JPH07185315A - Method for reforming surface of solid material and device therefor - Google Patents
Method for reforming surface of solid material and device thereforInfo
- Publication number
- JPH07185315A JPH07185315A JP33299393A JP33299393A JPH07185315A JP H07185315 A JPH07185315 A JP H07185315A JP 33299393 A JP33299393 A JP 33299393A JP 33299393 A JP33299393 A JP 33299393A JP H07185315 A JPH07185315 A JP H07185315A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- dielectric
- solid material
- barrier discharge
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プラスチックス、ゴ
ム、布、金属、半導体、セラミックス、木材、動植物体
の表面の改質に関する。FIELD OF THE INVENTION The present invention relates to surface modification of plastics, rubber, cloth, metals, semiconductors, ceramics, wood and animals and plants.
【０００２】[0002]
【従来の技術】プラスチックスや金属は、一般に化学的
に不活性であり、接着したり、印刷したりすることが難
かしい材料が多い。これらの材料表面をサンドペーパー
で擦ったり、プラズマ、スパッタ、コロナ放電などによ
り物理的に表面に微細な傷を付ける物理的方法や、薬品
に浸漬する化学的方法、紫外線レーザーの光化学的性質
を使って官能基を置換して材料表面を改質する方法が知
られている。2. Description of the Related Art Plastics and metals are generally chemically inert and are often difficult to bond or print. Using the physical method of rubbing the surface of these materials with sandpaper, physically scratching the surface by plasma, spatter, corona discharge, etc., the chemical method of dipping in chemicals, the photochemical property of ultraviolet laser There is known a method of substituting a functional group to modify the surface of the material.
【０００３】[0003]
【発明が解決しようとする課題】しかし上記紫外線レー
ザーを用いた方法以外は、いづれも材料表面の特定箇所
に選択的に官能基を置換することはできない。一方、紫
外線レーザー法では処理時間がかかることと、装置が大
きいことが欠点である。However, except for the method using the ultraviolet laser described above, it is not possible to selectively substitute a functional group at a specific position on the surface of the material. On the other hand, the ultraviolet laser method has drawbacks in that it requires a long processing time and a large apparatus.
【０００４】したがって本発明は小規模な装置で、短時
間の処理時間で材料表面を改質することを目的とする。Therefore, the object of the present invention is to modify the material surface in a short time by a small-scale apparatus.
【０００５】すなわち、本発明は、プラスチックス、金
属、木材などの材料表面を光化学と電気化学的手法を用
いて、選択的に種々の官能基を置換させ、その材料表面
に接着性、染着性、耐薬品性などの機能性を持たせた
り、あるいは材料表面をエッチングしたり、化学種や金
属を堆積させるための装置および方法を提供することを
目的とする。That is, according to the present invention, various functional groups are selectively substituted on the surface of a material such as plastics, metal or wood by using photochemical and electrochemical methods, and the surface of the material is adhered or dyed. It is an object of the present invention to provide an apparatus and method for imparting functionality such as chemical resistance and chemical resistance, etching a material surface, and depositing chemical species and metals.
【０００６】[0006]
【課題を解決するための手段】誘電体バリヤ放電（別名
オゾナイザ放電「改訂新版 放電ハンドブック」平成１
年６月１日再版７刷発行（電気学会）第２６３頁以下参
照）を利用した誘電体バリヤ放電ランプ（以下、バリヤ
ランプと略称するが、バリヤランプはウシオ電機（株）
の商標である。）により放射される紫外光または真空紫
外光は誘電体を挟んで配置された電極間に存在するガス
による放電スペクトルであり、そのスペクトル光を取り
出す為の窓材として紫外線に透明な誘電体例えば合成石
英ガラスが用いられている。[Means for Solving the Problems] Dielectric Barrier Discharge (also known as Ozonizer Discharge "Revised New Edition Discharge Handbook" Heisei 1
Dielectric barrier discharge lamp (hereinafter abbreviated as "barrier lamp") using the 7th edition of the 1st edition of the 7th edition (see page 263 onwards of the Institute of Electrical Engineers of Japan). The barrier lamp is Ushio Electric Co., Ltd.
Is a trademark of ) Is the discharge spectrum due to the gas existing between the electrodes arranged with the dielectric material sandwiched between them, and a dielectric material transparent to ultraviolet rays such as a synthetic material is used as a window material for extracting the spectrum light. Quartz glass is used.
【０００７】バリヤランプでは光の取り出し窓材として
の透明誘電体の外側にも電極が必要である。このため取
り出し光量を多くするために、メッシュ電極を利用する
ことが多い。ところが、被処理固体自身を電極として用
いれば、すなわち、被処理固体材料の裏面とバリヤラン
プ中の第１の電極との間に交流高電圧を印加すれば、バ
リヤランプが被処理固体材料表面に接している箇所およ
びその近傍でのみ放電を起こすことが出来る。したがっ
て、被処理固体材料表面への照射効率が最も高くなる。
さらに、バリヤランプの誘電体と被処理固体材料表面間
の間隔を極く薄くすると、毛管現象により、処理用流体
としての化合物の溶液がその間に入り込む。この液層は
極く薄いため、バリヤランプから発生する紫外光や真空
紫外光によって、液層および固体材料表面を光励起する
ことができる。これによって光化学反応域を真空やＮ2
あるいはＨｅなどの不活性ガスで覆わなくても大気中で
固体材料表面の改質処理が可能となる。In the barrier lamp, an electrode is also required on the outside of the transparent dielectric material as a light extraction window material. Therefore, in order to increase the amount of extracted light, a mesh electrode is often used. However, if the treated solid itself is used as an electrode, that is, if a high AC voltage is applied between the back surface of the treated solid material and the first electrode in the barrier lamp, the barrier lamp contacts the treated solid material surface. It is possible to generate a discharge only in the place where it exists and its vicinity. Therefore, the irradiation efficiency on the surface of the solid material to be treated is the highest.
Furthermore, if the distance between the dielectric of the barrier lamp and the surface of the solid material to be treated is made extremely small, the solution of the compound as the treatment fluid will enter between them due to the capillary phenomenon. Since this liquid layer is extremely thin, the liquid layer and the surface of the solid material can be photoexcited by the ultraviolet light or vacuum ultraviolet light generated from the barrier lamp. This allows the photochemical reaction area to be vacuumed or N 2
Alternatively, the surface of the solid material can be modified in the atmosphere without being covered with an inert gas such as He.
【０００８】本発明ではこの合成石英ガラスからなる誘
電体に、処理用流体としての化合物の水溶液薄層や材料
ガス層を介して被処理固体材料であるプラスチックスな
どの誘電体や金属板などを密着させ、その後方に第２の
電極を接触させ、この電極とバリヤランプの第１の電極
との間に交流高電圧を印加する。これにより被処理固体
材料表面とバリヤランプの透明誘電体との間やその近傍
で放電が起こり、ここに存在する処理用液体やガス体を
電離したり、わずかではあるがここで発生した紫外光ま
たは真空紫外光によって固体材料表面が励起される。こ
れと同時に、バリヤランプ内の誘電体バリヤ放電用のガ
スも放電して、そのガスの種類によって特定波長の紫外
光や真空紫外光を放出する。In the present invention, a dielectric material such as plastics, which is a solid material to be processed, a metal plate, or the like is added to the dielectric made of synthetic quartz glass through a thin aqueous solution layer of a compound as a processing fluid or a material gas layer. The second electrode is brought into close contact with the second electrode, and a high alternating voltage is applied between this electrode and the first electrode of the barrier lamp. This causes a discharge between the surface of the solid material to be treated and the transparent dielectric of the barrier lamp or in the vicinity thereof to ionize the processing liquid or gas existing there, or to generate a slight amount of ultraviolet light generated here. The vacuum ultraviolet light excites the surface of the solid material. At the same time, the dielectric barrier discharge gas in the barrier lamp is also discharged, and depending on the type of the gas, ultraviolet light of a specific wavelength or vacuum ultraviolet light is emitted.
【０００９】この特定波長の光を吸収する固体材料や化
合物の液体または材料ガスを選んでおけば、固体材料表
面で化学反応が起こり、化学種が置換される。このよう
に、一つの系で電気化学と光化学反応とを同時に起こさ
せるため、高い改質効率が得られる。If a liquid or a material gas of a solid material or compound that absorbs light of this specific wavelength is selected, a chemical reaction occurs on the surface of the solid material and the chemical species are replaced. In this way, since one system causes the electrochemical reaction and the photochemical reaction at the same time, high reforming efficiency can be obtained.
【００１０】この第２の電極の形状としては、固体材料
表面の形状もしくは性状に応じて柱状、板状、球状、ド
ーナツ状、針状、あるいはそれらの組合わせであっても
よく、また、第２の電極の表面は固体材料表面の形状も
しくは性状に応じて、導電塗料仕上げ、金属蒸着仕上
げ、もしくは金属箔の粘着仕上げとしてもよい。また、
第２の電極を固体材料に埋設してもよいし、固体材料に
埋設された導電体に第２の電極を兼務させてもよい。The shape of the second electrode may be a columnar shape, a plate shape, a spherical shape, a donut shape, a needle shape, or a combination thereof, depending on the shape or property of the surface of the solid material. The surface of the second electrode may be a conductive paint finish, a metal vapor deposition finish, or a metal foil adhesive finish, depending on the shape or property of the surface of the solid material. Also,
The second electrode may be embedded in the solid material, or the conductor embedded in the solid material may also serve as the second electrode.
