例示したものが使えるし、粗化に関しても、前述の
膜形成用域のみの粗化のいずれのものでも利用可能であ
る。The conductive film is selectively formed without a resist mask by utilizing the fact that the nucleating agent that has entered the concave portion of the roughened surface is more difficult to be removed by washing than the nucleating agent that has adhered to the unroughened surface.
As the base material, those exemplified so far such as a resin base material such as liquid crystal polymer, polyimide, epoxy or a ceramic base material such as alumina can be used. Either one can be used.

【００６７】具体的には、図６の処理例にしたがって、
無電解めっきで銅膜を付け、電気めっきで銅膜を形成
し、プリント配線板を得た。湿式粗化が不要であり、選
択エッチング用のレジストマクス形成も不要である。レ
ジスト塗布、露光、現像が省略できる。 −実施例１３− 実施例１３では、図２２にみるように、基材１の表面の
膜形成用域（回路パターンに相当）のみに紫外レーザを
照射し、基材表面の膜形成用域のみを粗化し、無電解め
っき用の核（Ｐｄ等）付けを全面に行い、無電解めっき
および電気めっきを全面に行った後、レジスト塗布、露
光、現像によりレジストマスクを形成したあと、選択的
エッチングを行うことにより、所定パターンの導電膜２
を有するプリント配線板を得る。Specifically, according to the processing example of FIG.
A copper film was formed by electroless plating, and a copper film was formed by electroplating to obtain a printed wiring board. There is no need for wet roughening and no need for resist mask formation for selective etching. Resist coating, exposure and development can be omitted. Example 13 In Example 13, as shown in FIG. 22, only the film forming area (corresponding to a circuit pattern) on the surface of the base material 1 was irradiated with an ultraviolet laser, and only the film forming area on the base material surface was irradiated. After performing nucleation (Pd, etc.) for electroless plating on the entire surface, performing electroless plating and electroplating on the entire surface, forming a resist mask by resist coating, exposure, and development, and then selectively etching Is performed, the conductive film 2 having a predetermined pattern is formed.
Is obtained.

【００６８】基材は、液晶ポリマー、ポリイミド、エポ
キシ等の樹脂基材あるいはアルミナ等のセラミック基材
など、これまでに例示したものが使えるし、粗化に関し
ても、前述の膜形成用域のみの粗化のいずれのものでも
利用可能である。具体的には、図５の処理例にしたがっ
て、無電解めっきで銅膜を付け、電気めっきで銅膜を形
成し、プリント配線板を得た。As the base material, those exemplified so far such as a resin base material such as liquid crystal polymer, polyimide and epoxy or a ceramic base material such as alumina can be used. Any of the roughenings can be used. Specifically, according to the processing example of FIG. 5, a copper film was formed by electroless plating, and a copper film was formed by electroplating to obtain a printed wiring board.

【００６９】湿式粗化が不要であり、選択エッチングの
際、除去部分では粗化がなされていないため容易に除去
でき、サイドエッチを防止しつつ絶縁不良の原因となる
不要金属の残留を防止できる。 −実施例１４− 実施例１４では、基材１の表面の膜形成用域（回路パタ
ーンに相当）のみに紫外レーザを照射して基材表面の膜
形成用域のみを粗化し、その後、図２３にみるように、
基材１を、チャンバ内に入れ、基材１の表面に対しウイ
ンドウより光を照射しつつレーザＣＶＤ（熱ＣＶＤ）に
よる膜の形成を行っている。レーザＣＶＤは、反応性ガ
スの導入と同反応性ガスに対するレーザの照射を行い膜
形成する方法である。反応性ガスとしては、Ａｌ（Ｃ
Ｈ）₃ 、Ｃｕ（ＨＣＯＯ）₂ ・２Ｈ ₂ Ｏ、Ｃｕヘキサフ
ルオロアセチルアセトネート、Ｎｉ（ＣＯ）₄ 等が挙げ
られる。照射する光は、Ａｒレーザ、ＹＡＧレーザ、Ｃ
Ｏ₂ レーザ等のいわゆる熱レーザが例示される。この光
の照射は粗化面のみに行う。Since wet roughening is unnecessary, selective etching is not required.
When removing, it is easily removed because it is not roughened
Can cause insulation failure while preventing side etch
Unnecessary metal can be prevented from remaining. -Example 14-In Example 14, a film formation area (circuit pattern) on the surface of the substrate 1 was used.
Irradiates only an ultraviolet laser to the film on the substrate surface
Only the formation area is roughened, and then, as shown in FIG.
The substrate 1 is placed in the chamber, and the surface of the substrate 1 is
Laser CVD (thermal CVD) while irradiating light from window
The formation of a film is performed. Laser CVD uses reactive gas.
Film is introduced by introducing laser and irradiating laser to the same reactive gas.
It is a method of forming. As the reactive gas, Al (C
H)_Three, Cu (HCOO)_Two・ 2H _TwoO, Cu hexafu
Fluoroacetylacetonate, Ni (CO)_FourEtc.
Can be Irradiation light is Ar laser, YAG laser, C
O_TwoA so-called thermal laser such as a laser is exemplified. This light
Is applied only to the roughened surface.

