JP2012528452A - プラズマ化学のための電極表面の材料および構造 - Google Patents
プラズマ化学のための電極表面の材料および構造 Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B18/00—Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body
- A61B18/04—Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body by heating
- A61B18/042—Surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body by heating using additional gas becoming plasma
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32348—Dielectric barrier discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
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- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
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- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
- H05H1/2418—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the electrodes being embedded in the dielectric
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
- H05H1/2431—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes using cylindrical electrodes, e.g. rotary drums
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
- H05H1/2443—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube
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- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/2406—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes
- H05H1/2443—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube
- H05H1/245—Generating plasma using dielectric barrier discharges, i.e. with a dielectric interposed between the electrodes the plasma fluid flowing through a dielectric tube the plasma being activated using internal electrodes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
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Abstract
Description
本願は、国際出願US2009/045708号(2009年5月29日出願、Moore他)を基礎とする優先権の利益を主張する。該出願は、米国仮出願第61/057,667号(2008年5月30日出願、Moore他、名称「PLASMA−BASED CHEMICAL SOURCE DEVICE AND METHOD OF USE THEREOF」)を基礎とする優先権の利益を主張する。これらの出願の全内容が、参照により本明細書に引用される。
本開示は、表面加工および材料の除去または堆積のためのプラズマデバイスおよび加工に関する。特に、本開示は、選択された含有物に特有の励起状態化学種(例えば、励起光子)と共に、プラズマデバイス内の化学反応性のプラズマ生成された化学種を生成および方向付けるための装置および方法に関する。
