JP5892581B2 - Plasma process equipment - Google Patents
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- JP5892581B2 JP5892581B2 JP2011178544A JP2011178544A JP5892581B2 JP 5892581 B2 JP5892581 B2 JP 5892581B2 JP 2011178544 A JP2011178544 A JP 2011178544A JP 2011178544 A JP2011178544 A JP 2011178544A JP 5892581 B2 JP5892581 B2 JP 5892581B2
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Description
本発明は、プラズマプロセス装置に関し、特にプラズマ生成部で分解されることで分解種を生成するためのガスに加えて、当該分解されたガスと気相反応をさせるためのガスを別途供給するプラズマプロセス装置に関する。 The present invention relates to a plasma process apparatus, and in particular, plasma that separately supplies a gas for generating a decomposition species by being decomposed by a plasma generation unit and a gas for causing a gas phase reaction with the decomposed gas. It relates to process equipment.
本願発明をこの分野に限定するものではないが、アモルファスシリコン薄膜を製造するためのプラズマプロセス装置は、従来から、いくつか知られている。 Although the present invention is not limited to this field, several plasma processing apparatuses for producing an amorphous silicon thin film have been conventionally known.
例えば、特許文献１には、アノード表面に基板を設置し、カソード板を反応容器内に反応ガスを基板面内に均一に導入するシャワーヘッド型導入口と一体化し、カソード板表面形状を長円筒状の窪みを格子状に並べたものを溝で連結させた凹凸のあるものとし、長円筒状の凹部にその径より小さな径の孔を作製し反応ガス導入口とするプラズマＣＶＤ装置が開示されている。 For example, Patent Document 1 discloses that a substrate is installed on the anode surface, the cathode plate is integrated with a shower head type inlet for uniformly introducing the reaction gas into the reaction vessel into the reaction vessel, and the cathode plate surface shape is a long cylinder. A plasma CVD apparatus has been disclosed in which a hollow having a shape smaller than the diameter of a long cylindrical recess is formed as a reaction gas inlet by providing a concave and convex shape in which hollows arranged in a grid are connected by grooves. ing.
特許文献１に記載の方法によると、カソード電極表面の長円筒状の凹部付近に高密度のプラズマスポットが生成し、ガス分解に有効な高密度プラズマがアノード上に設置された基板から空間的に分離生成されることによるラジカル分離効果により、高品質な薄膜シリコンの高速・大面積作製が可能である（このようにプラズマスポットを生成させる凹部を「スポット型凹部」と呼ぶ）。しかし、アモルファスシリコンには、特性の光劣化という問題があり、その問題解決のためには、上記効果だけでは十分でなく、光劣化率の増大に繋がる高次シラン種の膜成長への寄与を他のメカニズムでさらに削減する必要がある。
According to the method described in Patent Document 1, a high-density plasma spot is generated in the vicinity of a long cylindrical recess on the surface of the cathode electrode, and a high-density plasma effective for gas decomposition is spatially generated from the substrate placed on the anode. Due to the radical separation effect by the separation and generation, high-quality thin-film silicon can be manufactured at high speed and in a large area (the recess that generates a plasma spot is called a “spot-type recess”). However, amorphous silicon has a problem of photodegradation of the characteristics, and in order to solve the problem, the above effect is not sufficient, and it contributes to the film growth of higher order silane species that leads to an increase in the photodegradation rate. It needs to be further reduced by other mechanisms.
本発明の課題は、プラズマプロセス装置において、気相中に含まれるところのプロセス上有害な成分（例えば、アモルファスシリコン膜について言えば、その光劣化と関連する高次シラン系ラジカル）を低減させる等の、プラズマ生成部を通過したガスの気相反応支援を行い、プラズマプロセス装置による製膜性能、その他の表面処理性能を更に向上させることにある。 An object of the present invention is to reduce a process harmful component (for example, a high-order silane radical related to photodegradation in the case of an amorphous silicon film) contained in a gas phase in a plasma processing apparatus. The object is to support the gas phase reaction of the gas that has passed through the plasma generation unit, and to further improve the film forming performance by the plasma process apparatus and other surface treatment performance.
本発明の一側面によれば、反応容器と、前記反応容器内に収容された放電用の電極体と、前記電極体上に設けられたプラズマ生成領域と、前記電極体上の前記プラズマ生成領域に第１のガスを導入する第１のガス導入部と、前記反応容器内の前記プラズマ生成領域と異なる箇所に前記第１の種類のガスとは異種の第２のガスを導入する第２のガス導入部とを設け、前記反応容器中に入れた部材を処理するプラズマプロセス装置が与えられる。
ここにおいて、前記第１のガスは、前記プラズマ生成領域中で分解して分解種を生成するガスであり、前記第２のガスは、前記分解種の少なくとも一部と気相反応するガスであってよい。
また、前記第１のガス導入部は前記第１のガスを輸送する少なくとも１本の第１のガス導入管路と、前記第１のガス導入管路に連通して前記第１のガスを前記プラズマ生成領域に導入する少なくとも１つの第１の導入孔とを有し、前記第２のガス導入部は前記第２のガスを輸送する少なくとも１本の第２のガス導入管路と、前記第２のガス導入管路に連通して前記第２のガスを前記反応容器内に導入する少なくとも１つの第２の導入孔とを有してよい。
また、複数の前記第１の導入孔を前記電極体表面に所定パターンで設けてよい。
また、前記第１の導入孔は前記電極体に設けられた凹部内に開口してよい。
また、前記第２の導入孔は前記電極体上であって前記凹部内以外の箇所に開口してよい。
また、前記電極体は第１電極と第２電極とを有する平行電極であり、前記第１の導入孔は前記第１電極の前記第２電極側の表面に開口してよい。
また、前記凹部は複数のスポット型凹部と前記スポット型凹部間を接続する溝型凹部とを含んでよい。
また、前記第１の導入孔は前記スポット型凹部内に開口してよい。
また、前記第２の導入孔を前記第１電極の前記第２電極側の表面に開口してよい。
また、前記第２の導入孔を前記第１電極の前記第２電極側の表面上の前記溝型凹部内に開口してよい。
また、前記第２の導入孔を前記第１電極の前記第２電極側の表面上であって前記凹部が設けられていない箇所に開口してよい。
また、前記電極体は前記第２電極の前記第１電極側でない側に第３電極を更に有し、前記第２電極は前記第１電極側から前記第３電極側に貫通する複数の貫通孔を有し、前記第２電極は更に前記第２の導入孔を開口し、前記第３の電極の前記第２の電極に対向する表面に置かれた部材を処理してよい。
また、前記電極体は前記第２電極の前記第１電極側でない側に第３電極を更に有し、前記第２電極は前記第１電極側から前記第３電極側に貫通するとともに前記第１電極上の前記スポット型凹部に整列した複数の貫通孔を有し、前記第２電極は更に前記第２の導入孔を開口し、前記第３の電極の前記第２の電極に対向する表面に置かれた部材を処理してよい。
According to one aspect of the present invention, a reaction vessel, a discharge electrode body accommodated in the reaction vessel, a plasma generation region provided on the electrode body, and the plasma generation region on the electrode body A first gas introduction part for introducing a first gas into the second gas, and a second gas for introducing a second gas different from the first type gas into a location different from the plasma generation region in the reaction vessel. There is provided a plasma processing apparatus provided with a gas introduction part and processing a member placed in the reaction vessel.