【００１１】本発明で用いられる処理用流体としては、
液体であれば、液体化合物、溶質と溶媒からなる溶液、
もしくは懸濁液などが用いられ、気体であれば、気体化
合物、気体元素、超微小粉体もしくは液滴が分散された
気体、もしくはキャリアガスによって稀釈されたガスな
どを用いることができる。具体的には、純水、水道水、
重水、ＮＨ3 、ヒドラジン、Ｈ2 Ｏ2 、石油精製オイ
ル、フォンブリンオイル、シリコーンオイル、半導体装
置生産用エッチングガス、もしくは液状芳香族化合物、
酸もしくはアルカリ類の溶液、ハロゲン化合物、硫黄化
合物、フロン類、ニトリル類、ニトロ類、アミン類、炭
化水素類、有機酸、空気、Ｎ2 、Ｏ2 、ＣＯ2 、Ｃ
Ｈ4 、ＣＦ4 、Ｎ2 Ｏ、ＳＯ2 、水蒸気などを用いるこ
とができる。The processing fluid used in the present invention includes:
If it is a liquid, a liquid compound, a solution consisting of a solute and a solvent,
Alternatively, a suspension or the like is used, and if it is a gas, a gas compound, a gas element, a gas in which ultrafine powder or liquid droplets are dispersed, a gas diluted with a carrier gas, or the like can be used. Specifically, pure water, tap water,
Heavy water, NH 3 , hydrazine, H 2 O 2 , refined petroleum oil, fomblin oil, silicone oil, etching gas for semiconductor device production, or liquid aromatic compound,
The solution of acid or alkali, halogen compounds, sulfur compounds, fluorocarbons, nitriles, nitro, amines, hydrocarbons, organic acids, air, N 2, O 2, CO 2, C
H 4 , CF 4 , N 2 O, SO 2 , steam or the like can be used.
【００１２】この処理用流体となる供給物質と供給方法
が決まれば、処理用流体供給手段は任意に設計すること
ができる。The processing fluid supply means can be designed arbitrarily if the supply substance and the supply method to be the processing fluid are determined.
【００１３】図１ないし図８は、本発明の固体材料表面
改質装置の種々の実施例を示している。1 to 8 show various embodiments of the solid material surface reforming apparatus of the present invention.
【００１４】すなわち、図１の例は内面に第１の電極１
を設けた石英などの誘電体からなる筒体２と、この筒体
２の外側に間隙を設けて同軸的に配置された紫外光の透
過可能な石英などからなる円筒状誘電体３と、これら筒
体２と円筒状誘電体３との間に充填されたキセノンガス
などの誘電体バリヤ放電用のガス雰囲気４とからなるバ
リヤランプ５と、このバリヤランプ５の外側に配置され
たゴムローラー６とからなり、被処理固体材料７はこの
バリヤランプ５とゴムローラー６との間に導入されるよ
うになっている。この場合、被処理固体材料７としては
金属などの導電性のものが選ばれ、電源装置８と接続さ
れて第２の電極としても機能し、同じく電源装置８と接
続された第１の電極１との間に交流高電圧または直流パ
ルス高電圧が印加され、同時に処理用流体（図示しな
い）が円筒状誘電体３と被処理固体材料７との間に導
入、介在されるようになっている。なお、この場合、被
処理固体材料７を矢線のようにバリヤランプ５に対して
移動させてもよいし、あるいはバリヤランプ５を被処理
固体材料７に対して移動させてもよい。That is, in the example of FIG. 1, the first electrode 1 is formed on the inner surface.
A cylindrical body 2 made of a dielectric material such as quartz, and a cylindrical dielectric body 3 made of quartz or the like which is coaxial with the outer space of the cylindrical body 2 and which is transparent to ultraviolet light and is coaxially arranged. From a barrier lamp 5 composed of a gas atmosphere 4 for discharging a dielectric barrier such as xenon gas filled between a cylindrical body 2 and a cylindrical dielectric body 3, and a rubber roller 6 arranged outside the barrier lamp 5. The solid material 7 to be treated is introduced between the barrier lamp 5 and the rubber roller 6. In this case, a conductive material such as a metal is selected as the solid material 7 to be processed, and it also functions as a second electrode by being connected to the power supply device 8 and also by the first electrode 1 also connected to the power supply device 8. A high AC voltage or a high DC pulse voltage is applied between and, and at the same time, a processing fluid (not shown) is introduced and interposed between the cylindrical dielectric 3 and the solid material 7 to be processed. . In this case, the solid material 7 to be treated may be moved with respect to the barrier lamp 5 as indicated by an arrow, or the barrier lamp 5 may be moved with respect to the solid material 7 to be treated.
【００１５】被処理固体材料が金属の場合は、図１のよ
うにそれ自身が第２の電極と成る為何ら問題は無いが、
材料が金属以外の場合には、被処理固体材料を挟んで、
被処理固体材料表面にバリヤランプを、そして被処理固
体材料の反対面（裏面）または内部に第２の電極を置く
必要がある。図２ないし図５はそのような場合の装置の
構成例を示している。When the solid material to be treated is a metal, there is no problem because it becomes the second electrode itself as shown in FIG.
If the material is other than metal, sandwich the solid material to be treated,
It is necessary to place a barrier lamp on the surface of the solid material to be treated and a second electrode on the opposite (back) or inside the solid material to be treated. 2 to 5 show a configuration example of the apparatus in such a case.
【００１６】まず、図２において上記図１と異なる点は
図１のゴムローラー６の部分を第２の電極として機能す
る金属製ローラー９を設けた点であり、したがって電源
装置８は被処理固体材料７に対してでなく回転可能なロ
ーラー電極９に接続されている。他の構成については図
１のものと実質的に同一であるので同一符号を付すこと
により説明を省略する。First, FIG. 2 is different from FIG. 1 in that the rubber roller 6 of FIG. 1 is provided with a metal roller 9 functioning as a second electrode. It is connected to a rotatable roller electrode 9 rather than to the material 7. Since other configurations are substantially the same as those in FIG. 1, the description thereof will be omitted by giving the same reference numerals.
【００１７】図３の例は、図２のローラー電極９の代わ
りに板状電極１０を第２の電極として用いたものであ
り、その他の構成については図２とまったく同一であ
り、同一部分については同一符号が付されている。In the example of FIG. 3, a plate electrode 10 is used as the second electrode instead of the roller electrode 9 of FIG. 2, and the other structure is exactly the same as that of FIG. Are given the same reference numerals.
【００１８】図４の例は、平面状電極１１が被処理固体
材料７の内部に挿入ないしモールドされているものであ
り、この平面状電極１１が電源装置８と接続されてい
る。その他の構成については図２とまったく同一であ
り、同一部分については同一符号が付されている。In the example of FIG. 4, the planar electrode 11 is inserted or molded in the solid material 7 to be treated, and the planar electrode 11 is connected to the power supply device 8. Other configurations are exactly the same as those in FIG. 2, and the same parts are denoted by the same reference numerals.
【００１９】図５の例では、図２のものと同様に管軸中
心に回転自在の２重管構造のバリヤランプ５が用いら
れ、図２のローラー電極９の代わりに水平移動自在の第
２の電極としてのキャタピラ状帯電極１２が設けられ、
バリヤランプ５とキャタピラ状帯電極１２との間に、シ
ート状の被処理固体材料７を圧接し、被処理固体材料７
の表面とバリヤランプ５の誘電体３との接する部分に処
理用流体として化合物の水溶液１３をスポイト１４を介
して、または雰囲気ガス１５を噴射ノズル１６を介して
流し、同時に、バリヤランプ５の第１の電極１とキャタ
ピラ状帯電極１２との間に交流高電圧を印加し、これに
より発生する放電と、バリヤランプ５からの紫外光ある
いは真空紫外光により、被処理固体材料７の表面を改質
するようにしている。なお、この場合の被処理固体材料
７の圧接手段としては、第２の電極としてのキャタピラ
状帯電極１２が兼務するようにしてもよいし、別部材、
例えばスプリング（図示しない）などを用いて圧接させ
るようにしてもよい。In the example of FIG. 5, a barrier lamp 5 having a double tube structure that is rotatable around the tube axis is used as in the case of FIG. 2, and instead of the roller electrode 9 of FIG. A caterpillar band electrode 12 as an electrode is provided,
A sheet-shaped solid material 7 to be treated is pressed between the barrier lamp 5 and the track-shaped strip electrode 12 to form the solid material 7 to be treated.
An aqueous solution 13 of a compound as a processing fluid is made to flow through a dropper 14 or an atmospheric gas 15 is made to flow through a jet nozzle 16 to a portion where the surface of the barrier lamp 5 is in contact with the dielectric 3 of the barrier lamp 5. An AC high voltage is applied between the electrode 1 and the caterpillar band electrode 12, and the surface of the solid material 7 to be treated is modified by the discharge generated thereby and the ultraviolet light or vacuum ultraviolet light from the barrier lamp 5. I have to. In this case, the caterpillar band electrode 12 as the second electrode may also serve as the pressure contact means for the solid material 7 to be treated, or a separate member,
For example, a spring (not shown) or the like may be used for the pressure contact.
