JP4861257B2 - Fine particle film manufacturing method and manufacturing apparatus using coaxial vacuum arc deposition source - Google Patents
Fine particle film manufacturing method and manufacturing apparatus using coaxial vacuum arc deposition source Download PDFInfo
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Description
本発明は、カーボンナノチューブの下地膜（触媒層）や、燃料電池や車の排ガス触媒金属の微粒子膜の製造に使用される。 The present invention is used for the production of a carbon nanotube substrate film (catalyst layer) and a fine particle film of an exhaust gas catalyst metal for fuel cells and vehicles.
従来のポリマフィルム上への微粒子膜の製造方法には、スパッタ法や電子ビーム蒸着法がある。 Conventional methods for producing a fine particle film on a polymer film include a sputtering method and an electron beam evaporation method.
まず、スパッタ法よる場合を説明する。
スパッタ法は、被蒸着物である基板と蒸着材料であるターゲットを対向させておき、数Ｐａ〜数１０Ｐａ程度のＡｒガス雰囲気中でターゲットに数ＫＶの負の高電圧を印加し、放電させるとＡｒガスは正イオンとなってターゲットに衝突し、ターゲットの原子を叩き出す。原子は基板上に堆積し薄膜を形成する。
First, the case using the sputtering method will be described.
In the sputtering method, when a substrate as a deposition target and a target as a deposition material are opposed to each other and a negative high voltage of several KV is applied to the target in an Ar gas atmosphere of about several Pa to several tens Pa, and then discharged. Ar gas becomes positive ions and collides with the target to knock out atoms of the target. The atoms are deposited on the substrate to form a thin film.
ここで、スパッタ法では基板とターゲットの距離が５０〜１５０ｍｍ程度であり、ターゲットへ投入する電力にもよるが、堆積によって伝わった熱により、基板の温度は約８０℃〜１５０℃程度上昇してしまう。これは基板ステージが熱伝導性の良いものの場合であり、基板がポリマ等の高分子フィルムでは、熱伝導性が悪く、さらに表面温度が２００℃以上になる場合があり、そうなれば特殊な耐熱フィルム（例えば、ポリイミド、ポリテトラフルオロエチレン（ＰＴＦＥ））以外（例えば、ポリエチレンテレフタレート（ＰＥＴ）、ナイロン）には蒸着できない。 Here, in the sputtering method, the distance between the substrate and the target is about 50 to 150 mm, and depending on the electric power supplied to the target, the temperature of the substrate is increased by about 80 to 150 ° C. due to the heat transferred by the deposition. End up. This is the case where the substrate stage has a good thermal conductivity. When the substrate is a polymer film such as a polymer, the thermal conductivity is poor and the surface temperature may be 200 ° C. or higher. Vapor deposition cannot be performed on films other than films (for example, polyimide, polytetrafluoroethylene (PTFE)) (for example, polyethylene terephthalate (PET), nylon).
また、スパッタ法で蒸着した白金ナノ粒子は１０ｎｍ程度の棒状に分散してしまう。
さらに、基板の温度を下げるために、スパッタの投入パワーを落として室温近傍で成膜するとさらに大きな（３０ｎｍ程度）粒子が存在するようになる。
In addition, platinum nanoparticles deposited by sputtering are dispersed in a rod shape of about 10 nm.
Further, when the film is formed near the room temperature by lowering the sputtering input power in order to lower the temperature of the substrate, larger particles (about 30 nm) are present.
次に、電子ビーム蒸着法による場合を説明する。
電子ビーム蒸着源は蒸着材料を入れるルツボと電子ビーム発生機構及び電子ビームの偏向磁極などから構成されている。フィラメントで発生した熱電子は数１０ＫＶの負の高電圧で加速され磁場により偏向された後、ルツボ内の蒸着材料に当てられ、蒸着材料を加熱して蒸発させる。
Next, the case of the electron beam evaporation method will be described.
The electron beam evaporation source is composed of a crucible for depositing an evaporation material, an electron beam generating mechanism, an electron beam deflection magnetic pole, and the like. The thermoelectrons generated in the filament are accelerated by a negative high voltage of several tens of KV and deflected by a magnetic field, and then applied to the vapor deposition material in the crucible, and the vapor deposition material is heated and evaporated.