Here, the first gas is a gas that decomposes in the plasma generation region to generate decomposition species, and the second gas is a gas that reacts in a gas phase with at least a part of the decomposition species. It's okay.
In addition, the first gas introduction unit communicates with the first gas introduction conduit and at least one first gas introduction conduit that transports the first gas, and the first gas is introduced into the first gas introduction passage. At least one first introduction hole for introducing into the plasma generation region, and the second gas introduction section includes at least one second gas introduction conduit for transporting the second gas; And at least one second introduction hole that communicates with two gas introduction pipes and introduces the second gas into the reaction vessel.
A plurality of the first introduction holes may be provided in a predetermined pattern on the surface of the electrode body.
The first introduction hole may be opened in a recess provided in the electrode body.
The second introduction hole may be opened on the electrode body at a place other than the inside of the recess.
The electrode body may be a parallel electrode having a first electrode and a second electrode, and the first introduction hole may be opened on a surface of the first electrode on the second electrode side.
The recess may include a plurality of spot-type recesses and a groove-type recess that connects the spot-type recesses.
The first introduction hole may be opened in the spot-type recess.
The second introduction hole may be opened on the surface of the first electrode on the second electrode side.
The second introduction hole may be opened in the groove-type recess on the surface of the first electrode on the second electrode side.
Further, the second introduction hole may be opened at a location on the surface of the first electrode on the second electrode side where the concave portion is not provided.
The electrode body further includes a third electrode on a side of the second electrode that is not on the first electrode side, and the second electrode has a plurality of through holes penetrating from the first electrode side to the third electrode side. The second electrode may further open the second introduction hole, and may process a member placed on the surface of the third electrode facing the second electrode.
The electrode body further includes a third electrode on a side of the second electrode that is not on the first electrode side, and the second electrode penetrates from the first electrode side to the third electrode side and the first electrode. A plurality of through-holes aligned with the spot-type recesses on the electrode, the second electrode further opening the second introduction hole, and a surface of the third electrode facing the second electrode; The placed member may be processed.
本発明によれば、分解種の生成を目的としたプラズマ生成部へのガス導入の他に、分解種との気相反応を目的としたガスを独立に導入することで、分解種の所望の気相反応を促進し、製膜等の処理対象となる基板におけるプロセス反応種の選択性・制御性を向上させることができる。 According to the present invention, in addition to introducing the gas into the plasma generation unit for the purpose of generating the decomposition species, the gas intended for the gas phase reaction with the decomposition species is independently introduced, so that the desired decomposition species can be obtained. The gas phase reaction can be promoted, and the selectivity and controllability of the process reaction species in the substrate to be processed such as film formation can be improved.
本発明のプラズマプロセス装置によれば、プラズマ生成部へガス分解を用途とするガスを、それ以外の空間へ気相反応を用途とするガスを別々に供給することにより、分解種の所望の気相反応を促進し、基板におけるプロセス反応種の選択性・制御性の向上が可能となる。なお、これらのガスは通常は互いに異種のものを使用するが、ここで言う「異種のガス」とは、種類の異なるガス又は混合比を異にする混合ガスを意味する。 According to the plasma processing apparatus of the present invention, a gas for gas decomposition is supplied to the plasma generation unit, and a gas for gas phase reaction is separately supplied to the other space, thereby obtaining a desired gas of decomposition species. The phase reaction is promoted, and the selectivity and controllability of process reaction species on the substrate can be improved. Although these gases are usually different from each other, the “different gases” referred to here mean different types of gases or mixed gases having different mixing ratios.
これにより、例えばアモルファスシリコン製膜を目的とするＳｉＨ４又はＳｉＨ４／Ｈ２プラズマにおいては、ガス分解による膜堆積種の生成を目的としたプラズマ生成部へのＳｉＨ４ガス又はＳｉＨ４／Ｈ２混合ガスの導入とは別に、分解種との気相反応を目的としたＨ２ガスをそれ以外の空間へ独立に導入し、反応性の高い分解種ＳｉＨｘ（ｘ≦２）とＨ２との反応を促進して、ＳｉＨｘ（ｘ≦２）とＳｉＨ４親分子との反応を抑制することができる。かくして、ＳｉＨ４へのＳｉＨ２の挿入反応が引き金となる高次シラン種の生成が抑制可能となり、水素化アモルファスシリコンの光劣化率と相関関係が認められている高次シラン系ラジカル（Ｓｉ４Ｈ９等）の膜成長への寄与率をより一層低減して、光安定性に優れたアモルファスシリコンの製膜が可能となる効果が得られる。（ＳｉＨ４との反応による分解種ＳｉＨ２の消失：ＳｉＨ２＋ＳｉＨ４→Ｓｉ２Ｈ６の反応速度定数は、Ｈ２との反応による分解種ＳｉＨ２の消失ＳｉＨ２＋Ｈ２→ＳｉＨ４の反応速度定数よりも大きく、ＳｉＨ４との反応は起こりやすいが、Ｈ２密度増加によってＨ２との反応を促進することにより、抑制が可能と考えられる。） Thereby, for example, in SiH 4 or SiH 4 / H 2 plasma for the purpose of forming an amorphous silicon film, SiH 4 gas or SiH 4 / H 2 for the plasma generation unit for the purpose of generating a film deposition species by gas decomposition. Separately from the introduction of the mixed gas, H 2 gas intended for gas phase reaction with the decomposed species is independently introduced into the other space, and the highly reactive decomposed species SiH x (x ≦ 2) and H 2 The reaction of SiH x (x ≦ 2) and the SiH 4 parent molecule can be suppressed. Thus, the generation of higher order silane species triggered by the insertion reaction of SiH 2 into SiH 4 can be suppressed, and higher order silane radicals (Si 4 ) that have been recognized to correlate with the photodegradation rate of hydrogenated amorphous silicon. H 9 etc.) can be further reduced in the rate of contribution to film growth, and an effect can be obtained that enables amorphous silicon film excellent in light stability to be formed. (Disappearance of decomposition species SiH 2 due to reaction with SiH 4 : The reaction rate constant of SiH 2 + SiH 4 → Si 2 H 6 is the disappearance of decomposition species SiH 2 due to reaction with H 2. Reaction of SiH 2 + H 2 → SiH 4 It is larger than the rate constant, and the reaction with SiH 4 is likely to occur. However, it is considered that the reaction can be suppressed by promoting the reaction with H 2 by increasing the H 2 density.