大気圧および大気圧に近い液体および気体等の密度の高い媒体内の放電により、適切な条件において、プラズマ形成を生じることができる。プラズマは、イオン、ラジカル、電子、励起状態(例えば、準安定)種、分子断片、光子等の大量の化学種を作成するための独自の能力を有する。プラズマ電子温度および電子密度を調節することにより、種々の内部エネルギー状態または外部運動エネルギー分散においてプラズマ化学種が生成され得る。さらに、プラズマの空間的、時間的および温度特性を調整することにより、プラズマ種および関連付けられた光子束によって照射される材料に特定の変化が生じる。プラズマは、プラズマ光子によって照射される生物学的および他の材料内の光化学および光触媒反応経路を開始するために十分なエネルギーを有する励起紫外光子を含む光子を生成することもできる。
一実施形態では、前駆体は、電源14からの電気エネルギーによって着火される場合、またはイオン化媒体16から形成される粒子(電子、光子、または制限されたおよび選択的な化学反応性の他のエネルギー伝達種)との衝突を実行する場合に、イオン、電子、励起状態(例えば、準安定)種、分子断片(例えば、ラジカル)等の、反応種を形成可能ないずれかの化学種であり得る。特に、適合される前駆体は、ハロゲン化アシル、アルコール、アルデヒド、アルカン、アルケン、アミド、アミン、ブチル、石炭酸、シアン酸塩、イソシアン酸塩、エステル、エーテル、エチル、ハロゲン化合物、ハロアルカン、ヒドロキシル、ケトン、メチル、硝酸塩、ニトロ、ニトリル、亜硝酸塩、ニトロソ、過酸化物、ヒドロペルオキシド、酸素、水素、窒素、およびその組み合わせ等の種々の反応性官能基を含み得る。実施形態において、化学的前駆体は、ジクロロメタン、トリクロロメタン、四塩化炭素、ジフルオロメタン、トリフルオロメタン、四フッ化炭素等、過酸化炭素、アセトン過酸化物、ベンゾイル過酸化物等のハロゲン化アルキル、メタノール、エタノール、イソプロパノール、エチレングリコール等の過酸化物、プロピレングリコール等のアルコール、NaOH、KOH、アミン、アルキル、アルケン等のアルカリであり得る。かかる化学的前駆体は、実質的に純粋、混合された、または溶解可能な形態で適用され得る。
(1)γ=Γsecondary/Γion
式(1)において、γは二次電子放射収率または係数、Γsecondaryは、電子束であり、Γionはイオン束である。二次放射は、イオン衝撃衝突が二次電子放射を誘発するために十分なエネルギーを有する場合に、コーティング24上へのプラズマ種(イオン)の衝撃によって生じ、このためγモード放出を生じさせる。概して、放出は、気体内(αモード放出)よりも、電極表面において優先的に生じる(つまりγ>1)場合、γモードであると言われる。言い換えると、コーティング24と衝突するイオン毎に、所定の数の二次電子が放射される。このため、γは、Γsecondary(例えば、電子束)とΓion(例えば、イオン束)との割合として考えられ得る。
(2)厚さ=1/Nσ
式(2)において、Nは散乱中心の数であり、散乱中心は、イオン化媒体、前駆体および大気気体の分子であり得る。このため、Nは媒体密度を定義する。変数σは散乱中心の平均粒子断面である。シース層33の厚さはNとσとの積に反比例する。このため、Nおよびσの減少により、より厚いシース層33が提供される。より低いσが、水素およびヘリウム等の小さい断面を有する分子を持つ特定のイオン化媒体化合物を使用して提供され得る。変数Nは、気体密度を低減するためにイオン化媒体を加熱し、プラズマ反応を維持するために必要な最低量に、提供される媒体量を制限することで、小さくし得る。
式(3)は、エネルギーEの電子e(E)が、気体粒子Xと相互作用する、非弾性(エネルギー消費)衝突を示す反応速度Rに関する。衝突の結果、電子は、エネルギーをXに移転し得る。衝突後、電子および粒子は異なるエネルギーを有する。この反応速度または効率は、特定の反応のエネルギー依存断面σ(E)によって制御される。
図18Aは、さらに、内部電極1122が組織「T」(図16を参照)に触れ、従ってDT<0となる条件を示す。内部電極1122が組織「T」に触れると、化学的効果は大部分がブロックされ、一方でバルク加熱効果が強化される。この場合は、I2Rまたはj2ρ(オームの)加熱が優勢となっている(dominated)。内部電極1122が組織「T」に触れると、内部電極は、組織へ熱を熱的に伝導させる。さらに、内部電極1122が、組織「T」(触れる場合)に静電結合され、そこへエネルギーを電気的に伝導させる。さらに、内部電極1122が組織に触れると、反応した組織は移動し、反応していない組織が露出する。