しかしながら、電子ビーム蒸着法によりポリマフィルム上に蒸着した白金の粒子は、ステップ状に集まる傾向があり、分散させて均一に蒸着することが出来ない。
また、電子ビーム蒸着法ではルツボ内で蒸着材料を溶融させるため、その輻射熱を考慮すると、耐熱性に劣るフィルムを基板として使うことはできない。
However, the platinum particles deposited on the polymer film by the electron beam deposition method tend to gather in a step shape and cannot be dispersed and uniformly deposited.
In addition, since the evaporation material is melted in the crucible in the electron beam evaporation method, a film having poor heat resistance cannot be used as the substrate in consideration of the radiant heat.
以上のように、スパッタ法や電子ビーム蒸着法では、蒸着材料を蒸発させるときに使用するエネルギーが大きい傾向にあるため、その影響を受けて基板の温度も高くなり、ポリマ等の高分子フィルムを基板として用いる場合には不向きであった。
そこで、真空中でのアーク放電を用いて、蒸着材料を点乃至狭い領域で蒸発させることにより、スパッタ法や電子ビーム蒸着法よりも加熱に使用するエネルギーを減少させることのできる蒸着方法が注目された。これは、真空中でのアーク放電により薄膜形成用の蒸着材料が殆ど溶融することなく、カソードスポットと呼ばれる領域に放電電流の集中が起こる形態の真空アーク蒸着法である。
As described above, in the sputtering method and the electron beam evaporation method, the energy used for evaporating the evaporation material tends to be large. It was not suitable for use as a substrate.
Therefore, a vapor deposition method that can reduce the energy used for heating more than sputtering or electron beam vapor deposition by evaporating the vapor deposition material in a point or narrow region by using arc discharge in vacuum attracts attention. It was. This is a vacuum arc deposition method in which the discharge current is concentrated in a region called a cathode spot without almost melting a deposition material for forming a thin film by arc discharge in vacuum.
すなわち、図４の概念図に示す同軸型真空アーク蒸着源１０５による真空中でのアーク放電を用いる方法では、真空アーク放電の蒸着源１０５は、円柱状のカソード電極１１２と、これに取り付けた円柱状の蒸着材料１１１の周囲に円筒状のアノード電極１２３を設け、蒸着材料１１１の近傍に配置したトリガ電極１１３と蒸着材料１１１との間に高電圧パルスを加えて、トリガ放電させる。このトリガ放電により、蒸着材料１１１上に電流が集中する点乃至領域（カソードスポット）が発生し、次いで、このカソードスポットとアノード電極１２３との間で主放電が始まって、カソードスポットの成長と移動が起こり、カソードスポット中で生成したイオンが放出される。これが、被蒸着物である基板１０４方向に加速移動されて膜を形成するというものである。例えば、高分子材料フィルム上に鉄薄膜を形成させた例がある（特許文献１参照）。 That is, in the method using arc discharge in vacuum by the coaxial vacuum arc deposition source 105 shown in the conceptual diagram of FIG. 4, the vacuum arc discharge deposition source 105 includes a cylindrical cathode electrode 112 and a circle attached to the cathode electrode 112. A cylindrical anode electrode 123 is provided around the columnar vapor deposition material 111, and a high voltage pulse is applied between the trigger electrode 113 disposed in the vicinity of the vapor deposition material 111 and the vapor deposition material 111 to cause trigger discharge. By this trigger discharge, a point or region (cathode spot) where current concentrates on the vapor deposition material 111 is generated, and then a main discharge starts between the cathode spot and the anode electrode 123 to grow and move the cathode spot. And ions generated in the cathode spot are released. This is to be accelerated and moved in the direction of the substrate 104 that is the deposition target to form a film. For example, there is an example in which an iron thin film is formed on a polymer material film (see Patent Document 1).
しかしながら、例えば真空中でのアーク放電を用いたポリマフィルム上への白金のナノ粒子膜の形成（ナノ粒子の担時）では、成膜レートが低かった。 However, for example, in the formation of a platinum nanoparticle film on a polymer film using arc discharge in a vacuum (when nanoparticles are carried), the film formation rate is low.