ＳｉＨ４／Ｈ２プラズマを用いた微結晶シリコン製膜の場合は、欠陥密度の増大に繋がるＳｉＨｘ（ｘ≦２）短寿命種の膜成長への寄与率の低減が必要である。このため、ＳｉＨ４親分子との反応によりＳｉＨｘ（ｘ≦２）種の消失が図られることが多いが、微結晶の形成に重要な水素原子がＳｉＨ４との反応（ＳｉＨ４＋Ｈ→ＳｉＨ３＋Ｈ２）により消失してしまうため、ＳｉＨ４との反応によるＳｉＨｘ（ｘ≦２）種の消失促進には限界がある。 In the case of a microcrystalline silicon film using SiH 4 / H 2 plasma, it is necessary to reduce the contribution ratio of SiH x (x ≦ 2) short-lived species to the film growth that leads to an increase in defect density. Therefore, it is often SiH 4 SiH x (x ≦ 2 ) by reaction of the parent molecule species loss is achieved, the reaction (SiH 4 + H → SiH important hydrogen atoms in the formation of crystallites and SiH 4 (3 + H 2 ) disappears, and there is a limit to the promotion of disappearance of SiH x (x ≦ 2) species by reaction with SiH 4 .
本発明のプラズマプロセス装置によれば、分解種との気相反応を目的としたＨ２ガスの単独導入により、ＳｉＨ４ガス流量の増加によるＨ原子の消失を伴うことなく、Ｈ２との反応によってＳｉＨｘ（ｘ≦２）種の消失促進が可能であり、結晶性の低下を防ぎながら高品質膜を作製することができる。 According to the plasma process apparatus of the present invention, the reaction with H 2 without the disappearance of H atoms due to an increase in the flow rate of SiH 4 gas by introducing H 2 gas alone for the purpose of gas phase reaction with decomposition species. Thus, the disappearance of SiH x (x ≦ 2) species can be promoted, and a high-quality film can be produced while preventing a decrease in crystallinity.
さらに、パウダー生成を抑制して、製膜等のプロセス装置の稼働率を向上する効果も得られる。また、電極表面からの面内均一なガス導入により、大面積上への均一なガス供給が可能である。そのため、シリコン系薄膜、特に太陽電池用アモルファスシリコンの生産設備として工業的価値が大きい。また、本発明はアモルファスシリコンや微結晶シリコンの製膜用途に限定されるものではなく、プラズマ生成部を通過したガスの改質が有効である分野であれば、他の半導体薄膜，絶縁体薄膜，金属又は導体薄膜の製造、エッチング，表面処理などのプラズマプロセスへも適用可能である。 Furthermore, it is possible to obtain the effect of suppressing the generation of powder and improving the operating rate of the process apparatus such as film formation. In addition, uniform gas supply over a large area is possible by in-plane uniform gas introduction from the electrode surface. Therefore, industrial value is large as a production facility for silicon-based thin films, particularly amorphous silicon for solar cells. In addition, the present invention is not limited to film formation of amorphous silicon or microcrystalline silicon, and other semiconductor thin films and insulator thin films can be used as long as the modification of the gas that has passed through the plasma generator is effective. It can also be applied to plasma processes such as metal or conductor thin film manufacturing, etching, and surface treatment.
本発明のプラズマプロセス装置に、先に本発明者らが提案した特許文献１に記載のプラズマＣＶＤ装置発明を適用し、電極表面に所定パターンで形成された凹部にプラズマ分解用ガスを導入すれば、当該凹部の内部及び／又はその近傍に、多数の高密度なプラズマスポットが生成される（プラズマ生成部；凹部の形状やプロセス条件により、凸部（つまり、電極表面上で凹部が掘り込まれていない「台地」状部分）近傍に生成される場合もある）。これにより、電極表面においてプラズマ生成部とそれ以外の部分とが区別され、分解種の生成を用途とするガスをプラズマ生成部から、分解種との気相反応を用途とするガスをそれ以外の電極表面から、反応器内に別々に導入することが可能になる。なお、気相反応用ガスの導入孔の配置は、プラズマ生成部を通過したガスが処理対象の部材上で製膜などに使用される前に当該導入口を出た気相反応用ガスと混合されて所望の気相反応が起こる限り、電極表面に限られることなく、反応容器内の他の適切な箇所に設けてよいことに注意されたい。また、電極を第１電極と第２電極とを有する平行電極構成とし、第１電極表面上にプラズマによる分解用ガスの導入口とプラズマ生成部を設けることができる。 If the plasma CVD apparatus invention described in Patent Document 1 previously proposed by the present inventors is applied to the plasma process apparatus of the present invention and a gas for plasma decomposition is introduced into the recesses formed in a predetermined pattern on the electrode surface, A large number of high-density plasma spots are generated in and / or in the vicinity of the concave portion (plasma generating portion; depending on the shape of the concave portion and process conditions, the concave portion is dug on the electrode surface). Not "plateau" -like part) may be generated in the vicinity). As a result, the plasma generating part is distinguished from the other parts on the electrode surface, the gas for use in the generation of decomposition species is supplied from the plasma generation part, and the gas for use in the gas phase reaction with the decomposition species is supplied to the other parts. It can be introduced separately from the electrode surface into the reactor. The gas-phase reaction gas introduction hole is arranged so that the gas that has passed through the plasma generation unit is mixed with the gas-phase reaction gas exiting the introduction port before being used for film formation on the member to be processed. It should be noted that as long as the desired gas phase reaction occurs, it is not limited to the electrode surface and may be provided at other suitable locations in the reaction vessel. In addition, the electrode may be configured as a parallel electrode having a first electrode and a second electrode, and an inlet for a decomposition gas by plasma and a plasma generation unit may be provided on the surface of the first electrode.