【００２０】さらに、図６は、すでにある形状を有する
キャビネット、ナベ、カマ、フライパンなどの製品や、
車体、船体、航空機ボデー、プラント反応容器などの製
品構造物の表面を処理する場合の表面改質装置を示して
いる。すなわち、それら製品構造物１７が導電性である
場合は、それ自身を第２の電極とし、導電性が無い物に
対しては、被処理固体材料の裏側または内部に導電性材
料を置き、被処理固体材料である製品構造物１７の表面
に処理用流体として化合物の水溶液層または材料ガス層
を介して回転移動自在の円筒型バリヤランプ５を製品構
造物１７の表面に沿って回転／スライドさせながら、両
電極間に交流高電圧を印加し、これにより発生する放電
とバリヤランプからの紫外光あるいは真空紫外光によ
り、複雑な形状を有する製品構造物表面を改質すること
ができる。なお、この場合の円筒型バリヤランプ５の構
造は図１のものと同様であり、同一符号を付すことによ
り説明を省略する。Further, FIG. 6 shows products such as cabinets, pans, sesame, and frying pans having existing shapes,
1 shows a surface modification device for treating the surface of a product structure such as a car body, a hull, an aircraft body, and a plant reaction vessel. That is, when those product structures 17 are conductive, the product structure 17 itself is used as the second electrode, and for those having no conductivity, the conductive material is placed on the back side or inside of the solid material to be treated, While rotating / sliding the cylindrical barrier lamp 5 rotatably movable on the surface of the product structure 17, which is the treated solid material, through the aqueous solution layer or the material gas layer of the compound as the treatment fluid, along the surface of the product structure 17. By applying an AC high voltage between both electrodes, the discharge generated thereby and the ultraviolet light or vacuum ultraviolet light from the barrier lamp can modify the surface of the product structure having a complicated shape. The structure of the cylindrical barrier lamp 5 in this case is similar to that of FIG. 1, and the description thereof will be omitted by giving the same reference numerals.
【００２１】図７の例は、平板状の透明誘電体を備えた
面発光型バリヤランプを使用した装置を示している。す
なわち、図７に示す固体材料表面改質装置は、紫外光の
透過可能な石英などからなり上下面が平坦な箱型誘電体
１８と、その上面に設けられた平板状の第１の電極１９
と、箱型誘電体１８内に封入されたキセノンガスなどの
誘電体バリヤ放電用のガス雰囲気２０とからなる面発光
型バリヤランプ２１と、箱型誘電体１８の下方に配置さ
れた第２の電極としての導電体２２からなる。プラスチ
ックスなどの被処理固体材料２３は箱型誘電体１８の下
面と導電体２２との間に導入され、箱型誘電体１８の下
面と処理用流体として化合物の水溶液の薄層を介して密
着した状態で第１の電極１９と第２の電極２２間に交流
高電圧が印加されて被処理固体材料２３の表面が均一に
改質されるようになっている。なお、被処理固体材料２
３に予め導電体２２を被着させた状態で被処理固体材料
２３を箱型誘電体１８の下面に処理用流体の薄層を介し
て密着し、同様に改質するようにしてもよい。また、被
処理固体材料２３自体が導電性の場合は被処理固体材料
２３に第２の電極を兼務させることもできる。The example of FIG. 7 shows an apparatus using a surface emitting barrier lamp provided with a flat transparent dielectric material. That is, the solid material surface reforming apparatus shown in FIG. 7 is made of quartz or the like that can transmit ultraviolet light and has a box-shaped dielectric 18 having flat upper and lower surfaces, and a flat plate-shaped first electrode 19 provided on the upper surface thereof.
And a surface-emitting barrier lamp 21 composed of a gas atmosphere 20 for discharging a dielectric barrier such as xenon gas enclosed in the box-shaped dielectric 18, and a second electrode arranged below the box-shaped dielectric 18. As the conductor 22. A solid material 23 to be treated such as plastics is introduced between the lower surface of the box-shaped dielectric 18 and the conductor 22, and adheres to the lower surface of the box-shaped dielectric 18 through a thin layer of an aqueous solution of a compound as a processing fluid. In this state, an AC high voltage is applied between the first electrode 19 and the second electrode 22 so that the surface of the solid material 23 to be treated is uniformly modified. Incidentally, the solid material to be treated 2
Alternatively, the solid material 23 to be processed may be adhered to the lower surface of the box-shaped dielectric 18 via a thin layer of the processing fluid in a state where the conductor 22 is applied to the surface 3 in advance and similarly modified. When the solid material 23 to be processed is electrically conductive, the solid material 23 to be processed can also serve as the second electrode.
【００２２】さらに、図７の装置の変形例として図８に
示すように面発光型バリヤランプ２１の誘電体１８と被
処理固体材料基板２３の表面との間に数ｍｍから数ｃｍ
の間隙を形成した状態で真空容器２４を構成し、この間
隙の中に、処理用流体として低圧の材料ガスまたはＨｅ
やＡｒなどで希釈された混合ガスを流し、被処理固体材
料基板の裏面に置かれたヒーター兼務の第２の平板電極
２５と面発光型バリヤランプ２１の第１の平板電極１９
との間に交流高電圧または直流パルス高電圧を印加する
ことにより、被処理固体材料基板２３の表面を異質化し
たりエッチングしたりＣＶＤを行なうようにしてもよ
い。Further, as a modified example of the apparatus of FIG. 7, as shown in FIG. 8, between the dielectric 18 of the surface emitting barrier lamp 21 and the surface of the solid material substrate 23 to be processed, several mm to several cm.
The vacuum container 24 is formed in a state in which the gap is formed, and a low-pressure material gas or He is used as a processing fluid in the gap.
The second plate electrode 25 also serving as a heater and the first plate electrode 19 of the surface emission type barrier lamp 21 placed on the back surface of the solid material substrate to be processed are caused to flow a mixed gas diluted with Ar or the like.
By applying an AC high voltage or a DC pulse high voltage between and, the surface of the solid material substrate 23 to be processed may be made heterogeneous, etched, or CVD may be performed.
【００２３】本発明で用いられるバリヤランプの誘電体
の他方の側の面（処理されるべき固体材料表面と対向す
る面）は、固体材料表面の形状もしくは性状に応じて平
面、曲面、もしくは凹凸面、あるいはそれらの組合わせ
であってもよい。例えばパイプ状、板状、球状などであ
ってもよい。The surface on the other side of the dielectric of the barrier lamp used in the present invention (the surface facing the surface of the solid material to be treated) is a flat surface, a curved surface, or an uneven surface depending on the shape or property of the solid material surface. , Or a combination thereof. For example, it may have a pipe shape, a plate shape, a spherical shape, or the like.
【００２４】バリヤランプの誘電体が円筒状であれば、
シート状の被処理固体材料をコンベアーベルトのように
高速流れ作業で処理が出来る。If the dielectric of the barrier lamp is cylindrical,
Sheet-like solid material to be processed can be processed by high-speed flow work like a conveyor belt.
【００２５】またバリヤランプの誘電体が平板状であれ
ば、ＣＶＤ、エッチング、リソグラフィーなど半導体装
置の生産プロセス用として、またバリヤランプの誘電体
が球状の場合はころがすことにより、あらゆる形状の固
体材料の処理に利用出来る。このバリヤランプと被処理
固体材料の間に、水やＨ2 Ｏ2 の薄膜を作っておくと、
放電による溶液の電離とバリヤランプの紫外光あるいは
真空紫外光による溶液および被処理固体表面の励起によ
り、材料表面を酸化処理することが出来る。特にバリヤ
ランプと被処理固体材料表面との間の放電を空気や他の
材料ガス雰囲気中で行なうと、材料表面の極く近傍で放
電が起こるため、分解したガス中の化学種がバリヤラン
プの紫外光および／または真空紫外光に助長され、効果
的にガス中の化学種で被処理材料表面の化学種を置換す
ることが出来る。If the dielectric of the barrier lamp is flat, it can be used for the production process of semiconductor devices such as CVD, etching and lithography, and if the dielectric of the barrier lamp is spherical, it can be rolled to treat solid materials of any shape. Can be used for If a thin film of water or H 2 O 2 is made between this barrier lamp and the solid material to be treated,
The surface of the material can be oxidized by the ionization of the solution by discharge and the excitation of the solution and the surface of the solid to be treated by the ultraviolet light or vacuum ultraviolet light of the barrier lamp. Especially, when the discharge between the barrier lamp and the surface of the solid material to be treated is performed in the atmosphere of air or other material gas, the discharge occurs in the vicinity of the material surface, and the chemical species in the decomposed gas are the ultraviolet light of the barrier lamp. The chemical species in the gas can be effectively replaced with the chemical species in the gas by being promoted by the vacuum ultraviolet light and / or.
【００２６】本発明では、例えばＸｅガス入りバリヤラ
ンプを用い、大気中で実施すれば波長１７２ｎｍの真空
紫外光を発光するため、空気中の酸素原子だけを選択的
に励起するため、一般の空気中におけるコロナ放電処理
よりも、材料表面の酸化処理効果は大である。In the present invention, a barrier lamp containing Xe gas, for example, is used to emit vacuum ultraviolet light having a wavelength of 172 nm when it is carried out in the atmosphere, so that only oxygen atoms in the air are selectively excited. The effect of oxidation treatment on the surface of the material is greater than that of the corona discharge treatment in.
【００２７】本発明を半導体装置の生産プロセスとして
用いる場合には、バリヤランプとＳｉやＳｉＯ2 などの
被処理材料基板とを真空容器の中で数ｍｍ〜数ｃｍ隔
て、この中にエッチングガスやＣＶＤ用ガスを封入また
は流通させる。この状態で、被処理材料基板とバリヤラ
ンプの誘電体との間で放電を起こさせ、バリヤランプの
発生する紫外光や真空紫外光と前記の放電による電離作
用あるいはこれによる発光とによって化学反応が助長さ
れ、被処理基板および材料ガスが励起され効率の高いエ
ッチングやＣＶＤが行なわれる。When the present invention is used as a production process of a semiconductor device, a barrier lamp and a material substrate to be processed such as Si or SiO 2 are separated by several mm to several cm in a vacuum container, and an etching gas or a CVD gas is put therein. Fill or distribute the gas for use. In this state, a discharge is caused between the material substrate to be processed and the dielectric of the barrier lamp, and the chemical reaction is promoted by the ultraviolet light or vacuum ultraviolet light generated by the barrier lamp and the ionization action or the light emission by the discharge. The substrate to be processed and the material gas are excited to perform highly efficient etching or CVD.