これは、絶縁体であるポリマフィルムに、アーク放電によるイオンが到達し、イオンから移った電荷が滞留することによるものと考えられる。 This is considered to be due to the arrival of ions by arc discharge and the charge transferred from the ions stays on the polymer film which is an insulator.
上記の課題は、トリガ電極と微粒子作成用金属材料で少なくとも先端部が構成されたカソード電極とが、絶縁碍子を挟んで隣接して配置されてなり、前記カソード電極と前記トリガ電極との周りに同軸状に筒状のアノード電極が配置されている同軸型真空アーク蒸着源を用い、前記トリガ電極と前記アノード電極との間にトリガ放電をパルス的に発生させて、前記カソード電極と前記アノード電極との間にアーク放電を断続的に誘起させ、被蒸着物である絶縁基板上に、所定の粒径の微粒子からなる前記金属材料の微粒子を付着せしめる微粒子膜の製造方法において、前記絶縁基板を除電しながら、前記絶縁基板に微粒子を付着させる微粒子膜の製造方法によって解決される。 The above-described problem is that a trigger electrode and a cathode electrode having at least a tip formed of a metal material for creating fine particles are arranged adjacent to each other with an insulator interposed therebetween, and the cathode electrode and the trigger electrode are arranged around the cathode electrode and the trigger electrode. Using a coaxial vacuum arc evaporation source in which a cylindrical anode electrode is coaxially disposed, a trigger discharge is generated in a pulse manner between the trigger electrode and the anode electrode, and the cathode electrode and the anode electrode are generated. In the method for producing a fine particle film in which arc discharge is intermittently induced between the metal material and the metal material fine particles having a predetermined particle diameter are adhered to the insulating substrate as a deposition target, The problem can be solved by a method of manufacturing a fine particle film in which fine particles are adhered to the insulating substrate while removing electricity.
具体的に、例えば、同軸型真空アーク蒸着源を用いたポリマフィルム上へ微粒子膜を製造する方法において、イオンから移ったポリマフィルム上の電荷を除去することにより成膜レートを向上させる。 Specifically, for example, in a method for producing a fine particle film on a polymer film using a coaxial vacuum arc deposition source, the film formation rate is improved by removing the charge on the polymer film transferred from the ions.
また、上記の課題は、真空槽と、トリガ電極と微粒子作成用金属材料で少なくとも先端部が構成されたカソード電極とが、絶縁碍子を挟んで隣接して配置されてなり、前記カソード電極と前記トリガ電極との周りに同軸状に筒状のアノード電極が配置されている同軸型真空アーク蒸着源と、絶縁基板を載せるための基板ステージと、前記絶縁基板を除電する除電手段とを備えた微粒子膜の製造装置によって解決される。 In addition, the above-described problem is that a vacuum chamber, a trigger electrode, and a cathode electrode having at least a tip formed of a metal material for creating fine particles are disposed adjacent to each other with an insulator interposed therebetween, and the cathode electrode and the cathode electrode Fine particles comprising a coaxial vacuum arc vapor deposition source in which a cylindrical anode electrode is coaxially disposed around a trigger electrode, a substrate stage for placing an insulating substrate, and a charge eliminating means for discharging the insulating substrate Solved by membrane production equipment.
具体的に、例えば、同軸型真空アーク蒸着源を有するポリマフィルム上へ微粒子膜を製造する装置において、イオンから移ったポリマフィルム上の電荷を除去する除電手段である電気配線を設け、ポリマフィルムをアースに接続することによって成膜レートを向上させる。 Specifically, for example, in an apparatus for producing a fine particle film on a polymer film having a coaxial vacuum arc deposition source, an electrical wiring is provided as a charge eliminating means for removing charges on the polymer film transferred from ions, and the polymer film is The film formation rate is improved by connecting to ground.
本発明は、ポリマフィルムの基板上に同軸型真空アーク蒸着源を用いて白金の微粒子膜を形成させるとき、基板上に粒子を均一かつ高レートで付着させることが出来る。 According to the present invention, when a platinum fine particle film is formed on a polymer film substrate using a coaxial vacuum arc deposition source, the particles can be uniformly deposited at a high rate on the substrate.