これにより、分解種の所望の気相反応を促進し、基板表面におけるプロセス反応種の選択性や制御性の向上が可能となる。さらに、スポット状高密度プラズマ生成部へガス分解を用途とするガスを導入することにより、原料ガスを高い効率で分解・利用しながら薄膜製造などの高速プロセスが可能となる。また、電極表面にパターン状に均一にガス導入を行なう構成は、均一製膜に有効である。 Thereby, the desired gas phase reaction of the decomposition species is promoted, and the selectivity and controllability of the process reaction species on the substrate surface can be improved. Furthermore, by introducing a gas intended for gas decomposition into the spot-shaped high-density plasma generator, a high-speed process such as thin film manufacturing can be performed while the source gas is decomposed and used with high efficiency. In addition, a configuration in which gas is uniformly introduced into the electrode surface in a pattern is effective for uniform film formation.
例えば薄膜シリコン製膜の場合、ＳｉＨ４ガス又はＳｉＨ４／Ｈ２混合ガスを高密度プラズマ生成部（通常は凹部）に導入し、また電極表面上のそれ以外の箇所からＨ２ガス単体を導入すると、高密度プラズマ生成部でＳｉＨ４の分解種と水素原子が高密度に生成され、分解種が基板へ輸送される過程で、反応性の高いＳｉＨｘ（ｘ≦２）はプラズマ生成部以外の電極表面から単体で導入されるＨ２ガス分子との二次反応により消失する。これより、長寿命なＳｉＨ３ラジカルの基板への選択輸送が可能になり、高品質膜成長が達成される。 For example, in the case of thin film silicon film, SiH 4 gas or SiH 4 / H 2 mixed gas is introduced into the high-density plasma generation part (usually a concave part), and H 2 gas alone is introduced from other places on the electrode surface. Then, SiH 4 decomposition species and hydrogen atoms are generated at high density in the high density plasma generation unit, and in the process in which the decomposition species are transported to the substrate, highly reactive SiH x (x ≦ 2) is other than the plasma generation unit. It disappears by a secondary reaction with H 2 gas molecules introduced alone from the electrode surface. As a result, long-life SiH 3 radicals can be selectively transported to the substrate, and high-quality film growth is achieved.
本構成によれば、本発明者らが先に提案した特開２００４−２９６５２６号に記載のプラズマＣＶＤ装置と同様に、電極表面の各凹部付近でのスポット状高密度プラズマの生成により、局所的な高効率ガス分解が可能になる。この構成では、高周波プラズマのシースの振動による電子の統計的加熱及びホロー効果による電子の閉じ込めが起こり、各凹部（入り口）付近でスポット状高密度プラズマが安定に生成されると考えられる。また、第１電極（カソード電極）表面へのイオンの衝突による二次電子の放出（γ作用）は、広い電極表面積によって効果的に起こると考えられる。なお、凹部の形状・プロセス条件により、凸部近傍にスポット状高密度プラズマが生成される場合もある。 According to this configuration, as in the plasma CVD apparatus described in Japanese Patent Application Laid-Open No. 2004-296526 previously proposed by the present inventors, the generation of spot-like high-density plasma in the vicinity of each concave portion on the electrode surface causes local Highly efficient gas decomposition becomes possible. In this configuration, statistical heating of electrons due to vibration of the sheath of the high-frequency plasma and electron confinement due to the hollow effect occur, and it is considered that spot-like high-density plasma is stably generated near each recess (entrance). In addition, it is considered that secondary electron emission (γ action) due to ion collision with the surface of the first electrode (cathode electrode) is effectively caused by a large electrode surface area. Depending on the shape and process conditions of the recess, spot-like high-density plasma may be generated near the protrusion.
これによれば、ガス分解に有効な（高密度）プラズマが基板から離れた位置で生成されることにより、ガス分解により生成した分解種が基板へ輸送される過程で反応性の高い短寿命種が気相反応により消失し、長寿命ラジカルが選択的に基板表面へ輸送されるラジカル分離効果が得られる。 According to this, a (high density) plasma effective for gas decomposition is generated at a position distant from the substrate, so that a short-lived species having high reactivity in the process of transporting the decomposed species generated by gas decomposition to the substrate. Disappears by the gas phase reaction, and a radical separation effect is obtained in which long-lived radicals are selectively transported to the substrate surface.
本構成をＳｉＨ４／Ｈ２プラズマによる薄膜シリコン作製に適用した場合、欠陥密度の高い膜成長の原因となるＳｉＨｘ（ｘ≦２）及びアモルファスシリコンの光劣化率と相関性を有するＳｉ−Ｈ２結合含有量の多い膜成長の原因となるＳｉ４Ｈ９等の高次シランラジカル等の短寿命種が、基板への輸送過程において気相反応により消失し、製膜種として好ましい長寿命なＳｉＨ３ラジカルが基板へ選択的に輸送され、高品質膜の作製が達成される。 When this configuration is applied to the production of thin film silicon by SiH 4 / H 2 plasma, SiH x (x ≦ 2) that causes film growth with a high defect density and Si—H 2 having a correlation with the photodegradation rate of amorphous silicon. Short-lived species such as higher order silane radicals such as Si 4 H 9 that cause film growth with a high bond content disappear due to gas phase reaction in the transport process to the substrate, and long-life SiH preferred as a film-forming species Three radicals are selectively transported to the substrate, and production of a high quality film is achieved.
さらに、高密度プラズマ生成により高効率ガス分解が行われ、且つ電極間に網状グリッドの挿入が無い条件下で、上記ラジカル分離効果を有することは、高品質薄膜シリコンの高速製膜に有効である。 Furthermore, having the above-mentioned radical separation effect under conditions where high-efficiency gas decomposition is performed by high-density plasma generation and no mesh grid is inserted between the electrodes is effective for high-speed film formation of high-quality thin-film silicon. .