【００７０】粗化面の凸部で熱集中が起こり、反応性ガ
スが粗化面で分解し所定パターンの膜形成が行える。基
材は、液晶ポリマー、ポリイミド、エポキシ等の樹脂基
材あるいはアルミナ等のセラミック基材など、これまで
に例示したものが使えるし、粗化に関しても、前述の膜
形成用域のみの粗化のいずれのものでも利用可能であ
る。Heat concentration occurs at the convex portion of the roughened surface, and the reactive gas is decomposed on the roughened surface to form a film having a predetermined pattern. As the base material, those exemplified so far such as a resin base material such as liquid crystal polymer, polyimide, epoxy or a ceramic base material such as alumina can be used. Either one can be used.

【００７１】具体的には、図７の処理例にしたがって、
ＣＶＤで銅膜を付け、電気めっきで銅膜を形成し、プリ
ント配線板を得た。湿式粗化が不要であり、選択エッチ
ング用のレジストマクス形成も不要である。レジスト塗
布、露光、現像が省略できる。Specifically, according to the processing example of FIG.
A copper film was formed by CVD and a copper film was formed by electroplating to obtain a printed wiring board. There is no need for wet roughening and no need for resist mask formation for selective etching. Resist coating, exposure and development can be omitted.

【００７２】[0072]

【発明の効果】この発明のパターン膜形成方法では、基
材表面の粗化を紫外レーザ照射により行うため、湿式粗
化を用いずとも、凹みの深い粗化が実現でき、粗化面に
形成される膜は密着力の十分なものとなる。粗化された
基材表面を光照射により加熱すると、粗化面の凸部の先
端のみが太くアンカー効果が備わり、膜と基材の混在域
が出来るため膜の密着力はより十分なものとなる。According to the pattern film forming method of the present invention, since the surface of the substrate is roughened by ultraviolet laser irradiation, deep roughening of the dent can be realized without using wet roughening, and the roughened surface is formed. The resulting film has a sufficient adhesion. When the roughened substrate surface is heated by light irradiation, only the tip of the convex portion of the roughened surface is thick and has an anchor effect, and a mixed area of the film and the substrate is formed, so that the adhesion of the film is more sufficient. Become.

【００７３】紫外レーザの照射を特定域に選択的に行う
場合は、特定域以外の領域に膜が残ったり、特定域に残
る膜にサイドエッチを起こさずに、特定域への膜形成が
容易に行える。基材表面に対する紫外レーザを、レーザ
ＣＶＤの反応ガスへの照射レーザとしても用い、基材表
面に対し粗化と同時にレーザＣＶＤによる膜形成を行う
と、粗化と膜形成が同時に行える利点がある。When the irradiation of the ultraviolet laser is selectively performed in a specific region, the film can be easily formed in the specific region without leaving a film in a region other than the specific region or causing side etching in the film remaining in the specific region. Can be done. The use of an ultraviolet laser for the substrate surface as an irradiation laser for the reaction gas of laser CVD and the formation of a film by laser CVD at the same time as the surface roughening of the substrate surface have the advantage that the roughening and film formation can be performed simultaneously. .

【００７４】紫外レーザの照射によっても除去されにく
い粒子が表面部分に分散されている樹脂基材を用いる
と、粒子の大きさや混合量の調節により深い凹みのある
粗化ができる。紫外レーザの照射により除去され易い粒
子が表面部分に分散されている樹脂基材を用いると、粒
子の大きさや混合量の調節により深い凹みの粗化ができ
る。When a resin base material in which particles which are hardly removed even by irradiation with an ultraviolet laser are dispersed on the surface is used, roughening with a deep dent can be achieved by adjusting the size and mixing amount of the particles. By using a resin base material in which particles which are easily removed by irradiation with ultraviolet laser are dispersed on the surface, deep dents can be roughened by adjusting the size and mixing amount of the particles.