以下、本発明を適用した具体的な実施の形態について図面を参照しながら詳細に説明する。
本発明の触媒担持用の同軸型真空アーク蒸着源５を用いた微粒子膜の製造装置１について図１に基いて説明する。真空槽２は、円筒状をしている。基板ステージ３は、真空槽２内に収容されている。ホルダ３ａの中心には回転機構３ｂが接続されている。
Hereinafter, specific embodiments to which the present invention is applied will be described in detail with reference to the drawings.
An apparatus 1 for producing a fine particle film using a coaxial vacuum arc deposition source 5 for supporting a catalyst according to the present invention will be described with reference to FIG. The vacuum chamber 2 has a cylindrical shape. The substrate stage 3 is accommodated in the vacuum chamber 2. A rotation mechanism 3b is connected to the center of the holder 3a.
除電手段である除電ユニット７は、基板ステージ３の端に金属製の板ばね７２が取付けられており、板ばね７２には電気配線としての金属配線が接続されている。金属配線は電流導入端子７１を介してアースに接続されている。金属配線は板ばね７２の中に収納されている。 In the static elimination unit 7 which is a static elimination means, a metal leaf spring 72 is attached to the end of the substrate stage 3, and a metal wiring as an electrical wiring is connected to the leaf spring 72. The metal wiring is connected to the ground via the current introduction terminal 71. The metal wiring is accommodated in the leaf spring 72.
同軸型真空アーク蒸着源５のカソードである蒸着材料１１及びカソード電極１２は円柱状をしている。蒸着材料１１の材質は白金である。カソード電極１２の材質は銅である。
絶縁碍子１４は、ハット型碍子と呼称される。絶縁碍子１４の材質はアルミナである。
トリガ電極１３は、円筒状をしており、材質はステンレスである。
カソード電極１２、絶縁碍子１４、トリガ電極１３のこれら３つの部品は特に詳細に図示しないが、同心円状に密着させて取付けられている。
The vapor deposition material 11 and the cathode electrode 12 which are the cathodes of the coaxial vacuum arc vapor deposition source 5 have a cylindrical shape. The material of the vapor deposition material 11 is platinum. The material of the cathode electrode 12 is copper.
The insulator 14 is referred to as a hat-type insulator. The material of the insulator 14 is alumina.
The trigger electrode 13 has a cylindrical shape and is made of stainless steel.
Although not shown in detail in detail, these three components, the cathode electrode 12, the insulator 14, and the trigger electrode 13, are attached in close contact with each other concentrically.
アノード電極２３は、円筒状をしており、材質はステンレスで出来ている。このアノード電極２３は、カソード電極１２及び蒸着材料１１と同心円状に取付けられている。 The anode electrode 23 has a cylindrical shape and is made of stainless steel. The anode electrode 23 is attached concentrically with the cathode electrode 12 and the vapor deposition material 11.
また、図中には簡易な電気配線図を記載している。
電源装置６は、トリガ電源３１、アーク電源３２、コンデンサユニット３３で構成されている。
コンデンサユニット３３は、容量が２２００μＦ（耐圧：１００Ｖ）のコンデンサを４つ並列に接続している。
In addition, a simple electrical wiring diagram is shown in the figure.
The power supply device 6 includes a trigger power supply 31, an arc power supply 32, and a capacitor unit 33.
The capacitor unit 33 has four capacitors having a capacitance of 2200 μF (withstand voltage: 100 V) connected in parallel.
トリガ電源３１は、パルストランスからなり、入力２００Ｖのμｓ単位のパルス電圧を約１７倍に変圧して３．４ＫＶ（数μＡ）の正極性の高電圧パルスを出力する。 The trigger power supply 31 is composed of a pulse transformer, and transforms a pulse voltage in units of μs with an input of 200 V to about 17 times and outputs a positive high voltage pulse of 3.4 KV (several μA).
アーク電源３２は、１００Ｖ 数Ａの容量の直流電源であり、コンデンサユニット３３を充電するようになっている。
このコンデンサユニット３３の充電には、約１秒を要するので、本システムでは、放電を繰り返し行う場合の周期は１Ｈｚで行っている。
The arc power supply 32 is a DC power supply with a capacity of 100V and several A, and charges the capacitor unit 33.