また、スポット型凹部間を溝型凹部で相互接続する構成とした場合、スポット型凹部に生成するスポット状プラズマが孤立せずに溝型凹部によって相互に連結可能となるため、特に大面積プロセスにおいて、条件によっては問題となる（スポット状プラズマが電極面上を動き回るなどの）不安定なプラズマ生成状態を防止できる。 In addition, when the spot-type recesses are interconnected by the groove-type recesses, the spot-shaped plasma generated in the spot-type recesses can be connected to each other by the groove-type recesses without being isolated. Depending on the conditions, an unstable plasma generation state (such as spot-like plasma moving around on the electrode surface) can be prevented.
また、更に第２電極に貫通孔を開設するとともに、第２電極の裏面（第１電極と反対側の面）に第３電極を設置した構成では、第１と第２電極間にプラズマが生成され、上述の貫通孔から第３電極へは、分解種が主に拡散により輸送される。第１電極と第２電極間のプラズマ生成領域にガス分解を用途とするガスを、第２と第３電極間に分解種との気相反応を用途とするガスを、別々に供給して分解種の所望の気相反応を促進すれば、第３電極の第２電極側に置かれた基板の表面に与えられるプロセス反応種の選択性や制御性が向上する。 Further, in the configuration in which a through-hole is further opened in the second electrode and the third electrode is installed on the back surface (the surface opposite to the first electrode) of the second electrode, plasma is generated between the first and second electrodes. The decomposed species are transported mainly from the through hole to the third electrode by diffusion. Gas for gas decomposition is applied to the plasma generation region between the first electrode and the second electrode, and gas for gas phase reaction with decomposition species is separately supplied between the second and third electrodes for decomposition. If the desired gas phase reaction of the seed is promoted, the selectivity and controllability of the process reactive species given to the surface of the substrate placed on the second electrode side of the third electrode is improved.
また、第２電極の表裏を貫通する孔が、第１電極へ配置されたスポット型凹部と同じパターンで配置されるようにする（つまり、第２電極の貫通孔が第１電極のスポット型凹部と整列、すなわち位置合わせされたように配置されているようにする）ことにより、第１電極表面に所定パターンで形成された凹部の内部及び／又はその近傍に生成された多数の高密度なプラズマスポットからのガス分解種が高効率で第３電極へ輸送される。 In addition, the holes penetrating the front and back of the second electrode are arranged in the same pattern as the spot-type concave portion arranged in the first electrode (that is, the through-hole of the second electrode is the spot-type concave portion of the first electrode). A plurality of high-density plasmas generated in and / or in the vicinity of the recesses formed in a predetermined pattern on the surface of the first electrode. Gas decomposition species from the spot are transported to the third electrode with high efficiency.
以下、添付図面を参照しながら、本発明を実施するための最良の形態をさらに具体的に説明する。 Hereinafter, the best mode for carrying out the present invention will be described more specifically with reference to the accompanying drawings.
［実施例１］
本実施例では、第１電極の表面のうちの第２電極に対向する側に、多数の凹部、及び異種のガスを独立に導入する多数のガス導入孔を、夫々所定パターンで設ける。製膜などの処理対象の部材である基板は、通常は第２電極の表面のうちの第１電極に対向する側に置く。
[Example 1]
In the present embodiment, a number of recesses and a number of gas introduction holes for independently introducing different kinds of gases are provided in a predetermined pattern on the side of the surface of the first electrode facing the second electrode. A substrate, which is a member to be processed such as film formation, is usually placed on the side of the surface of the second electrode facing the first electrode.
図１は本発明の実施例１に係るプラズマプロセス装置を正面から見た概観図である。 FIG. 1 is a schematic view of a plasma processing apparatus according to a first embodiment of the present invention as viewed from the front.
このプラズマプロセス装置は、反応容器１と、この反応容器内に反応ガスを導入する導入管４、５と、図示しない真空ポンプにより排気する排気管７と、上記反応器内に収容された放電用平行電極（第１電極（カソード電極）２と第２電極（アノード電極）３）と、第１電極２及び第２電極３に電力を供給する電源９とを有する。第２電極３上に基板８などの処理対象部材を設置することで、その表面に薄膜を形成するなどの処理を行う。 The plasma process apparatus includes a reaction vessel 1, introduction pipes 4 and 5 for introducing a reaction gas into the reaction vessel, an exhaust pipe 7 for exhausting by a vacuum pump (not shown), and a discharge vessel accommodated in the reactor. A parallel electrode (first electrode (cathode electrode) 2 and second electrode (anode electrode) 3) and a power source 9 for supplying power to the first electrode 2 and the second electrode 3 are provided. By installing a processing target member such as the substrate 8 on the second electrode 3, processing such as forming a thin film on the surface thereof is performed.
なお、図１では、ガス導入は電極表面に開口した多数のガス導入孔から行なっているが、反応容器１の側方などに設けたガス導入管６に連通するガス導入口からも補助的なガス導入（特に、軽くて拡散しやすいガス分子の場合）を行うことができる。電源９は、通常、高周波又は超高周波を用いるが、直流とすることも可能である。 In FIG. 1, the gas is introduced from a large number of gas introduction holes opened on the surface of the electrode. However, the gas introduction port communicates with the gas introduction pipe 6 provided on the side of the reaction vessel 1 or the like. Gas introduction (especially in the case of gas molecules that are light and easily diffuse) can be performed. The power source 9 normally uses a high frequency or a super high frequency, but may be a direct current.
ここに示した放電用平行電極、つまり第１電極２及び第２電極３、のうち、特に第１電極２の構造に特徴がある。以下、図２及び図３も参照しながら第１電極２を中心に説明する。 Of the discharge parallel electrodes shown here, that is, the first electrode 2 and the second electrode 3, the structure of the first electrode 2 is particularly characteristic. Hereinafter, the first electrode 2 will be mainly described with reference to FIGS.
図２は、本実施例中の放電用平行電極の第１電極（カソード電極）２を示し、具体的には第２電極（アノード電極）３に対向する面の凹凸パターンを示している。図３は図２のＡ−Ａ縦断面図である。 FIG. 2 shows the first electrode (cathode electrode) 2 of the discharge parallel electrode in the present embodiment, and more specifically shows an uneven pattern on the surface facing the second electrode (anode electrode) 3. 3 is a vertical cross-sectional view taken along the line AA of FIG.