【００７５】紫外レーザの照射によっても除去されにく
い粒子と紫外レーザの照射により除去され易い粒子の両
方の粒子が表面部分に分散されている樹脂基材を用いる
と、やはり、粒子の大きさや混合量の調節により深い凹
みのある粗化ができる。表面部分の一部を紫外レーザの
照射により粗化されやすい樹脂材料で形成した樹脂基材
を用いると、他の部分が紫外レーザでも粗化され難い樹
脂材料で出来ている樹脂基材であっても、基材表面の必
要部分の選択的粗化が可能となる。When a resin base material is used in which both particles that are hardly removed by irradiation with ultraviolet laser and particles that are easily removed by irradiation with ultraviolet laser are dispersed on the surface, the size and mixing amount of the particles are also increased. By adjusting the depth, roughening with a deep dent can be achieved. When using a resin base material whose surface part is formed of a resin material that is easily roughened by irradiation with an ultraviolet laser, the other part is a resin base material that is made of a resin material that is hardly roughened even by an ultraviolet laser. Also, it is possible to selectively roughen a required portion of the substrate surface.

【００７６】膜形成物質と結合し易い物質を表面部分に
含有する樹脂基材を用いると、膜の密着力がより高ま
る。表面に金属材料を分散付着させた樹脂基材を用いる
と、深い凹みが分散現出し十分な深さの粗化が出来る。
この発明の表面粗化方法により基材表面の特定域が選択
的に粗化された基材を用いる場合、特定域以外の領域が
粗化されていないため、特定域への選択的な膜形成や、
膜形成用域以外の領域上の膜の除去が容易に行え、特定
域だけへサイドエッチのない膜を設けることが容易に行
える。When a resin base material containing a substance which easily binds to the film-forming substance on the surface is used, the adhesion of the film is further increased. When a resin base material having a metal material dispersed and adhered to the surface is used, a deep dent is dispersed and the surface is roughened to a sufficient depth.
When using a substrate in which a specific region of the substrate surface is selectively roughened by the surface roughening method of the present invention, since a region other than the specific region is not roughened, selective film formation on the specific region is performed. And
The film on the region other than the region for film formation can be easily removed, and a film without side etching can be easily provided only in a specific region.

【００７７】加えて、膜形成を、反応性ガスの導入と同
反応性ガスに対する光照射を伴うＣＶＤにより行うと同
時に光照射により基材表面の粗化面の加熱をも行う場合
は、膜の密着力はより十分なものとなる。In addition, when the film is formed by CVD involving the introduction of a reactive gas and light irradiation to the reactive gas, and simultaneously heating the roughened surface of the substrate surface by light irradiation, The adhesion is more sufficient.

【図面の簡単な説明】[Brief description of the drawings]

【図１】この発明での紫外レーザの照射形態を示す概略
説明図。FIG. 1 is a schematic explanatory view showing an irradiation mode of an ultraviolet laser according to the present invention.

【図２】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 2 is a process explanatory view showing a processing example of a processing method of a substrate surface according to the present invention.

【図３】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 3 is a process explanatory view showing a processing example of a method for treating a substrate surface according to the present invention.

【図４】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 4 is a process explanatory view showing a processing example of a method for treating a substrate surface according to the present invention.

【図５】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 5 is a process explanatory view showing a processing example of a method for treating a substrate surface according to the present invention.

【図６】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 6 is a process explanatory view showing a processing example of a method for treating a substrate surface according to the present invention.

【図７】この発明での基材表面の処理方法の処理例を示
す工程説明図。FIG. 7 is a process explanatory view showing a processing example of a method of processing a substrate surface according to the present invention.

【図８】実施例１での基材表面の処理の様子を示す概略
説明図。FIG. 8 is a schematic explanatory view showing a state of processing of a substrate surface in Example 1.

【図９】実施例２での基材表面の参考にする処理の様子
を示す概略説明図。FIG. 9 is a schematic explanatory view showing a state of a process of referring to the surface of a base material in Example 2.

【図１０】実施例２での基材表面の処理の様子を示す概
略説明図。FIG. 10 is a schematic explanatory view showing a state of processing of a substrate surface in Example 2.

【図１１】実施例３での基材表面の処理の様子を示す概
略説明図。FIG. 11 is a schematic explanatory view showing a state of processing of a substrate surface in Example 3.

【図１２】実施例４での基材表面の処理の様子を示す概
略説明図。FIG. 12 is a schematic explanatory view showing a state of processing of a substrate surface in Example 4.