Since charging of the capacitor unit 33 takes about 1 second, in this system, the cycle when discharging is repeated is 1 Hz.
トリガ電源３１の出力のプラス端子は、トリガ電極１３に接続され、トリガ電源３１の出力のマイナス端子は、アーク電源３２の出力のマイナス端子とともにカソード電極１２に接続されている。 The positive terminal of the output of the trigger power supply 31 is connected to the trigger electrode 13, and the negative terminal of the output of the trigger power supply 31 is connected to the cathode electrode 12 together with the negative terminal of the output of the arc power supply 32.
アーク電源３２のプラス端子は、グランド電位に接地されている。コンデンサユニット３３の両端子はそれぞれ、アーク電源３２のプラスおよびマイナス端子に接続されている。 The plus terminal of the arc power supply 32 is grounded to the ground potential. Both terminals of the capacitor unit 33 are connected to the plus and minus terminals of the arc power supply 32, respectively.
ターボ分子ポンプ５１、仕切りバルブ５２、ロータリポンプ５３までは金属製の真空配管で接続されており、真空槽２内の真空排気を行っている。真空排気を行うことで真空槽２内は１０-5Ｐａの真空に保たれている。 The turbo molecular pump 51, the partition valve 52, and the rotary pump 53 are connected by a metal vacuum pipe, and the vacuum chamber 2 is evacuated. The inside of the vacuum chamber 2 is kept at a vacuum of 10 −5 Pa by performing evacuation.
次に、本発明の微粒子膜の製造装置１の動作につき図に基いて説明する。まず、本発明の同軸型真空アーク蒸着源５の動作につき図１を参照して説明する。 Next, the operation of the fine particle film manufacturing apparatus 1 of the present invention will be described with reference to the drawings. First, the operation of the coaxial vacuum arc deposition source 5 of the present invention will be described with reference to FIG.
はじめに、アーク電源３２により、コンデンサユニット３３に１００Ｖで電荷を充電する。なお、コンデサユニット３３は８８００μＦの容量を持っている。 First, the capacitor unit 33 is charged with 100V by the arc power source 32. The capacitor unit 33 has a capacity of 8800 μF.
次に、トリガ電極１３にトリガ電源３１から３．４ＫＶのパルスを出力し、蒸着材料１１とトリガ電極との間に絶縁碍子１４を介して印加することで、絶縁碍子１４の表面で沿面放電が発生し、蒸着材料１１と絶縁碍子１４のつなぎ目から電子が発生する。 Next, a pulse of 3.4 KV is output from the trigger power supply 31 to the trigger electrode 13 and applied between the vapor deposition material 11 and the trigger electrode via the insulator 14, thereby causing creeping discharge on the surface of the insulator 14. And electrons are generated from the joint between the vapor deposition material 11 and the insulator 14.
ここで、蒸着材料１１と、アノード電極２３の内面との間にコンデンサユニット３３に充電された電荷が放電され、蒸着材料１１に多量の電流が流入し、カソード電極１２に取付けられた蒸着材料１１である白金が液層から気相、さらにはプラズマが形成される。 Here, the electric charge charged in the capacitor unit 33 is discharged between the vapor deposition material 11 and the inner surface of the anode electrode 23, a large amount of current flows into the vapor deposition material 11, and the vapor deposition material 11 attached to the cathode electrode 12. Is formed from the liquid layer into the gas phase and further plasma.
さらに、蒸着材料１１と絶縁碍子１４のつなぎ目から発生した電子は、円筒状のアノード電極２３の内面に向かって飛行する。この時、蒸着材料１１に比較的多量の電流（２０００Ａ〜５０００Ａ）が、２００μｓ〜５５０μの間流れるので、カソード電極１２に磁場が形成される。プラズマ中の電子が、カソード電極１２の形成した磁場によるローレンツ力を受けて、同軸型真空アーク蒸着源５の前方へ飛行するようになる。 Further, electrons generated from the joint between the vapor deposition material 11 and the insulator 14 fly toward the inner surface of the cylindrical anode electrode 23. At this time, since a relatively large amount of current (2000 A to 5000 A) flows through the deposition material 11 for 200 μs to 550 μ, a magnetic field is formed on the cathode electrode 12. Electrons in the plasma fly under the coaxial vacuum arc deposition source 5 under the Lorentz force generated by the magnetic field formed by the cathode electrode 12.