【００２８】なお、改質領域の間隙位置決め手段とし
て、バリヤランプと第２の電極を連結する伸縮自在な連
結部を設けたり、バリヤランプの誘電体に対して第２の
電極の位置を決めるための手段を設けてもよい。As a gap positioning means for the reformed region, a stretchable connecting portion for connecting the barrier lamp and the second electrode is provided, or means for determining the position of the second electrode with respect to the dielectric of the barrier lamp. May be provided.
【００２９】このように誘電体バリヤ放電から放射され
る紫外光や真空紫外光を取り出すためには、それら波長
域で透明な誘電体材料が不可決であり、そのための材料
は合成石英ガラス、サファイアー、ＫＲＳ−５、ＭｇＯ
や、ＭｇＦ2 、ＬｉＦ、ＮａＦ、ＣａＦ2 、ＢａＦ2 、
ＫＣｌ、ＮａＣｌ、ＫＢｒ、ＣｓＢｒ、ＣｓＩなどのハ
ロゲン化合物結晶でなくてはならない。In order to extract the ultraviolet light or vacuum ultraviolet light radiated from the dielectric barrier discharge in this way, a dielectric material transparent in these wavelength ranges is inevitable, and the material therefor is synthetic quartz glass or sacrificial glass. Fire, KRS-5, MgO
, MgF 2 , LiF, NaF, CaF 2 , BaF 2 ,
It must be a halogen compound crystal such as KCl, NaCl, KBr, CsBr, CsI.
【００３０】とくに従来のアーク放電ランプやグロー放
電ランプによってでは、被処理材料表面や材料ガスを効
率良く励起することが出来ない場合があった。そこで本
発明のように、被処理固体材料表面近傍での放電にバリ
ヤランプの発光を重畳することによって励起する。そし
てバリヤランプ内に封入する誘電体バリヤ放電用のガス
を選択すれば種々の波長の紫外光を出すことができる。
例えばフッ素樹脂を処理するためには、波長１７２ｎｍ
の放射波長をもつＸｅガス、ポリエチレンやポリプロピ
レンなどＣ−Ｈ結合を有する材料を処理する為には、波
長２２２ｎｍの放射波長を有するＫｒとＣｌの混合ガス
や波長３０８ｎｍの放射波長を有するＸｅやＣｌの混合
ガス、ＳｉやＳｉＯ2 のＣＶＤやエッチングには波長１
４６ｎｍの放射波長を有するＫｒガスや波長１７２ｎｍ
の放射波長を有するＸｅガスを用いることにより、より
効率の高い表面処理が可能となる。In particular, the conventional arc discharge lamp or glow discharge lamp may not be able to efficiently excite the surface of the material to be treated or the material gas. Therefore, as in the present invention, excitation is performed by superimposing the light emission of the barrier lamp on the discharge near the surface of the solid material to be treated. Then, by selecting a dielectric barrier discharge gas to be sealed in the barrier lamp, it is possible to emit ultraviolet light of various wavelengths.
For example, to process fluororesin, the wavelength is 172 nm.
In order to process Xe gas having an emission wavelength of, and a material having a C—H bond such as polyethylene or polypropylene, a mixed gas of Kr and Cl having an emission wavelength of 222 nm or Xe or Cl having an emission wavelength of 308 nm is used. Wavelength 1 for mixed gas of Si, CVD and etching of Si and SiO 2.
Kr gas with a radiation wavelength of 46 nm or a wavelength of 172 nm
By using the Xe gas having a radiation wavelength of 1, the surface treatment with higher efficiency becomes possible.
【００３１】本発明によれば、さらに以下の装置および
方法が提供される。According to the present invention, the following apparatus and method are further provided.
【００３２】（ｉ）１個の電極（第２の電極）に接触し
た被処理固体材料の被処理面と、透明セラミックス誘電
体を窓材とし、その窓材の前記被処理面と反対側に１個
の電極（第１の電極）を有する誘電体バリヤ放電ランプ
との間隙またはセラミックス誘電体にモールドされた電
極（第２の電極）のセラミックス部分との間隙を、化合
物の溶液層または材料ガス層を介して密着し、両電極間
に交流高電圧または直流パルス高電圧を印加することに
より被処理面とバリヤランプの透明セラミックス誘電体
との間で発生する放電およびバリヤランプから発生する
真空紫外光または紫外光によって上記被処理面と化合物
の溶液または材料ガスとが励起され、上記被処理面の化
学種を化合物の溶液または材料ガスの化学種で置換し、
あるいは被処理面に他の物質を堆積させ、またはエッチ
ングさせることを特徴とする固体表面の改質方法。(I) A surface to be processed of a solid material to be processed which is in contact with one electrode (second electrode) and a transparent ceramic dielectric material as a window material, and the window material is provided on the opposite side of the surface to be processed. The gap between the dielectric barrier discharge lamp having one electrode (first electrode) and the gap between the ceramic portion of the electrode (second electrode) molded in the ceramic dielectric and the solution layer of the compound or the material gas. Discharge that occurs between the surface to be treated and the transparent ceramic dielectric of the barrier lamp by applying AC high voltage or DC pulse high voltage between both electrodes and vacuum ultraviolet light generated from the barrier lamp or The surface to be treated and the solution or material gas of the compound are excited by ultraviolet light, and the chemical species on the surface to be treated are replaced by the chemical species of the solution or material gas of the compound,
Alternatively, a method for modifying a solid surface, which comprises depositing or etching another substance on the surface to be processed.
【００３３】（ii）回転自在に設けられた丸棒状電極
（第２の電極）と、透明セラミックスパイプを紫外光の
透光窓材としている誘電体バリヤ放電ランプとの間に、
シート状被処理固体材料を通過させる手段と、丸棒電極
と誘電体バリヤ放電ランプの透明セラミックスパイプと
を、上記シート状被処理固体材料を介して圧接する手段
とを具備し、かつ、上記誘電体バリヤ放電ランプとシー
ト状被処理固体材料との近接部分に必要に応じて雰囲気
材料ガスを流す手段と、上記シート状被処理固体材料と
誘電体バリヤ放電ランプとの間に毛管現象を利用して化
合物の溶液の薄層、あるいは材料ガス層を介在させ、被
処理固体材料の裏面に接している丸棒状電極と誘電体バ
リヤ放電ランプの第１の電極との間に交流高電圧を与
え、誘電体バリヤ放電ランプの放射する紫外光または真
空紫外光と被処理固体材料表面と、誘電体バリヤ放電ラ
ンプの透明セラミックスパイプとの間で発生する放電と
により、被処理固体材料、化合物の溶液、あるいは材料
ガスを励起し、固体表面を連続的に改質することを特徴
とする固体表面改質装置。(Ii) Between a rotatably provided round rod-shaped electrode (second electrode) and a dielectric barrier discharge lamp using a transparent ceramics pipe as a window for transmitting ultraviolet light,
And a means for pressing the round rod electrode and the transparent ceramics pipe of the dielectric barrier discharge lamp through the sheet-shaped solid material to be treated, and the dielectric material. By utilizing a capillary phenomenon between the sheet-shaped solid material to be treated and the dielectric barrier discharge lamp, a means for flowing an atmosphere material gas in the vicinity of the body barrier discharge lamp and the sheet-shaped solid material to be treated as necessary. A thin layer of the compound solution or a material gas layer is interposed, and a high AC voltage is applied between the round bar electrode contacting the back surface of the solid material to be treated and the first electrode of the dielectric barrier discharge lamp, Solids to be treated by the ultraviolet light or vacuum ultraviolet light emitted from the dielectric barrier discharge lamp and the surface of the solid material to be treated and the discharge generated between the transparent ceramic pipe of the dielectric barrier discharge lamp. Fee, a solution of the compound or excites the material gas, a solid surface modifying apparatus characterized by continuously modifying the solid surface.
【００３４】(iii) 回転自在に設けられた透明セラミッ
クスパイプを窓材とした誘電体バリヤ放電ランプと、車
体、船体、航空機ボデー、プラント反応容器、キャビネ
ット、ナベ、カマ、フライパンなどの導電体構造物や、
プラスチックス製バンパーの中に電極材料をモールドし
た構造のように、内部に導電体を有する誘電体構造物、
または木材や導電体材料裏面に沿って薄い金属箔を貼っ
た構造物などの導電体部分を電極とし、これらの電極と
反対側の被処理構造物表面との間、またはその近傍に化
合物の溶液の薄層を介在させ、回転自在に設けられた透
明セラミックスパイプを窓材とした誘電体バリヤ放電ラ
ンプ内の電極と被処理構造物本体あるいはその内部また
は接触している電極との間に交流高電圧を印加し、回転
自在に設けられた透明セラミックスパイプを窓材とした
誘電体バリヤ放電ランプを構造物表面に沿ってスライド
して、構造物表面を連続的に改質することを特徴とする
固体表面改質装置。(Iii) A dielectric barrier discharge lamp using a rotatably provided transparent ceramic pipe as a window material, and a conductor structure such as a car body, a hull, an aircraft body, a plant reaction vessel, a cabinet, a pan, a pot, and a frying pan. Things,
A dielectric structure having a conductor inside, such as a structure in which an electrode material is molded in a plastic bumper,
Alternatively, a conductor solution such as a structure in which a thin metal foil is adhered along the back surface of wood or a conductor material is used as an electrode, and a solution of the compound is provided between these electrodes and the surface of the structure to be treated on the opposite side or in the vicinity thereof. , A transparent ceramic pipe rotatably provided with a thin layer between the electrodes inside the dielectric barrier discharge lamp and the structure body to be treated or the electrode inside or in contact therewith. A dielectric barrier discharge lamp using a transparent ceramic pipe rotatably provided with a voltage applied as a window material is slid along the surface of the structure to continuously modify the surface of the structure. Solid surface reformer.