【図１３】実施例５での基材表面の処理の様子を示す概
略説明図。FIG. 13 is a schematic explanatory view showing a state of processing of a substrate surface in Example 5.

【図１４】実施例６での基材と基材表面の処理の様子を
示す概略説明図。FIG. 14 is a schematic explanatory view showing a state of processing of a substrate and a substrate surface in Example 6.

【図１５】実施例７での基材と基材表面の処理の様子を
示す概略説明図。FIG. 15 is a schematic explanatory view showing a state of processing of a base material and a base material surface in Example 7.

【図１６】実施例８での基材と基材表面の処理の様子を
示す概略説明図。FIG. 16 is a schematic explanatory view showing a state of processing of a substrate and a substrate surface in Example 8.

【図１７】実施例９での基材と基材表面の処理の様子を
示す概略説明図。FIG. 17 is a schematic explanatory view showing a state of processing of a base material and a base material surface in Example 9.

【図１８】実施例９での基材作製の様子を示す概略説明
図。FIG. 18 is a schematic explanatory view showing how a substrate is produced in Example 9.

【図１９】実施例１０での基材と基材表面の処理の様子
を示す概略説明図。FIG. 19 is a schematic explanatory view showing a state of processing of the base material and the base material surface in Example 10.

【図２０】実施例１１での基材と基材表面の処理の様子
を示す概略説明図。FIG. 20 is a schematic explanatory view showing a state of processing of a base material and a base material surface in Example 11.

【図２１】実施例１２での基材表面の処理の様子を示す
概略説明図。FIG. 21 is a schematic explanatory view showing a state of processing of a substrate surface in Example 12.

【図２２】実施例１３での基材表面の処理の様子を示す
概略説明図。FIG. 22 is a schematic explanatory view showing a state of processing of a substrate surface in Example 13.

【図２３】実施例１４での基材表面の処理の様子を示す
概略説明図。FIG. 23 is a schematic explanatory view showing a state of processing of a base material surface in Example 14.

【図２４】従来の基材表面の処理の様子を示す概略説明
図。FIG. 24 is a schematic explanatory view showing a state of processing of a conventional substrate surface.

【符号の説明】[Explanation of symbols]

１ 基材 ２ 所定パターンの導電膜 ３ 金属膜 DESCRIPTION OF SYMBOLS 1 Base material 2 Conductive film of a predetermined pattern 3 Metal film

───────────────────────────────────────────────────── フロントページの続き (72)発明者 内野々良幸 大阪府門真市大字門真1048番地松下電工 株式会社内 (72)発明者 中嶋 勲二 大阪府門真市大字門真1048番地松下電工 株式会社内 (72)発明者 鈴木 俊之 大阪府門真市大字門真1048番地松下電工 株式会社内 (72)発明者 北村 啓明 大阪府門真市大字門真1048番地松下電工 株式会社内 (56)参考文献 特開 平４−280494（ＪＰ，Ａ) 特開 平４−187389（ＪＰ，Ａ) (58)調査した分野(Int.Cl.⁷，ＤＢ名) B23K 26/00 C08J 7/00 C08J 7/04 H05K 3/14 H05K 3/18 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Uchino Matsushita Electric Works Co., Ltd., 1048 Kadoma, Kadoma, Osaka Prefecture (72) Inventor Isuji Nakajima 1048 Kadoma Kadoma, Kadoma, Osaka Prefecture Inventor Toshiyuki Suzuki 1048 Kazuma Kadoma, Kadoma City, Osaka Pref. (72) Inventor Hiroaki Kitamura 1048 Kadoma Kadoma, Kadoma City, Osaka Pref. Matsushita Electric Works Co., Ltd. JP, A) JP-A-4-187389 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B23K 26/00 C08J 7/00 C08J 7/04 H05K 3/14 H05K 3 / 18