一方、プラズマ中の蒸着材料である白金のイオンは、分極することでクーロン力により、同軸型真空アーク蒸着源５の前方へ飛行する電子に引き付けられるようにして同軸型真空アーク蒸着源５の前方へ飛行する。その結果、白金のイオンは、ポリマフィルムである絶縁基板４上で凝集し、ナノメートル単位の白金粒子が形成される。 On the other hand, platinum ions, which are vapor deposition materials in the plasma, are polarized so that they are attracted to electrons flying in front of the coaxial vacuum arc deposition source 5 by Coulomb force. Fly to. As a result, platinum ions aggregate on the insulating substrate 4 which is a polymer film, and platinum particles in nanometer units are formed.
このとき、絶縁基板４に到達した白金イオンの電荷は絶縁基板４に移ることとなる。この電荷が絶縁基板４に滞留すると、後から到達した白金イオンとの間に反発力が生じる。この反発力は、後から到達した白金イオンを絶縁基板４から遠ざける方向に働くので、その結果、絶縁基板４上への成膜レートが下がるという問題が生じることになる。 At this time, the charge of platinum ions reaching the insulating substrate 4 moves to the insulating substrate 4. When this electric charge stays in the insulating substrate 4, a repulsive force is generated between the platinum ions that have arrived later. This repulsive force works in a direction to move away platinum ions that have arrived later from the insulating substrate 4, and as a result, a problem arises in that the film formation rate on the insulating substrate 4 decreases.
そこで、先に絶縁基板４に到達したイオンの電荷を基板上から除去するために、除電ユニット７によってアースに電荷を逃がすように構成したところ、成膜レートが増加した。 Therefore, in order to remove the charge of ions that have reached the insulating substrate 4 from the substrate, the charge removal unit 7 allows the charge to escape to the ground, and the film formation rate increased.
すなわち、図１の除電ユニット７は、基板ステージ３の端に金属製の板ばね７２が取付けられており、板ばね７２には金属配線が接続されている。金属配線は電流導入端子７１を介してアースに接続されている。配線は板ばね７２の中に収納されている。 That is, in the static elimination unit 7 of FIG. 1, a metal leaf spring 72 is attached to the end of the substrate stage 3, and a metal wiring is connected to the leaf spring 72. The metal wiring is connected to the ground via the current introduction terminal 71. The wiring is housed in the leaf spring 72.
絶縁基板４の上面から電荷を除去するために、板ばね７２の一端が絶縁基板４の絶縁基板４の上面に接触されている。また、絶縁基板４は、金属製の基板ステージ３は上に載せられている。板ばね７２は、基板ステージにねじ７２で止められている。板ばね７２と、基板ステージは、ねじ７２で止められている部分で、電気的な接続を確保されている。板ばね７２の他端は、真空槽２の壁面を貫通する電流導入端子７１を用いて真空槽２の外部に配線し、アースに接続させている。 In order to remove charges from the upper surface of the insulating substrate 4, one end of the leaf spring 72 is in contact with the upper surface of the insulating substrate 4 of the insulating substrate 4. The insulating substrate 4 is placed on the metal substrate stage 3. The leaf spring 72 is fixed to the substrate stage with a screw 72. The plate spring 72 and the substrate stage are secured by screws 72, and electrical connection is ensured. The other end of the leaf spring 72 is wired to the outside of the vacuum chamber 2 using a current introduction terminal 71 penetrating the wall surface of the vacuum chamber 2 and connected to the ground.
以上のように、本発明の微粒子膜の製造方法では、除電手段７によって、成膜レートが増加した。また、絶縁基板４の上面に白金粒子を極めて均一に付着させることができた。 As described above, in the method of manufacturing the fine particle film of the present invention, the film forming rate is increased by the charge eliminating means 7. Further, the platinum particles could be adhered extremely uniformly on the upper surface of the insulating substrate 4.