第１電極２の表面形状は、図２及び図３に示すように長円筒状のスポット型凹部１３を格子状に並べ、このスポット型凹部１３の隣接するもの同士を溝型凹部１４で連通することにより所定パターンの凹凸を形成したものである。スポット型凹部１３の奥端面（図３ではスポット側凹部１３の最下部（底）にある面）にはガス導入用小孔１２ａが形成されている。凸部、すなわち電極表面のうちの凹状部を掘り込んでいない「台地」状部分には、ガス導入用小孔１２ｂが形成されている。スポット型凹部１３の奥（つまり底よりも下にある部分）にはガス導入管４に連通するガス通路１６が設けられていて、ガス導入用小孔１２ａはガス通路１６を介してガス導入管４に連通している。上述した凸部にはガス導入管５に連通するガス空間が設けてあり、ガス導入用小孔１２ｂはこのガス空間を介してガス導入管５に連通している。なお、ガス導入用小孔１２ｂは凸部上ではなく溝型凹部１４内に開口するようにしても良い。 As shown in FIGS. 2 and 3, the surface shape of the first electrode 2 is such that long cylindrical spot-shaped concave portions 13 are arranged in a lattice shape, and adjacent ones of the spot-shaped concave portions 13 communicate with each other by a groove-shaped concave portion 14. As a result, irregularities of a predetermined pattern are formed. A gas introduction small hole 12a is formed in the back end surface of the spot-type recess 13 (the surface at the bottom (bottom) of the spot-side recess 13 in FIG. 3). A small hole 12b for gas introduction is formed in the “plateau” -shaped portion where the convex portion, that is, the concave portion of the electrode surface is not dug. A gas passage 16 communicating with the gas introduction pipe 4 is provided in the back of the spot-type recess 13 (that is, a portion below the bottom), and the gas introduction small hole 12 a is connected to the gas introduction pipe via the gas passage 16. 4 communicates. The above-described convex portion is provided with a gas space communicating with the gas introduction pipe 5, and the gas introduction small holes 12 b communicate with the gas introduction pipe 5 through this gas space. The gas introduction small hole 12b may be opened in the groove-type recess 14 instead of on the protrusion.
実施例１と実施例２の細部の構造や動作その他は共通するところが多いので、実施例の項の末尾付近でまとめて説明する。 Since the detailed structure and operation of the first embodiment and the second embodiment are common in many cases, they will be described together in the vicinity of the end of the section of the embodiment.
［実施例２］
本発明を特許文献２に開示された電極構成（第２電極の第１電極と対向しない側に第３電極を設ける構成）と組み合わせることも可能である。実施例２はそのような組合せの一例を示す。
[Example 2]
It is also possible to combine the present invention with the electrode configuration disclosed in Patent Document 2 (configuration in which the third electrode is provided on the side of the second electrode not facing the first electrode). Example 2 shows an example of such a combination.
本実施例においては、第２電極内部に気相反応用のガスを供給する空間を設けるとともに、このガス空間には連通せず、第１電極側から第３電極側へ貫通する複数の孔を設ける。また、第２電極の第３電極と対向する表面に複数のガス導入孔を設け、これらのガス導入孔を上述のガス空間に連通させる。第１電極側から第３電極側へ貫通する複数の孔は、第１電極側で供給されたガスの分解種が輸送される経路となり、他方、第２電極表面に開口した複数のガス導入孔からは、上記経路を通して輸送されてきた分解種と気相反応するガスを第２電極内に配設されたガス空間を通して導入する。 In the present embodiment, a space for supplying gas for gas phase reaction is provided inside the second electrode, and a plurality of holes penetrating from the first electrode side to the third electrode side are provided without communicating with the gas space. . Further, a plurality of gas introduction holes are provided on the surface of the second electrode facing the third electrode, and these gas introduction holes are communicated with the above gas space. The plurality of holes penetrating from the first electrode side to the third electrode side serve as a path for transporting decomposed species of the gas supplied on the first electrode side, and on the other hand, a plurality of gas introduction holes opened on the surface of the second electrode Is introduced through a gas space disposed in the second electrode, a gas which reacts with the decomposed species transported through the path.
第２電極の厚みは、第１電極側から第３電極側への分解種の輸送効率を高くするために厚すぎないことが必要で、好ましくは５ｍｍ以下とする。第２電極のガス導入孔は、通常は第３電極と対向する表面上へ設けることが好ましいが、圧力、投入電力、第１電極から導入するガスの条件（混合比）等により、第１電極と対向する表面上に設けることが好ましい場合もある。第２電極の両面（第１電極への対向面と第３電極への対向面の両方）へガス導入孔を設ける構成も可能である。 The thickness of the second electrode needs to be not too thick in order to increase the transport efficiency of the decomposed species from the first electrode side to the third electrode side, and is preferably 5 mm or less. Normally, the gas introduction hole of the second electrode is preferably provided on the surface facing the third electrode, but the first electrode depends on the pressure, input power, conditions of gas introduced from the first electrode (mixing ratio), and the like. It may be preferable to provide it on the surface which opposes. A configuration in which gas introduction holes are provided on both surfaces of the second electrode (both the surface facing the first electrode and the surface facing the third electrode) is also possible.
図４は本発明の実施例２に係るプラズマプロセス装置の放電用平行電極の第１電極（カソード電極）２、及び第２電極３の断面構造を示す概観図である。図５は、第１電極２の表面のうちの第２電極３に対向する側（図４では第１電極２の下向きの表面）の凹凸パターンを示す平面図である。図６は第２電極３の面のうちの第１電極２とは反対側の面（図４では第２電極３の下向きの表面）の平面図である。 FIG. 4 is a schematic view showing a cross-sectional structure of the first electrode (cathode electrode) 2 and the second electrode 3 of the discharge parallel electrode of the plasma processing apparatus according to the second embodiment of the present invention. FIG. 5 is a plan view showing a concavo-convex pattern on the side of the surface of the first electrode 2 facing the second electrode 3 (the downward surface of the first electrode 2 in FIG. 4). FIG. 6 is a plan view of the surface of the second electrode 3 opposite to the first electrode 2 (the surface facing downward in the second electrode 3 in FIG. 4).