実施例1について、プラズマ放出の実施例のグレイスケール写真を示す図21を参照する。写真は、本開示に従う種々の領域を示す図を伴っている。図21は、内部電極2102、外部電極2104、および励起電子シース層2106を示す。動作範囲LR、2およびLR、3が識別される。励起電子シース層2106は、内部電極2102を中心とする領域の周囲に概して紫色を有するものとして写真撮影された。概して紫色の励起電子シース層2106の一般的な厚さは、内部電極2102の遠位端付近の約LR、3の厚さと、電子シース2106が外部電極2104内に延在を開始する領域内の約LR、2の厚さとを有した。プラズマシステムは、イオン化媒体としてヘリウム気体を利用して図14および15に示されるようにセットアップされ、これは、比較的高いσAr(E)を有し、ヘリウム原子の比較的高い電子衝突断面のために、位置DTにおいてLR3が小さくなり、二次電子の欠如が生じる。原料化学のσfeedstock(E)は同様に作用する。
実施例2について、プラズマ放出の一実施例のカラー写真を示す図22を参照する。写真は、本開示に従う種々の領域を示す図面を伴っている。図22は、内部電極2108、外部電極2110、および励起電子シース層2112を示す。動作範囲LR、2およびLR、3が識別される。励起電子シース層2112は、内部電極2108を中心とする領域の周囲に概してオレンジ様の色を有するものとして撮影されている。概してオレンジ様の励起電子シース層2112の一般的な厚さは、内部電極2108の遠位端付近における約LR、3の厚さと、励起電子シース層2106が外部電極2110内への延在を開始する領域内の約LR、2の厚さとを有する。プラズマシステムが、比較的低いσを有するイオン化媒体としてアルゴン気体を利用して、図14および15に示されるようにセットアップされ、その結果として、LR3が大きくなり、位置DTにおいて、多数の励起二次電子が生じる。オレンジ様のシース層を含んだプラズマ流出物は、延長された領域LR3において、実施例1のLR3よりも明るくかつ大きく、励起電子との増大した衝突による気体原子のより効率的な励起を示す。さらに、プラズマ流出物は、作動距離LR3内の励起電子によって生成されると考えられる一致したより大きいオレンジ様の層を含んでいた。
本発明は、例えば、以下の項目も提供する。
(項目1)
内部電極と、該内部電極の周囲で同軸上に配置された外部電極とを含むプラズマデバイスであって、該内部電極および該外部電極のうちの少なくとも1つは、合金から形成され、かつ、少なくともその一部を覆う誘電体コーティングを含むプラズマデバイスと、
該プラズマデバイスに連結され、かつ、該プラズマデバイスにイオン化媒体を供給するように構成されたイオン化媒体源と、
該内部電極および該外部電極に連結され、かつ、該プラズマデバイスにおいて該イオン化媒体を着火してプラズマ流出物を形成するように構成された電源と
を備えている、プラズマシステム。
(項目2)
前記誘電体コーティングは、酸化物、窒化物、自然酸化物、および自然窒化物から成る群より選択される、項目1に記載のプラズマシステム。
(項目3)
前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、項目1に記載のプラズマシステム。
(項目4)
前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含む、項目1に記載のプラズマシステム。
(項目5)
前記複数の溝は、前記内部電極および前記外部電極のうちの少なくとも1つの縦軸に平行に配置されている、項目4に記載のプラズマシステム。
(項目6)
前記複数の溝は、らせん構成で配置されている、項目4に記載のプラズマシステム。
(項目7)
前記コーティングは、複数のナノ構造孔を含む、項目1に記載のプラズマシステム。
(項目8)
前記複数の孔は、該複数の孔の内部に配置された少なくとも1つの前駆体原料を含む、項目7に記載のプラズマシステム。
(項目9)
イオン化媒体を受け取るように構成されたプラズマデバイスであって、
実質的に円筒形の管形状を有する外部電極と、
該外部電極内で同軸上に配置された内部電極と
を備え、
該内部電極および該外部電極のうちの少なくとも1つは、合金から形成され、かつ、少なくともその一部を覆う自然酸化物または自然窒化物から形成されたコーティングを含む、
プラズマデバイス。
(項目10)
前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、項目9に記載のプラズマシステム。
(項目11)
前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含み、該複数の溝は、らせん構成、または、該内部電極および該外部電極のうちの少なくとも1つの縦軸と平行のうちの少なくとも1つで配置されている、項目9に記載のプラズマシステム。
(項目12)
前記コーティングは、複数のナノ構造孔を含む、項目9に記載のプラズマシステム。
(項目13)
前記複数の孔は、該複数の孔の内部に配置された少なくとも1つの前駆体原料を含む、項目12に記載のプラズマシステム。
(項目14)
プラズマデバイスであって、
実質的に円筒形の管形状を有する外部電極であって、合金から形成され、かつ、該外部電極の内面に配置された誘電体コーティングを含み、該誘電体コーティングは、第1の二次的放射電子源を提供するように構成されている、外部電極と、