本発明の実施の形態の微粒子膜の製造方法及び製造装置により、実際に成膜した例を図２に示す。これは、本発明の微粒子膜の製造装置１を用いて、同軸型真空アーク蒸着源５によるアーク放電を１０発行って、コロジオンフィルム上に付着させた白金粒子のＴＥＭ写真である。図から明らかなようにコロジオンフィルム上に白金が担持されている。なお、本発明の効果を調べるために、絶縁基板４としてはＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）観察用支援膜として用いられるコロジオンフィルムを使用した。これは、ポリマフィルムにコロジオンが付けられたものである。
FIG. 2 shows an example of actual film formation by the fine particle film manufacturing method and manufacturing apparatus according to the embodiment of the present invention. This is a TEM photograph of platinum particles deposited on a collodion film by issuing 10 arc discharges by a coaxial vacuum arc deposition source 5 using the fine particle film production apparatus 1 of the present invention. As is apparent from the figure, platinum is supported on the collodion film. In order to investigate the effect of the present invention, a collodion film used as a support film for TEM (Transmission Electron Microscope) observation was used as the insulating substrate 4. This is a polymer film with collodion attached.
以上のように、本発明の微粒子膜の製造装置１によれば、ポリマフィルム上にナノメートル単位（１〜１０ｎｍ）の白金を均一に担持することができる。 As described above, according to the fine particle film manufacturing apparatus 1 of the present invention, platinum in nanometer units (1 to 10 nm) can be uniformly supported on a polymer film.
以上のように、本発明の実施の形態について説明したが、本発明はこれらに限定されることなく、本発明の技術的思想に基づいて種々の変形が可能である。 As mentioned above, although embodiment of this invention was described, this invention is not limited to these, A various deformation | transformation is possible based on the technical idea of this invention.
例えば、実施例では、除電手段としての除電ユニット７として、電流導入端子７１、板ばね７２、ねじ７３を用いてホルダ３ａと絶縁基板４とを電気的に接続し、一緒にアース電位に接地したが、ホルダ３ａと絶縁基板４を個々にアース電位に接地するようにしても良い（図３Ａ参照）。 For example, in the embodiment, as the static elimination unit 7 as the static elimination means, the holder 3a and the insulating substrate 4 are electrically connected using the current introduction terminal 71, the leaf spring 72, and the screw 73, and grounded to the ground potential together. However, the holder 3a and the insulating substrate 4 may be individually grounded to the ground potential (see FIG. 3A).
また、負電荷の供給は、配線によりアースに接続するようにしたが、真空槽２の壁面に電子銃７６を設け、金属材料のイオンの発生量に応じて、電子を供給することにより行っても良い（図３Ｂ参照）。 The negative charge is supplied to the ground by wiring. However, an electron gun 76 is provided on the wall surface of the vacuum chamber 2, and electrons are supplied according to the amount of ions generated from the metal material. (See FIG. 3B).
また、実施例では、アーク放電電圧は、１００Ｖに設定したが、この場合はポリマフィルム上にへこみが形成される。このへこみは、２ｎｍ以下であるが、均一な成膜を行う上では好ましくない。そこで、放電電圧を６０Ｖ程度とすることで、へこみを０．５ｎｍ以下にすることが可能である。 In the embodiment, the arc discharge voltage is set to 100 V. In this case, a dent is formed on the polymer film. Although this dent is 2 nm or less, it is not preferable for uniform film formation. Therefore, the dent can be reduced to 0.5 nm or less by setting the discharge voltage to about 60V.