【００３５】(iv)板状透明セラミックスを窓材とし、放
電用ガスを介してその後方に板状電極を有する誘電体バ
リヤ放電ランプの前方と、導電性または背後あるいは内
部に電極を有する被処理固体材料表面との間に化合物の
溶液の薄層または材料ガス層を介し、両電極間に交流高
電圧または直流パルス高電圧を印加し、誘電体バリヤ放
電ランプの発生する紫外光または真空紫外光および被処
理固体材料近傍で発生する放電により、固体材料表面や
化合物の溶液または材料ガスなどを励起して固体材料表
面を異質化したり、エッチングしたり、または化学種や
金属を堆積させたりすることを特徴とする固体表面改質
装置。(Iv) Treated with a transparent transparent ceramics as a window material, a dielectric barrier discharge lamp having a plate-shaped electrode behind the transparent gas through a discharge gas, and an electrode which is conductive or behind or inside of the dielectric barrier discharge lamp. Ultraviolet light or vacuum ultraviolet light generated by a dielectric barrier discharge lamp by applying AC high voltage or DC pulse high voltage between both electrodes through a thin layer of compound solution or material gas layer with the surface of solid material. And the discharge that occurs in the vicinity of the solid material to be processed excites the surface of the solid material, the solution of the compound, or the material gas to make the surface of the solid material heterogeneous, etch it, or deposit chemical species or metal. A solid surface reforming device characterized by:
【００３６】(v) 板状透明セラミックスを窓材とした誘
電体バリヤ放電ランプと被処理固体材料の間を減圧され
た反応槽とし、この間にエッチングガスまたはＣＶＤガ
スを封入または流し、被処理固体材料側の電極とバリヤ
ランプ側の電極との間に交流高電圧または高繰返し高圧
直流パルスを印加し、材料ガス自身の放電とバリヤラン
プ自身の放電により発生した紫外光あるいは真空紫外光
により材料ガスの電離や光分解によって、被処理固体材
料を異質化したり、エッチングしたり、ＣＶＤを行うこ
とを特徴とする固体表面改質装置。(V) A reduced pressure reaction tank is provided between the dielectric barrier discharge lamp using the plate-shaped transparent ceramics as a window material and the solid material to be treated, and an etching gas or a CVD gas is filled or flowed between them to form the solid material to be treated. By applying AC high voltage or high repetition high voltage DC pulse between the electrode on the material side and the electrode on the barrier lamp side, the material gas is ionized by the discharge of the material gas itself and the ultraviolet light or vacuum ultraviolet light generated by the discharge of the barrier lamp itself. A solid surface reforming device characterized by heterogeneous treatment, etching, and CVD of a solid material to be treated by photolysis.
【００３７】[0037]
【作用】前述したように被処理固体材料の裏面の第２の
電極と、被処理固体材料の表面に水または化合物の水溶
液層、または、材料ガス層または大気層を介してバリヤ
ランプを密着した、または、ある間隙を隔てた状態で、
バリヤランプの第１の電極間に交流高電圧または直流パ
ルス高電圧を印加して、バリヤランプ内で発生する紫外
光または真空紫外光と、被処理固体材料の表面とバリヤ
ランプを構成する誘電体との間でおこる放電による溶液
や材料ガス等の電離作用や紫外光などの相乗効果によ
り、被処理固体材料の表面の化学種を処理用流体の水や
化合物の水溶液または材料ガスや大気中の化学種で置換
したり、表面をエッチングしたり、ＣＶＤを行なう。と
くに被処理部分のみに交流電流を流すためその近傍のみ
で改質が行なわれ、かつ、バリヤランプの発光も被処理
固体材料の接触部近傍のみで起こるため材料表面への照
射効率も高い。また被処理固体材料表面や処理用流体の
紫外光の吸収帯を考慮してバリヤランプ内に封入するガ
スの種類を選択し、それら紫外光の波長域に適合した紫
外光を放射せしめるようにすることが出来るので、さら
に効率の高い固体材料表面の改質ができる。As described above, the barrier electrode is adhered to the second electrode on the back surface of the solid material to be treated and the surface of the solid material to be treated through the aqueous solution layer of water or compound, or the material gas layer or the atmospheric layer. Or, with a certain gap,
By applying an AC high voltage or a DC pulse high voltage between the first electrodes of the barrier lamp, between the ultraviolet light or vacuum ultraviolet light generated in the barrier lamp and the surface of the solid material to be treated and the dielectric material forming the barrier lamp. The chemical species on the surface of the solid material to be treated are treated with water or the aqueous solution of the compound or the material gas or the chemical species in the atmosphere by the ionizing action of the solution or the material gas due to the discharge that occurs in Substitution, etching of the surface, or CVD is performed. In particular, since an AC current is passed only to the portion to be treated, the reforming is performed only in the vicinity thereof, and the light emission of the barrier lamp occurs only in the vicinity of the contact portion of the solid material to be treated, so that the irradiation efficiency on the material surface is high. In addition, the type of gas to be enclosed in the barrier lamp should be selected in consideration of the ultraviolet absorption band of the surface of the solid material to be treated and the processing fluid, and the ultraviolet light suitable for the wavelength range of those ultraviolet rays should be emitted. Therefore, the surface of the solid material can be reformed with higher efficiency.
【００３８】[0038]
［実施例１］図５に示す装置を用い、フッ素樹脂（ＰＴ
ＦＥ）シートの改質を大気中で行った。用いたバリヤラ
ンプ５は２本の合成石英ガラスパイプによる同軸円筒構
造を成し、そのパイプ間にＸｅガスを封入したもので、
外パイプを光取り出し窓材、内パイプの裏面側に第１の
電極１を設けた構造になっている。この第１の電極１と
前記シートの裏面に位置するキャタピラ形帯状電極１２
を第２の電極としてこの間に、９ｋＶ、２０ｋＨｚ、入
力２０Ｗの電力を印加した。Example 1 A fluororesin (PT
The FE) sheet was modified in the atmosphere. The barrier lamp 5 used has a coaxial cylindrical structure with two synthetic quartz glass pipes, and Xe gas is enclosed between the pipes.
The outer pipe is a light extraction window member, and the first electrode 1 is provided on the back surface side of the inner pipe. The first electrode 1 and the track-shaped strip electrode 12 located on the back surface of the sheet
Was used as the second electrode, and electric power of 9 kV, 20 kHz and an input of 20 W was applied during this period.
【００３９】まず、フッ素樹脂（ＰＴＦＥ）表面に水道
水を１滴づつ垂らしながら矢印方向にフッ素樹脂シート
を０．１ｍｍ／秒の割合で移動させた。これによって未
処理時には１００°であった水との接触角が、４５°に
なり改質されたことがわかった。またフッ素樹脂シート
の移動速度を０．０５ｍｍ／秒とすると、水との接触角
が３０°になった。なお、キセノンエキシマからの放射
光は、主に波長１７２ｎｍとその近傍であり、他方、水
道水は、波長１９０ｎｍより短い波長の光をよく吸収
し、ＰＴＦＥは波長１９０ｎｍ近傍の光をよく吸収す
る。First, while dropping one drop of tap water on the surface of the fluororesin (PTFE), the fluororesin sheet was moved in the direction of the arrow at a rate of 0.1 mm / sec. By this, it was found that the contact angle with water, which was 100 ° when untreated, was changed to 45 °. When the moving speed of the fluororesin sheet was 0.05 mm / sec, the contact angle with water was 30 °. The emitted light from the xenon excimer is mainly at a wavelength of 172 nm and its vicinity, on the other hand, tap water well absorbs light having a wavelength shorter than 190 nm, and PTFE well absorbs light near the wavelength of 190 nm.
【００４０】［実施例２］図５に示す装置を用い、フッ
素樹脂（ＦＥＰ）シートの改質を空気中で行った。バリ
ヤランプ５の動作条件は実施例１の場合と同じである。
空気中でフッ素樹脂シートを１ｍｍ／秒の速度で移動さ
せたところ、未処理時に水との接触角が１１０°であ
り、石油との接触角が５０°であった試料が、処理後
は、水との接触角７０°、石油との接触角が４０°にな
り改質された。この試料の未処理部分と処理された部分
にまたがって、油性マジックペンで線を引いたところ、
改質処理部分にはマジックインクの線が鮮やかに残り、
強い染着効果があることが実証された。このバリヤラン
プ５の放電用ガスはキセノンであり、したがって波長１
７２ｎｍとその近傍の光を放射し、他方、空気は、酸素
の関係で波長２００ｎｍ附近以下の光をよく吸収し、Ｆ
ＥＰも波長１９０ｎｍ附近でよく光を吸収する。Example 2 Using the apparatus shown in FIG. 5, the fluororesin (FEP) sheet was modified in air. The operating conditions of the barrier lamp 5 are the same as those in the first embodiment.