該外部電極内で同軸上に配置された内部電極であって、合金から形成され、かつ、該内部電極の外面に配置された誘電体コーティングを含み、該誘電体コーティングは、第2の二次的放射電子源を提供するように構成されている、内部電極と
を含むプラズマデバイスと、
該プラズマデバイスに連結され、かつ、該プラズマデバイスにイオン化媒体を供給するように構成されたイオン化媒体源と、
該内部電極および該外部電極に連結された電源と
を備え、
該電源は、該プラズマデバイスにおいて該イオン化媒体を着火することにより、プラズマ流出物を形成するように構成され、
該プラズマ流出物は、所定の厚さの第1の電子シース層であって、該第1の二次的放射電子源から形成された第1の電子シース層と、所定の厚さの第2の電子シース層であって、該第2の二次的放射電子源から形成される第2の電子シース層とを有する、
プラズマシステム。
(項目15)
前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、項目14に記載のプラズマシステム。
(項目16)
前記誘電体コーティングは、酸化物、窒化物、自然酸化物および自然窒化物から成る群より選択される、項目14に記載のプラズマシステム。
(項目17)
前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含み、該複数の溝は、らせん構成、または、該内部電極および該外部電極のうちの少なくとも1つの縦軸と平行のうちの少なくとも1つで配置されている、項目14に記載のプラズマシステム。
(項目18)
前記コーティングは、該コーティングの内部に配置された少なくとも1つの前駆体原料を有する複数のナノ構造孔を含む、項目14に記載のプラズマシステム。
(項目19)
前記第1の電子シース層および前記第2の電子シース層は、中空陰極効果を生じるように重複している、項目14に記載のプラズマシステム。
(項目20)
前記第1の電子シース層および前記第2の電子シース層が重複して中空陰極効果を生じるように、前記外部電極の誘電体コーティング、前記内部電極の誘電体コーティング、および前記電源のうちの少なくとも1つは、該第1の電子シース層および該第2の電子シース層の厚さを調整するように適合されている、項目14に記載のプラズマシステム。
Claims (20)
- 内部電極と、該内部電極の周囲で同軸上に配置された外部電極とを含むプラズマデバイスであって、該内部電極および該外部電極のうちの少なくとも1つは、合金から形成され、かつ、少なくともその一部を覆う誘電体コーティングを含むプラズマデバイスと、
該プラズマデバイスに連結され、かつ、該プラズマデバイスにイオン化媒体を供給するように構成されたイオン化媒体源と、
該内部電極および該外部電極に連結され、かつ、該プラズマデバイスにおいて該イオン化媒体を着火してプラズマ流出物を形成するように構成された電源と
を備えている、プラズマシステム。 - 前記誘電体コーティングは、酸化物、窒化物、自然酸化物、および自然窒化物から成る群より選択される、請求項1に記載のプラズマシステム。
- 前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、請求項1に記載のプラズマシステム。
- 前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含む、請求項1に記載のプラズマシステム。
- 前記複数の溝は、前記内部電極および前記外部電極のうちの少なくとも1つの縦軸に平行に配置されている、請求項4に記載のプラズマシステム。
- 前記複数の溝は、らせん構成で配置されている、請求項4に記載のプラズマシステム。
- 前記コーティングは、複数のナノ構造孔を含む、請求項1に記載のプラズマシステム。
- 前記複数の孔は、該複数の孔の内部に配置された少なくとも1つの前駆体原料を含む、請求項7に記載のプラズマシステム。
- イオン化媒体を受け取るように構成されたプラズマデバイスであって、
実質的に円筒形の管形状を有する外部電極と、
該外部電極内で同軸上に配置された内部電極と
を備え、
該内部電極および該外部電極のうちの少なくとも1つは、合金から形成され、かつ、少なくともその一部を覆う自然酸化物または自然窒化物から形成されたコーティングを含む、
プラズマデバイス。 - 前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、請求項9に記載のプラズマシステム。
- 前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含み、該複数の溝は、らせん構成、または、該内部電極および該外部電極のうちの少なくとも1つの縦軸と平行のうちの少なくとも1つで配置されている、請求項9に記載のプラズマシステム。
- 前記コーティングは、複数のナノ構造孔を含む、請求項9に記載のプラズマシステム。