１・・・微粒子膜の製造装置、２・・・真空槽、３・・・基板ステージ、３ａ・・・基板ホルダ、３ｂ・・・回転機構、４・・・絶縁基板、５・・・同軸型真空アーク蒸着源、６・・・電源装置、７・・・除電ユニット、７’・・・除電ユニット、７”・・・除電ユニット、８・・・ガス供給系、９・・・真空排気系、
１１・・・蒸着材料、１２・・・カソード電極、１３・・・トリガ電極、１４・・・絶縁碍子、
２３・・・アノード電極、
３１・・・トリガ電源、３２・・・アーク電源、３３・・・コンデンサユニット、
４１・・・ガス供給源、４２・・・仕切りバルブ、
５１・・・ターボ分子ポンプ、５２・・・仕切りバルブ、５３・・・ロータリポンプ、５４・・・調整バルブ、
７１・・・電流導入端子、７２・・・板ばね、７３・・・ねじ、７４・・・電流導入端子、７５・・・ビーム加速用電源、７６・・・電子銃、
１０４・・・基板、１０５・・・同軸型真空アーク蒸着源、１０６・・・電源装置、
１１１・・・蒸着材料、１１２・・・カソード電極、１１３・・・トリガ電極、１１４・・・絶縁碍子、１２３・・・アノード電極、
１３１・・・トリガ電源、１３２・・・アーク電源、１３３・・・コンデンサユニット、
DESCRIPTION OF SYMBOLS 1 ... Fine particle film manufacturing apparatus, 2 ... Vacuum chamber, 3 ... Substrate stage, 3a ... Substrate holder, 3b ... Rotation mechanism, 4 ... Insulating substrate, 5 ... Coaxial Type vacuum arc evaporation source, 6 ... power supply, 7 ... static elimination unit, 7 '... static elimination unit, 7 "... static elimination unit, 8 ... gas supply system, 9 ... vacuum exhaust system,
DESCRIPTION OF SYMBOLS 11 ... Evaporation material, 12 ... Cathode electrode, 13 ... Trigger electrode, 14 ... Insulator,
23 ... Anode electrode,
31 ... Trigger power supply, 32 ... Arc power supply, 33 ... Capacitor unit,
41 ... Gas supply source, 42 ... Partition valve,
51 ... turbo molecular pump, 52 ... partition valve, 53 ... rotary pump, 54 ... regulating valve,
71 ... current introduction terminal, 72 ... leaf spring, 73 ... screw, 74 ... current introduction terminal, 75 ... power source for beam acceleration, 76 ... electron gun,
104 ... Substrate, 105 ... Coaxial vacuum arc deposition source, 106 ... Power supply device,
111 ... Vapor deposition material, 112 ... Cathode electrode, 113 ... Trigger electrode, 114 ... Insulator, 123 ... Anode electrode,
131 ... Trigger power supply, 132 ... Arc power supply, 133 ... Capacitor unit,
Claims (8)
前記絶縁基板を除電しながら、前記絶縁基板に前記微粒子を付着させることを特徴とする微粒子膜の製造方法。 A trigger electrode and a cathode electrode having at least a tip formed of a metal material for forming fine particles are arranged adjacent to each other with an insulator interposed therebetween, and are coaxially formed around the cathode electrode and the trigger electrode. Using a coaxial vacuum arc deposition source in which an anode electrode is disposed, and generating a trigger discharge in a pulsed manner between the trigger electrode and the anode electrode, thereby generating an arc between the cathode electrode and the anode electrode. Discharge is intermittently induced to form a plasma of the metal material for producing the fine particles, and ions of the metal material for producing the fine particles in the plasma are caused to fly to the front of the coaxial vacuum arc deposition source. In a method for producing a fine particle film in which fine particles having a predetermined particle size of a metal material are attached on an insulating substrate ,
A method for producing a fine particle film, wherein the fine particles are adhered to the insulating substrate while removing electricity from the insulating substrate.
トリガ電極と微粒子作成用金属材料で少なくとも先端部が構成されたカソード電極とが、絶縁碍子を挟んで隣接して配置されてなり、前記カソード電極と前記トリガ電極との周りに同軸状に筒状のアノード電極が配置されている同軸型真空アーク蒸着源と、
絶縁基板を載せるための基板ステージと、
成膜中の前記絶縁基板を除電する除電手段とを備えた微粒子膜の製造装置。 A vacuum chamber;
A trigger electrode and a cathode electrode having at least a tip formed of a metal material for forming fine particles are arranged adjacent to each other with an insulator interposed therebetween, and are coaxially formed around the cathode electrode and the trigger electrode. A coaxial vacuum arc deposition source in which an anode electrode of
A substrate stage for mounting an insulating substrate;
An apparatus for producing a fine particle film , comprising: a neutralizing unit that neutralizes the insulating substrate during film formation .
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