When the fluororesin sheet was moved at a speed of 1 mm / sec in air, the sample which had a contact angle with water of 110 ° and a contact angle with petroleum of 50 ° when untreated was The contact angle with water was 70 °, and the contact angle with petroleum was 40 °. When a line was drawn with an oil-based magic pen across the untreated and treated parts of this sample,
The lines of magic ink remain vividly on the modified part,
It was proved to have a strong dyeing effect. The discharge gas of this barrier lamp 5 is xenon and therefore has a wavelength of 1
It emits light at 72 nm and its vicinity, while air absorbs light having a wavelength of around 200 nm or less due to oxygen, and F
EP also absorbs light well near the wavelength of 190 nm.
【００４１】さらに前記シートの送り速度を０．３ｍｍ
／秒としたところ、水との接触角は５０°、石油との接
触角は２０°となり、強い改質効果が得られた。この条
件で処理されたシート同士を、エポキシ接着剤例えばア
ラルダイト・スタンダード（商品名）で接着し、２５℃
で１０時間養生後、引張り剪断試験を行ったところ５０
ｋｇｆ／ｃｍ2 の引張り強度が得られた。Further, the feeding speed of the sheet is 0.3 mm.
/ Sec, the contact angle with water was 50 ° and the contact angle with petroleum was 20 °, and a strong reforming effect was obtained. Sheets treated under these conditions are bonded together with an epoxy adhesive, such as Araldite Standard (trade name), at 25 ° C.
After aging for 10 hours, a tensile shear test was conducted.
A tensile strength of kgf / cm 2 was obtained.
【００４２】［実施例３］図５に示す装置を用いたポリ
メチルメタクリレート（ＰＭＭＡ）シートを撥水性に改
質した。Example 3 A polymethylmethacrylate (PMMA) sheet using the apparatus shown in FIG. 5 was modified to be water repellent.
【００４３】バリヤランプの動作条件は実施例１と同じ
であった。The operating conditions of the barrier lamp were the same as in Example 1.
【００４４】ＰＭＭＡシートとバリヤランプの接触部分
の近傍に、フッ化炭素化合物（ＣＣｌ2 Ｆ2 ）をハーモ
ニカ状の噴射ノズルから噴射し、ＰＭＭＡシートを０．
５ｍｍ／秒の速度で移動したところ、未処理時には、水
との接触角が７０°であった前記シートが、処理後は９
０°と成り、撥水性に改質されたことが実証された。こ
こで、ＰＭＭＡの光の吸収は波長２３０ｎｍ附近から大
きくなり、他方ＣＣｌ2 Ｆ2 の方も波長２３０ｎｍ附近
から吸収が始まり、波長１９０ｎｍ附近で大きく、した
がって、バリヤランプの放電用ガスとしては、波長１７
２ｎｍの光をよく放射するキセノン、または波長２２２
ｎｍの光を良く放射するクリプトンクロライドが良い。A fluorocarbon compound (CCl 2 F 2 ) was sprayed from a harmonica-shaped spray nozzle in the vicinity of the contact portion between the PMMA sheet and the barrier lamp, and the PMMA sheet was sprayed with a 0.1.
When the sheet was moved at a speed of 5 mm / sec, the sheet that had a contact angle with water of 70 ° when untreated was 9% after the treatment.
It became 0 °, and it was proved that it was modified to be water repellent. Here, the absorption of light of PMMA increases near the wavelength of 230 nm, while the absorption of CCl 2 F 2 also starts to increase near the wavelength of 230 nm and is large near the wavelength of 190 nm. Therefore, the gas for discharging the barrier lamp has a wavelength of 17 nm.
Xenon that emits 2 nm light well or wavelength 222
Krypton chloride, which emits nm light, is preferable.
【００４５】［実施例４］図４に示す装置を用いポリプ
ロピレン（ＰＰ）の改質を行った。銅メッシュを第２の
電極１１としてモールドして射出成形したポリプロピレ
ンブロック表面に回転自在でスライド自在のバリヤラン
プ５を接触させ、バリヤランプ５側の第１の電極１と銅
メッシュとの間に２０ｋＶ、２０ｋＨｚ、入力２０Ｗの
動作条件で電力を供給した。Example 4 Polypropylene (PP) was modified using the apparatus shown in FIG. The surface of a polypropylene block injection-molded by molding a copper mesh as the second electrode 11 is brought into contact with a rotatable and slidable barrier lamp 5, and 20 kV and 20 kHz are provided between the first electrode 1 on the barrier lamp 5 side and the copper mesh. , Power was supplied under the operating condition of input 20 W.
【００４６】空気中で試料表面を０．５ｍｍ／秒の速度
で、バリヤランプをスライドさせたところ、未処理の時
に水との接触角が８５°であり、石油との接触角が３５
°あった試料が、処理後は水との接触角５０°、石油と
の接触角が２０°になり改質された。なお、ＰＰの光の
吸収係数は、波長２１０ｎｍ附近で大きく、空気は含有
される酸素の関係で波長２００ｎｍ附近以下の光をよく
吸収する。したがって、バリヤランプの放電用充填ガス
は、波長１７２ｎｍの光を放射するキセノンが良い。When a barrier lamp was slid on the surface of the sample in air at a speed of 0.5 mm / sec, the contact angle with water was 85 ° and the contact angle with petroleum was 35 ° when untreated.
After the treatment, the contact angle with water was 50 ° and the contact angle with petroleum was 20 ° and the sample was reformed. The light absorption coefficient of PP is large near the wavelength of 210 nm, and air absorbs light near the wavelength of 200 nm or less due to the oxygen contained therein. Therefore, the filling gas for discharging the barrier lamp is preferably xenon which emits light having a wavelength of 172 nm.
【００４７】［実施例５］図７に示す装置を用いて、フ
ッ素樹脂（ＰＴＦＥ）の親水性処理を行った。Example 5 Using the apparatus shown in FIG. 7, a fluororesin (PTFE) was subjected to hydrophilic treatment.
【００４８】第２のステンレス平板電極２２の上に、フ
ッ素樹脂シートを載せ、ここに純水を数滴垂らし、平面
状の合成石英ガラスを光取り出し窓材とした面発光型バ
リヤランプ２１で前記シートを押し付け、一様な薄い液
膜を、フッ素樹脂（ＰＴＦＥ）シート間に形成させ、バ
リヤランプ２１の第１の電極１９と第２のステンレス電
極２２間に９ｋＶ、２０ｋＨｚ、電力１５Ｗの交流高電
圧を印加し、２分間照射を続けたところ未処理時には、
水との接触角が１００°であった試料が一様な面上で４
０°になり改質された。なお、ＰＴＦＥの光の吸収は、
波長１９０ｎｍ附近で大きな吸収係数を有し、純水の方
は、波長１９０ｎｍより短い波長の光をよく吸収する。
したがって、バリヤランプにはキセノンのガスを充填す
るのが良い。このエキシマガスからは、波長１７２ｎｍ
の光が良く放射される。A fluororesin sheet is placed on the second stainless flat plate electrode 22, a few drops of pure water are dropped on the sheet, and the sheet is formed by the surface emitting type barrier lamp 21 using a plane synthetic quartz glass as a light extraction window material. Is pressed to form a uniform thin liquid film between the fluororesin (PTFE) sheets, and an alternating high voltage of 9 kV, 20 kHz and a power of 15 W is applied between the first electrode 19 and the second stainless steel electrode 22 of the barrier lamp 21. After applying the voltage and continuing irradiation for 2 minutes,
The sample with a contact angle with water of 100 ° is 4 on a uniform surface.
It became 0 ° and was reformed. The light absorption of PTFE is
Pure water has a large absorption coefficient near a wavelength of 190 nm, and pure water absorbs light having a wavelength shorter than 190 nm.
Therefore, it is preferable to fill the barrier lamp with xenon gas. From this excimer gas, the wavelength is 172 nm
The light is well emitted.
【００４９】［実施例６］図８に示す装置を用いてＳｉ
ウエハ上にＳｉ膜を成長させた。[Embodiment 6] Si is manufactured by using the apparatus shown in FIG.
A Si film was grown on the wafer.
【００５０】第２のステンレス平板電極兼加熱ヒーター
２５上にＳｉウエハを載せ、その上方５ｍｍの間隙を保
ち、平面状合成石英を光取り出し窓材とした面発光型バ
リヤランプ２１を置き、バリヤランプの第１の電極１９
と第２のステンレス平板電極２５との間に１５ｋＶ、２
０ｋＨｚ、入力２５Ｗの交流高電圧を印加した。このバ
リヤランプの光取り出し窓材とステンレス電極の間は真
空容器２４を成しており、ここに５Ｔｏｒｒのモノシラ
ンガス（ＳｉＨ4 ）を流した。基板加熱温度は３５０
℃、バリヤランプの発光ガスはＸｅで、発光波長は波長
１７２ｎｍとその近傍である。A Si wafer was placed on the second heater 25, which also serves as a flat plate electrode, and a surface emitting barrier lamp 21 having a flat synthetic quartz as a light extraction window material was placed with a gap of 5 mm above the Si wafer. One electrode 19
Between the second stainless flat plate electrode 25 and the
An alternating high voltage of 0 kHz and an input of 25 W was applied. A vacuum container 24 was formed between the light extraction window material of this barrier lamp and the stainless steel electrode, and 5 torr of monosilane gas (SiH 4 ) was flown therein. Substrate heating temperature is 350
The emission gas of the barrier lamp is Xe, and the emission wavelength is 172 nm and its vicinity.