- 前記複数の孔は、該複数の孔の内部に配置された少なくとも1つの前駆体原料を含む、請求項12に記載のプラズマシステム。
- プラズマデバイスであって、
実質的に円筒形の管形状を有する外部電極であって、合金から形成され、かつ、該外部電極の内面に配置された誘電体コーティングを含み、該誘電体コーティングは、第1の二次的放射電子源を提供するように構成されている、外部電極と、
該外部電極内で同軸上に配置された内部電極であって、合金から形成され、かつ、該内部電極の外面に配置された誘電体コーティングを含み、該誘電体コーティングは、第2の二次的放射電子源を提供するように構成されている、内部電極と
を含むプラズマデバイスと、
該プラズマデバイスに連結され、かつ、該プラズマデバイスにイオン化媒体を供給するように構成されたイオン化媒体源と、
該内部電極および該外部電極に連結された電源と
を備え、
該電源は、該プラズマデバイスにおいて該イオン化媒体を着火することにより、プラズマ流出物を形成するように構成され、
該プラズマ流出物は、所定の厚さの第1の電子シース層であって、該第1の二次的放射電子源から形成された第1の電子シース層と、所定の厚さの第2の電子シース層であって、該第2の二次的放射電子源から形成される第2の電子シース層とを有する、
プラズマシステム。 - 前記合金は、アルミニウム合金およびチタニウム合金から成る群より選択される、請求項14に記載のプラズマシステム。
- 前記誘電体コーティングは、酸化物、窒化物、自然酸化物および自然窒化物から成る群より選択される、請求項14に記載のプラズマシステム。
- 前記内部電極および前記外部電極のうちの少なくとも1つは、それぞれ、外部表面および内部表面に配置された複数の溝を含み、該複数の溝は、らせん構成、または、該内部電極および該外部電極のうちの少なくとも1つの縦軸と平行のうちの少なくとも1つで配置されている、請求項14に記載のプラズマシステム。
- 前記コーティングは、該コーティングの内部に配置された少なくとも1つの前駆体原料を有する複数のナノ構造孔を含む、請求項14に記載のプラズマシステム。
- 前記第1の電子シース層および前記第2の電子シース層は、中空陰極効果を生じるように重複している、請求項14に記載のプラズマシステム。
- 前記第1の電子シース層および前記第2の電子シース層が重複して中空陰極効果を生じるように、前記外部電極の誘電体コーティング、前記内部電極の誘電体コーティング、および前記電源のうちの少なくとも1つは、該第1の電子シース層および該第2の電子シース層の厚さを調整するように適合されている、請求項14に記載のプラズマシステム。
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JP2012513021A Ceased JP2012528452A (ja) | 2008-05-30 | 2009-09-30 | プラズマ化学のための電極表面の材料および構造 |
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JP2012528453A (ja) | 2012-11-12 |
EP2435206B1 (en) | 2016-11-09 |
WO2010138105A1 (en) | 2010-12-02 |
EP2435607A4 (en) | 2015-01-07 |
EP2297377B1 (en) | 2017-12-27 |
WO2010138104A1 (en) | 2010-12-02 |
EP2435206A1 (en) | 2012-04-04 |
JP2012528454A (ja) | 2012-11-12 |
EP2435206A4 (en) | 2015-01-14 |
JP2015134167A (ja) | 2015-07-27 |
US20110139751A1 (en) | 2011-06-16 |
EP2435607A1 (en) | 2012-04-04 |
EP2434975A1 (en) | 2012-04-04 |
EP2435607B1 (en) | 2016-07-20 |
WO2010138102A1 (en) | 2010-12-02 |
EP2434975A4 (en) | 2014-12-24 |
EP2297377A4 (en) | 2014-08-20 |
EP2297377A1 (en) | 2011-03-23 |
WO2010138103A1 (en) | 2010-12-02 |
EP2434975B1 (en) | 2018-07-11 |
US9288886B2 (en) | 2016-03-15 |
JP2011522381A (ja) | 2011-07-28 |
WO2009146432A1 (en) | 2009-12-03 |
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