第１電極２の表面形状は、図５に示すように長円筒状のスポット型凹部１３を格子状に並べ、このスポット型凹部１３の隣接するもの同士を溝型凹部１４で連通して所定パターンの凹凸を形成したものである。スポット型凹部１３の奥端面（図４で言えばスポット型凹部１３の「天井」となっている面）には、ガス導入用小孔１２ａが形成されている。スポット型凹部１３の奥端面と第１電極２の反対側の表面の間にはガス導入管４に連通するガス空間が設けてあり、ガス導入用小孔１２ａはこのガス空間を介してガス導入管４に連通している。 As shown in FIG. 5, the surface shape of the first electrode 2 is such that long cylindrical spot-shaped recesses 13 are arranged in a lattice pattern, and adjacent ones of the spot-shaped recesses 13 communicate with each other by a groove-shaped recess 14 to form a predetermined pattern. Are formed. A gas introduction small hole 12a is formed on the back end surface of the spot-type recess 13 (the surface that is the “ceiling” of the spot-type recess 13 in FIG. 4). A gas space communicating with the gas introduction pipe 4 is provided between the back end surface of the spot-type recess 13 and the surface on the opposite side of the first electrode 2, and the gas introduction small hole 12a is introduced through this gas space. It communicates with the tube 4.
第１電極２に対向する第２電極３は、第１電極２からプラズマのシース厚以下の距離に設置され、接地又は直流電圧が印加されている。この条件では、第１電極表面の凹部以外の部分では、第１と第２電極間にプラズマは生成しない。これにより、第１電極表面でガスのプラズマ分解によって生成された分解種の利用効率が高くなり、製膜速度が向上する。第２電極３には、第１電極２の長円筒状スポット型凹部１３と同パターンで且つ同径の円形の孔１５が第１電極２側からその反対側へと貫通している。図４からわかるように、これら貫通孔１５は夫々スポット型凹部１３と整列して設けられている。これにより、スポット型凹部１３付近のプラズマ生成部からの分解種が第２電極３の裏面側へ拡散するのを妨げないようにしている。第２電極３の第１電極２と対向しない面には所定パターンでガス導入用小孔１２ｂが設けられている。ガス導入用小孔１２ｂは、第２電極３の内部に設けられているガス空間を介してガス導入管５に連通している。基板は通常、第２電極３の第１電極２とは反対側（図４で言えば下側）の面に対向する第３電極表面上に設置される。第３電極は通常接地されている。 The second electrode 3 facing the first electrode 2 is installed at a distance equal to or less than the plasma sheath thickness from the first electrode 2 and is applied with ground or a DC voltage. Under this condition, plasma is not generated between the first and second electrodes in a portion other than the concave portion on the surface of the first electrode. Thereby, the utilization efficiency of the decomposition | disassembly seed | species produced | generated by the plasma decomposition of gas on the 1st electrode surface becomes high, and the film-forming speed | rate improves. In the second electrode 3, a circular hole 15 having the same pattern and the same diameter as the long cylindrical spot-type recess 13 of the first electrode 2 penetrates from the first electrode 2 side to the opposite side. As can be seen from FIG. 4, these through holes 15 are provided in alignment with the spot-type recesses 13. This prevents the decomposition species from the plasma generation part in the vicinity of the spot-type concave part 13 from diffusing to the back side of the second electrode 3. Gas introduction small holes 12b are provided in a predetermined pattern on the surface of the second electrode 3 not facing the first electrode 2. The gas introduction small hole 12 b communicates with the gas introduction pipe 5 through a gas space provided inside the second electrode 3. The substrate is usually placed on the surface of the third electrode facing the surface of the second electrode 3 opposite to the first electrode 2 (the lower side in FIG. 4). The third electrode is normally grounded.
その他の点は前記実施例１と同様なので説明を省略する。 Since other points are the same as those of the first embodiment, description thereof is omitted.
［実施例の細部及び使い方］
本発明の放電用平行電極における第１電極２の表面のうちの第２電極３に対向する側には、個々のスポット型凹部１３の集まりを含む所定パターンの凹部を設ける。個々のスポット型凹部１３の形状は、円筒状窪み、三角形、四角形、六角形など多角形筒状窪み・多角錐状窪み、円錐状窪みなどであってよい、好ましくは円筒状窪みとし、これら個々のスポット型凹部１３の大きさは好ましくは均一又は概ね均一とする。
[Details and usage of examples]
On the side of the surface of the first electrode 2 in the discharge parallel electrode of the present invention that faces the second electrode 3, a predetermined pattern of recesses including a collection of individual spot-type recesses 13 is provided. The shape of each spot-shaped recess 13 may be a cylindrical depression, a polygonal cylindrical depression such as a triangle, a quadrangle, or a hexagon, a polygonal pyramid depression, a conical depression, etc., preferably a cylindrical depression. The size of the spot-type recess 13 is preferably uniform or substantially uniform.
また、個々のスポット型凹部１３の配置（凹部の所定の全体パターン）は平面視で好ましくは格子状配置（格子を形成する交点に個々の凹部を設けた形状）、又は、最密充填状配置とする。隣接するスポット型凹部１３を溝型凹部で連結する場合は、格子状配置が好ましい。 Further, the arrangement of the individual spot-type concave portions 13 (predetermined overall pattern of the concave portions) is preferably a lattice arrangement (a shape in which individual concave portions are provided at intersections forming the lattice) or a close-packed arrangement in a plan view. And When connecting adjacent spot type | mold recessed parts 13 by a groove type recessed part, a grid | lattice-like arrangement | positioning is preferable.
第１電極２及び第２電極（対向電極）３の材料としては、融点の高いステンレスを用いることが好ましいが、アルミニウム、銅などの金属（合金）も可能である。 As the material of the first electrode 2 and the second electrode (counter electrode) 3, it is preferable to use stainless steel having a high melting point, but metals (alloys) such as aluminum and copper are also possible.
また、第１電極（通常は、カソード電極）２及び第２電極（対向電極）３の大きさ（面積）は、通常は４ｍ２（２ｍ平方）程度、好ましくは０．００５ｍ２（７ｃｍ平方）〜４ｍ２（２ｍ平方）程度、更に好ましくは０．０４ｍ２（２０ｃｍ平方）〜４ｍ２（２ｍ平方）程度の範囲が可能である。 The size (area) of the first electrode (usually the cathode electrode) 2 and the second electrode (counter electrode) 3 is usually about 4 m 2 (2 m square), preferably 0.005 m 2 (7 cm square). A range of about ˜4 m 2 (2 m square), more preferably about 0.04 m 2 (20 cm square) to 4 m 2 (2 m square) is possible.