【００５１】これらの条件下で、５分間のモノシランガ
スの放電およびバリヤランプからの真空紫外光照射を行
ったところ、厚さ５００オングストロームのＳｉ膜が形
成された。同様に、バリヤランプの発光ガスを、波長１
４６ｎｍの光を放射するクリプトンとして同一条件で照
射実験を行ったところ、厚さ１２００オングストローム
のＳｉ膜が形成された。なお、モノシランガスの光の吸
収は、波長１７５ｎｍ附近から始まる。Under these conditions, discharge of monosilane gas for 5 minutes and irradiation of vacuum ultraviolet light from a barrier lamp resulted in formation of a Si film having a thickness of 500 Å. Similarly, the luminous gas of the barrier lamp is changed to a wavelength of 1
When an irradiation experiment was performed under the same conditions as krypton that radiates light of 46 nm, a 1200 angstrom thick Si film was formed. It should be noted that the absorption of light of the monosilane gas starts near the wavelength of 175 nm.
【００５２】[0052]
【発明の効果】以上の実施例の説明からも理解できるよ
うに、誘電体バリヤ放電ランプからの紫外光と、処理用
流体と、被処理物表面と、その近傍における電気現象と
組合わせて、被処理物であるプラスチックや金属の表面
改質を小規模な装置で効率良く、かつ必要に応じて局所
的に実行できる。As can be understood from the above description of the embodiments, in combination with the ultraviolet light from the dielectric barrier discharge lamp, the processing fluid, the surface of the object to be processed, and the electrical phenomenon in the vicinity thereof, Surface modification of the plastic or metal that is the object to be processed can be efficiently performed locally with a small-scale device as needed.
【図１】本発明の１実施例に係わる固体材料表面改質装
置の側面図。FIG. 1 is a side view of a solid material surface reforming apparatus according to an embodiment of the present invention.
【図２】本発明の他の実施例に係わる固体材料表面改質
装置の側面図。FIG. 2 is a side view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図３】本発明の他の実施例に係わる固体材料表面改質
装置の側面図。FIG. 3 is a side view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図４】本発明の他の実施例に係わる固体材料表面改質
装置の側面図。FIG. 4 is a side view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図５】本発明の他の実施例に係わる固体材料表面改質
装置の斜視図。FIG. 5 is a perspective view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図６】本発明の他の実施例に係わる固体材料表面改質
装置の側面図。FIG. 6 is a side view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図７】本発明の他の実施例に係わる固体材料表面改質
装置の斜視図。FIG. 7 is a perspective view of a solid material surface reforming apparatus according to another embodiment of the present invention.
【図８】本発明の他の実施例に係わる固体材料表面改質
装置の斜視図。FIG. 8 is a perspective view of a solid material surface reforming apparatus according to another embodiment of the present invention.
１…第１の電極 ２…筒体 ３…円筒状誘電体 ４…誘電体バリヤ放電用のガス雰囲気 ５…バリヤランプ ６…ゴムローラー ７…被処理固体材料 ８…電源装置 ９…ローラー １０…板状電極 １１…平面状電極 １２…第２の電極としてのキャタピラ状帯電極 １３…化合物水溶液 １４…スポイト １５…雰囲気ガス １６…噴射ノズル １７…製品構造物 １８…箱型誘電体 １９…第１の電極 ２０…ガス雰囲気 ２１…面発光型バリヤランプ ２２…導電体 ２３…被処理固体材料 ２４…真空容器 ２５…第２の平板電極 DESCRIPTION OF SYMBOLS 1 ... 1st electrode 2 ... Cylindrical body 3 ... Cylindrical dielectric material 4 ... Dielectric barrier gas atmosphere for discharge 5 ... Barrier lamp 6 ... Rubber roller 7 ... Solid material to be treated 8 ... Power supply device 9 ... Roller 10 ... Plate shape Electrode 11 ... Planar electrode 12 ... Caterpillar band electrode as second electrode 13 ... Compound aqueous solution 14 ... Dropper 15 ... Atmosphere gas 16 ... Injection nozzle 17 ... Product structure 18 ... Box-shaped dielectric 19 ... First electrode 20 ... Gas atmosphere 21 ... Surface emitting type barrier lamp 22 ... Conductor 23 ... Solid material to be treated 24 ... Vacuum container 25 ... Second flat plate electrode
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２３Ｆ 4/00 Ａ 8417−4Ｋ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C23F 4/00 A 8417-4K
Claims (12)
と、この誘電体の一方の側に配置された誘電体バリヤ放
電用のガス雰囲気と第１の電極とを具える誘電体バリヤ
放電ランプと、 前記誘電体の他方の側に、処理用流体を介して配置され
た第２の電極と、 第１の電極と第２の電極とに交流高電圧または直流パル
ス高電圧を印加することのできる電源装置とより成り、 前記誘電体と第２の電極との間を、固体材料表面の改質
領域として構成したことを特徴とする固体材料表面改質
装置。1. A dielectric barrier discharge lamp comprising a dielectric material capable of transmitting ultraviolet light, a gas atmosphere for dielectric barrier discharge arranged on one side of the dielectric material, and a first electrode. And applying a high AC voltage or a high DC pulse voltage to the second electrode disposed on the other side of the dielectric through the processing fluid, and the first electrode and the second electrode. A solid material surface reforming device, comprising a power supply device capable of forming a reformed region on the surface of the solid material between the dielectric and the second electrode.
とも一方が、回転、摺動等が可能な可動型に設計されて
なる請求項１記載の固体材料表面改質装置。2. The solid material surface reforming apparatus according to claim 1, wherein at least one of the first electrode and the second electrode is designed as a movable type capable of rotating, sliding and the like.
２の電極としても機能させてなる請求項１記載の固体材
料表面改質装置。3. The solid material surface reforming apparatus according to claim 1, wherein the solid material is a metal, and the material also functions as a second electrode.
さらに備えてなる請求項１記載の固体材料表面改質装
置。4. The solid material surface reforming apparatus according to claim 1, further comprising a pressing means for pressing the solid material against the dielectric.
さらに備えてなる請求項１記載の固体材料表面改質装
置。5. The solid material surface reforming apparatus according to claim 1, further comprising positioning means for determining a gap in the reforming region.
と、パイプ状の誘電体の中に第１の電極と誘電体バリヤ
放電用のガスを配置した誘電体バリヤ放電ランプと、第
２の丸棒電極と誘電体との間にシート状の固体材料を通
過させる手段と、第２の丸棒電極と誘電体と固体材料を
接触もしくは近接せしめる手段と、誘電体と固体材料と
の間に処理用流体を供給する手段と、第１の電極と第２
の丸棒状電極との間に交流高電圧を印加する電源装置と
より成り、 電圧が印加された際、誘電体バリヤ放電ランプから放射
される紫外光と、処理用流体と、固体材料表面と、第２
の電極と誘電体との間の放電もしくは通電作用とからな
る相互作用によって、固体材料表面の改質を行なうこと
を特徴とする固体材料表面改質装置。6. A rotatably provided second round rod-shaped electrode, a dielectric barrier discharge lamp in which a first electrode and a gas for dielectric barrier discharge are arranged in a pipe-shaped dielectric, and A means for passing a sheet-shaped solid material between the second round bar electrode and the dielectric; a means for bringing the second round bar electrode, the dielectric and the solid material into contact with or in proximity to each other; Means for supplying a processing fluid between the first electrode and the second electrode
It consists of a power supply device that applies an alternating high voltage between the electrode and the round bar electrode, and when the voltage is applied, the ultraviolet light emitted from the dielectric barrier discharge lamp, the processing fluid, and the solid material surface, Second
2. A solid material surface reforming device, characterized in that the surface of a solid material is reformed by an interaction consisting of discharge or energization between the electrode and the dielectric.
の中に第１の電極と誘電体バリヤ放電用のガスを配置し
た誘電体バリヤ放電ランプと、 導電性の固体材料を第２の電極として機能させる電極形
成手段と、 誘電体と第２の電極とを接触もしくは近接させる手段
と、 誘電体と第２の電極との間に処理用流体を供給する手段
と、 誘電体バリヤ放電ランプもしくは第２電極の少なくとも
一方を移動させる手段と、 第１の電極と第２の電極との間に交流高電圧を印加する
電源装置とよりなり、 電圧が印加された際、誘電体バリヤ放電ランプから放射
される紫外光と、第２の電極の表面と、処理用流体と、
第２の電極と誘電体との間の放電もしくは通電作用とか
らなる相互作用によって、第２の電極として機能する固
体材料の表面の改質を行なうことを特徴とする固体材料
表面改質装置。7. A dielectric barrier discharge lamp in which a first electrode and a gas for dielectric barrier discharge are arranged in a pipe-shaped dielectric provided rotatably, and a conductive solid material is used as a second material. Electrode forming means for functioning as an electrode, means for bringing the dielectric and the second electrode into contact with or in proximity to each other, means for supplying a processing fluid between the dielectric and the second electrode, and a dielectric barrier discharge lamp Alternatively, it comprises a means for moving at least one of the second electrodes and a power supply device for applying an alternating high voltage between the first electrode and the second electrode, and when a voltage is applied, a dielectric barrier discharge lamp. Ultraviolet light emitted from the second electrode surface, the processing fluid,
A solid material surface reforming device, characterized in that the surface of a solid material that functions as a second electrode is modified by an interaction of discharge or energization between a second electrode and a dielectric.