Claims (11)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】基材表面に紫外レーザを照射して前記基材
表面の粗化を行う工程(a)と粗化された基材表面に膜を
形成する工程(b)を含む基材表面の処理方法であって、 基材表面への紫外レーザ照射を、反応ガスの導入と同反
応ガスへのレーザ照射を伴うレーザＣＶＤの前記反応ガ
スへのレーザ照射として用い、基材表面に対し粗化工程
(a)と同時に膜の形成工程(b)を行う 基材表面の処理方
法。(1) a step (a) of irradiating an ultraviolet laser to the surface of the substrate to roughen the surface of the substrate, and forming a film on the surface of the roughened substrate.
A method for treating a substrate surface including a step (b) of forming, wherein irradiation of an ultraviolet laser beam to the substrate surface is performed in the same manner as the introduction of a reactive gas.
Reaction gas for laser CVD with laser irradiation on reactive gas
Used for laser irradiation to the substrate surface
(a) A method for treating the surface of a base material, wherein the step (b) of forming a film is performed at the same time . 【請求項２】基材表面に紫外レーザを照射して前記基材
表面の粗化を行う工程(a)と粗化された基材表面に膜を
形成する工程(b)を含む基材表面の処理方法であって、 粗化工程(a)の後で、 膜の形成工程(b)を、反応性ガスの導入と同反応ガスへ
の光照射を伴うＣＶＤにより行うとともに、前記光照射
により基材表面の粗化面の加熱をも行う基材表面の処理
方法。 2. A base material surface comprising a step (a) of irradiating an ultraviolet laser to the base material surface to roughen the base material surface and a step (b) of forming a film on the roughened base material surface. a treatment method, after the roughening step (a), the step of forming the film (b), to introduce the same reaction gas in the reaction gas
And the above-mentioned light irradiation.
Treatment of the substrate surface that also heats the roughened surface of the substrate
Method. 【請求項３】紫外レーザの照射を基材表面の特定域だけ
に行う請求項１から２までのいずれかに記載の基材表面
の処理方法。3. A processing method of a substrate surface according to any of claims 1 to 2 for irradiation of the ultraviolet laser only certain areas of the substrate surface. 【請求項４】基材として、紫外レーザの照射によっても
除去されにくい粒子が表面部分に分散されている樹脂基
材を用いる請求項１から３までのいずれかに記載の基材
表面の処理方法。As wherein substrate processing method of the substrate surface according to any one of claims 1 to 3 using a resin base material is hard particles are also removed by the irradiation of the ultraviolet laser is dispersed in the surface portion . 【請求項５】基材として、紫外レーザの照射により除去
され易い粒子が表面部分に分散されている樹脂基材を用
いる請求項１から３までのいずれかに記載の基材表面の
処理方法。As wherein substrate processing method of the substrate surface according to any one of claims 1 to 3 using a resin substrate tends particles are removed by the irradiation of the ultraviolet laser is dispersed in the surface portion. 【請求項６】基材として、紫外レーザの照射によっても
除去され難い粒子と紫外レーザの照射により除去され易
い粒子の両方が表面部分に分散されている樹脂基材を用
いる請求項１から３までのいずれかに記載の基材表面の
処理方法。As 6. substrates claim 1 using a resin substrate both prone particles are removed by irradiation of hard particles and ultraviolet lasers are also removed by the irradiation of the ultraviolet laser is dispersed on the surface portion to 3 The method for treating a substrate surface according to any one of the above. 【請求項７】基材として、一部表面部分を紫外レーザの
照射により粗化されやすい樹脂材料で形成した樹脂基材
を用いる請求項１から３までのいずれかに記載の基材表
面の処理方法。As 7. substrates, treatment of the substrate surface according to any of the part of the surface portions of claims 1 to use a resin base material formed by roughened easily a resin material by irradiation of ultraviolet laser to 3 Method. 【請求項８】基材として、表面部分に金属材料を分散付
着させた樹脂基材を用いる請求項１から３までのいずれ
かに記載の基材表面の処理方法。As 8. The substrate processing method of the substrate surface according to any one of claims 1 to 3 using a resin substrate a metallic material dispersed attached to the surface portion. 【請求項９】基材として、表面部分に膜形成物質と結合
し易い物質が含まれている樹脂基材を用いる請求項１か
ら８までのいずれかに記載の基材表面の処理方法。9. The surface of a substrate according to any one of claims 1 to 8 , wherein a resin substrate having a surface portion containing a substance which easily binds to a film-forming substance is used as the substrate. Processing method. 【請求項１０】膜の形成を、基材表面の特定域に選択的
に行う請求項１から９までのいずれかに記載の基材表面
の処理方法。10. The formation of the film, the processing method of the substrate surface according to any of claims 1 to 9 selectively perform a particular region of the substrate surface. 【請求項１１】膜の形成を基材表面全面に行ったあと、
基材表面の特定域以外の膜だけを除去する請求項１から
１０までのいずれかに記載の基材表面の処理方法。11. After forming the film on the entire surface of the base material,
Claims 1 to remove only the film other than the specific area of the substrate surface
11. The method for treating a substrate surface according to any one of up to 10 .