の中に第１の電極と誘電体バリヤ放電用のガスを配置し
た誘電体バリヤ放電ランプと、 非導電性の固体材料の内部もしくは裏面に設けられた第
２の電極と、 誘電体と固体材料とを接触もしくは近接させる手段と、 誘電体と固体材料との間に処理用流体を供給する手段
と、 誘電体バリヤ放電ランプもしくは固体材料の少なくとも
一方を移動させる手段と、 第１の電極と第２の電極との間に交流高電圧を印加する
電源装置とより成り、 電圧が印加された際、誘電体バリヤ放電ランプから放射
される紫外光と、固体材料の表面と、処理用流体と、固
体材料と誘電体との間の放電もしくは通電作用とからな
る相互作用によって、固体材料表面の改質をおこなうこ
とを特徴とする固体材料表面改質装置。8. A dielectric barrier discharge lamp having a first electrode and a gas for dielectric barrier discharge arranged in a rotatably provided pipe-shaped dielectric, and a non-conductive solid material inside or A second electrode provided on the back surface, a means for bringing the dielectric and the solid material into contact with or in proximity to each other, a means for supplying a processing fluid between the dielectric and the solid material, a dielectric barrier discharge lamp or a solid It comprises a means for moving at least one of the materials and a power supply device for applying an alternating high voltage between the first electrode and the second electrode. When a voltage is applied, the dielectric barrier discharge lamp emits the radiation. Solid, characterized in that the surface of the solid material is modified by the interaction of the ultraviolet light, the surface of the solid material, the processing fluid, and the discharge or energization between the solid material and the dielectric. Material surface modification Quality equipment.
と、この誘電体の一方の側に配置された誘電体バリヤ放
電用のガス雰囲気と第１の電極とを具える誘電体バリヤ
放電ランプと、 前記誘電体の他方の側に、処理用流体を介して配置され
た第２の電極と、 第１の電極と第２の電極との間に交流高電圧もしくは直
流パルス高電圧を印加する電源装置とより成り、 前記処理用流体と第２の電極との間を固体材料表面の改
質領域として構成し、 電圧が印加された際、誘電体バリヤ放電ランプから放射
される紫外光と、処理用流体と、固体材料表面と、誘電
体と固体材料との間で生ずる放電もしくは通電作用との
相互作用によって、固体材料表面を異質化したり、エッ
チングしたり、化学種や金属を堆積させたりすることを
特徴とする固体材料表面改質装置。9. A dielectric barrier discharge lamp comprising a dielectric capable of transmitting ultraviolet light, a dielectric barrier discharge gas atmosphere disposed on one side of the dielectric, and a first electrode. And applying a high AC voltage or a high DC pulse voltage between the first electrode and the second electrode, and the second electrode disposed on the other side of the dielectric through the processing fluid. An ultraviolet ray emitted from the dielectric barrier discharge lamp when a voltage is applied, and a power source device is provided between the processing fluid and the second electrode as a modified region of the surface of the solid material. The interaction of the processing fluid, the surface of the solid material, and the electrical discharge or energization that occurs between the dielectric and the solid material causes the surface of the solid material to become heterogeneous, etched, and to deposit chemical species and metals. Solid material surface characterized by Quality equipment.
の誘電体と、この誘電体の一方の側に配置された誘電体
バリヤ放電用のガス雰囲気と第１の電極とを備えた誘電
体バリヤ放電ランプと、 前記誘電体の他方の側に配置された第２の電極と、 誘電体と第２の電極との間に処理用流体としてエッチン
グ用ガスもしくはＣＶＤ用ガスを供給する処理用流体供
給手段と、 第１の電極と第２の電極との間に交流高電圧もしくは高
繰り返し直流パルス高電圧を印加する電源装置とより成
り、 エッチング用ガスもしくはＣＶＤ用ガスと第２の電極と
の間を固体材料表面の改質領域として構成し、 電圧が印加された際、誘電体バリヤ放電ランプから放射
される紫外光と、エッチング用ガスもしくはＣＶＤ用ガ
スとそれらの中に生ずる放電と、固体材料表面との相互
作用によって、固体材料表面を異質化したり、エッチン
グしたり、被覆したりすることを特徴とする固体材料表
面改質装置。10. A dielectric material comprising a flat plate-shaped dielectric material capable of transmitting ultraviolet light, a gas atmosphere for dielectric barrier discharge arranged on one side of the dielectric material, and a first electrode. A barrier fluid discharge lamp, a second electrode arranged on the other side of the dielectric, and a processing fluid for supplying an etching gas or a CVD gas as a processing fluid between the dielectric and the second electrode. And a power supply device for applying an alternating high voltage or a high repetitive direct-current pulse high voltage between the first electrode and the second electrode. The etching gas or the CVD gas and the second electrode are connected to each other. Between the solid material surface and the modified region, the ultraviolet light emitted from the dielectric barrier discharge lamp when a voltage is applied, the etching gas or the CVD gas and the discharge generated in them, and the solid Material table Another by the action, or heterogeneity of the solid material surface, etching or the solid material surface modification apparatus characterized by or coated with.
と、この誘電体の一方の側に配置された誘電体バリヤ放
電用のガス雰囲気と第１の電極とを備えた誘電体バリヤ
放電ランプと、 前記誘電体の他方の側に処理用流体を介して配置された
第２の電極と、 第１の電極と第２の電極との間に交流高電圧または直流
パルス高電圧を印加することができる電源装置と、 被処理固体材料を供給する手段とを備えた固体材料表面
改質装置を用いて、 誘電体バリヤ放電ランプから放射される紫外光と、処理
用流体と、誘電体と第２電極との間で生ずる電気現象
と、固体材料表面との相互作用を利用して、固体材料表
面を改質することを特徴とする固体材料表面改質方法。11. A dielectric barrier discharge lamp comprising a dielectric capable of transmitting ultraviolet light, a gas atmosphere for dielectric barrier discharge arranged on one side of the dielectric, and a first electrode. And applying a high AC voltage or a high DC pulse voltage between the first electrode and the second electrode, and the second electrode disposed on the other side of the dielectric through the processing fluid. By using a solid material surface reforming device equipped with a power supply device capable of supplying the solid material to be treated, the ultraviolet light emitted from the dielectric barrier discharge lamp, the processing fluid, the dielectric material and the A method for modifying a surface of a solid material, characterized by modifying the surface of the solid material by utilizing an electrical phenomenon generated between two electrodes and an interaction with the surface of the solid material.
波長域と処理用流体の吸収波長域とが一致する波長域部
分を選択する請求項１１の固体材料表面改質方法。12. The method for modifying the surface of a solid material according to claim 11, wherein a wavelength range portion in which the wavelength range of the ultraviolet light, the absorption wavelength range of the surface of the solid material, and the absorption wavelength range of the processing fluid coincide with each other is selected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33299393A JP3316069B2 (en) | 1993-12-27 | 1993-12-27 | Solid material surface modification method and solid material surface modification device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33299393A JP3316069B2 (en) | 1993-12-27 | 1993-12-27 | Solid material surface modification method and solid material surface modification device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07185315A true JPH07185315A (en) | 1995-07-25 |
| JP3316069B2 JP3316069B2 (en) | 2002-08-19 |
Family
ID=18261103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33299393A Expired - Fee Related JP3316069B2 (en) | 1993-12-27 | 1993-12-27 | Solid material surface modification method and solid material surface modification device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3316069B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003515460A (en) * | 1999-12-01 | 2003-05-07 | フィエル・ヴォルフガング | A method for modifying wood surfaces by electrical discharge at atmospheric pressure |
| JP2009046710A (en) * | 2007-08-16 | 2009-03-05 | Fuji Electric Systems Co Ltd | Continuous manufacturing apparatus of semiconductor device |
| CN101835336A (en) * | 2010-05-21 | 2010-09-15 | 江苏大学 | Double-dielectric barrier discharge low-temperature plasma generator |
| JP2014527257A (en) * | 2011-06-28 | 2014-10-09 | エムティーアイエックス リミテッド | A method and apparatus for surface treatment of materials using a plurality of coupled energy sources. |
| US9605376B2 (en) | 2011-06-28 | 2017-03-28 | Mtix Ltd. | Treating materials with combined energy sources |
| WO2022024882A1 (en) * | 2020-07-27 | 2022-02-03 | ウシオ電機株式会社 | Fluorine resin surface modification method, surface-modified fluorine resin production method, joining method, material having surface-modified fluorine resin, and joined body |
-
1993
- 1993-12-27 JP JP33299393A patent/JP3316069B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003515460A (en) * | 1999-12-01 | 2003-05-07 | フィエル・ヴォルフガング | A method for modifying wood surfaces by electrical discharge at atmospheric pressure |
| JP2009046710A (en) * | 2007-08-16 | 2009-03-05 | Fuji Electric Systems Co Ltd | Continuous manufacturing apparatus of semiconductor device |
| CN101835336A (en) * | 2010-05-21 | 2010-09-15 | 江苏大学 | Double-dielectric barrier discharge low-temperature plasma generator |
| JP2014527257A (en) * | 2011-06-28 | 2014-10-09 | エムティーアイエックス リミテッド | A method and apparatus for surface treatment of materials using a plurality of coupled energy sources. |
| US9605376B2 (en) | 2011-06-28 | 2017-03-28 | Mtix Ltd. | Treating materials with combined energy sources |
| WO2022024882A1 (en) * | 2020-07-27 | 2022-02-03 | ウシオ電機株式会社 | Fluorine resin surface modification method, surface-modified fluorine resin production method, joining method, material having surface-modified fluorine resin, and joined body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3316069B2 (en) | 2002-08-19 |
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