電極の厚みは、スポット型凹部及び溝型凹部の深さより厚いものとする。個々のスポット型凹部１３の大きさ（凹部の径又は幅）は、シース厚さの２倍以上であることが必要である。この大きさの具体的な値はプロセス条件に依存するが、１〜４０ｍｍ程度が好ましく、より好ましくは２〜２０ｍｍ程度とする。 The thickness of the electrode is greater than the depth of the spot-type recess and the groove-type recess. The size (diameter or width of the recess) of each spot type recess 13 needs to be at least twice the sheath thickness. Although the specific value of this magnitude | size depends on process conditions, about 1-40 mm is preferable, More preferably, you may be about 2-20 mm.
スポット型凹部１３の深さは、径の１〜３倍程度又は２〜８０ｍｍ程度が好ましい。スポット型凹部１３の間隔（ピッチ）は、スポット型凹部１３の大きさ（凹部の径又は幅）の１〜４倍程度が可能であるが、好ましくは１〜１．５倍程度とする。凹部１３の間隔（ピッチ）が大きすぎると、製膜などプロセスの面内均一性のために好ましくない。 The depth of the spot-type recess 13 is preferably about 1 to 3 times the diameter or about 2 to 80 mm. The interval (pitch) between the spot-type recesses 13 can be about 1 to 4 times the size of the spot-type recess 13 (diameter or width of the recesses), but preferably about 1 to 1.5 times. If the interval (pitch) between the recesses 13 is too large, it is not preferable because of in-plane uniformity of processes such as film formation.
ガス導入用小孔（ガス導入孔）１２ａ、１２ｂの径は、スポット型凹部１３の径（又は幅）よりも小さいものとし、０．１〜１．５ｍｍ程度の範囲内が好ましく、より好ましくは０．５ｍｍ以下とする。 The diameters of the gas introduction small holes (gas introduction holes) 12a and 12b are smaller than the diameter (or width) of the spot-type recess 13 and are preferably in the range of about 0.1 to 1.5 mm, more preferably. 0.5 mm or less.
スポット型凹部１３の最適な大きさは圧力やプラズマ励起電源周波数などのプロセス条件に依存するが、凹部径又は幅が上記範囲にあって十分に小さいと、凹部（ホロー）による電子の閉じ込め効果が得られるので好ましい。 The optimum size of the spot-type recess 13 depends on process conditions such as pressure and plasma excitation power supply frequency, but if the recess diameter or width is in the above range and is sufficiently small, the electron confinement effect by the recess (hollow) is reduced. Since it is obtained, it is preferable.
凹部パターンのサイズ、ピッチ、深さなどは、プロセス条件によって、最適な値を選択することができる。 The optimum values for the size, pitch, depth, etc. of the concave pattern can be selected depending on the process conditions.
また、第１電極２の表面に高密度プラズマが滞在しやすい環境を作るため、第１電極２の（四）周端部では凸部表面と同等の高さの土手（帯状物）で囲むようにして、原料ガスを閉じ込めるようにすることが好ましい。 In order to create an environment where high-density plasma can easily stay on the surface of the first electrode 2, the (4) peripheral end portion of the first electrode 2 is surrounded by a bank (strip) having the same height as the convex surface. It is preferable to confine the source gas.
第１電極２と第２電極（対向電極）３の間の距離は、プロセスガス圧力などによって最適な値を選択することができる。上記電極間距離が十分に大きいと、長寿命ラジカルの選択的輸送や面内均一プロセスのためには有利であるが、高速プロセスのためには不利である。 The optimum distance between the first electrode 2 and the second electrode (counter electrode) 3 can be selected depending on the process gas pressure. A sufficiently large distance between the electrodes is advantageous for selective transport of long-lived radicals and in-plane uniform processes, but is disadvantageous for high-speed processes.
また、プロセス温度（基板温度）はヒーター等で制御され、通常は室温以上であり、好ましくは１００〜４００℃、より好ましくは１５０〜３５０℃である。 The process temperature (substrate temperature) is controlled by a heater or the like, and is usually room temperature or higher, preferably 100 to 400 ° C, more preferably 150 to 350 ° C.
プラズマ励起周波数は（電源９が直流でない場合）、１００ｋＨｚ〜１４０ＭＨｚの範囲が可能であり、好ましくは１０〜１００ＭＨｚ、更に好ましくは１３．５６ＭＨｚ（ＲＦ）とその整数倍（２〜１０倍。好ましくは２〜６倍）である。 The plasma excitation frequency (when the power supply 9 is not DC) can be in the range of 100 kHz to 140 MHz, preferably 10 to 100 MHz, more preferably 13.56 MHz (RF) and an integer multiple thereof (2 to 10 times, preferably). 2 to 6 times).
上記個々のスポット型凹部１３は、溝型凹部１４で相互に連結されていない独立したものとすることもできるが、好ましくは、隣接するスポット型凹部同士を溝型凹部１４で連結して、全体として網目状パターンを形成する。このときの溝型凹部１４の深さは、個々のスポット型凹部１３と同程度が好ましいが、ガス通路１６の構造にもよるが、それより浅いものであっても、あるいは深いものであってもよい。 The individual spot-type recesses 13 may be independent ones that are not mutually connected by the groove-type recesses 14, but preferably, the adjacent spot-type recesses are connected by the groove-type recesses 14, As a result, a mesh pattern is formed. The depth of the groove-type recess 14 at this time is preferably about the same as that of each spot-type recess 13, but depending on the structure of the gas passage 16, it may be shallower or deeper than that. Also good.
また、溝型凹部１４の幅は、スポット型凹部１３の径（又は幅）よりも小さいものとし、好ましくはその０．７倍よりも小さいものとし、更に好ましくはその１／５〜３／５程度とする。 Further, the width of the groove-type recess 14 is smaller than the diameter (or width) of the spot-type recess 13, preferably less than 0.7 times, more preferably 1/5 to 3/5. To the extent.
なお、隣接するスポット型凹部１３同士を溝型凹部１４で連結した場合、スポット型凹部１３と溝型凹部１４とをあわせたものを「所定パターンの凹部」等と総称する。 In addition, when adjacent spot type | mold recessed parts 13 are connected by the groove type recessed part 14, what united the spot type | mold recessed part 13 and the groove type recessed part 14 is named generically as "the recessed part of a predetermined pattern."
程度にもよるが、所定パターンの凹部の一部を欠落させたり、所定パターン状に配置したガス導入用小孔の一部を欠落させても本発明の効果を損なうことはない。 Although it depends on the degree, the effect of the present invention is not impaired even if a part of the concave portion of the predetermined pattern is omitted or a part of the small holes for gas introduction arranged in the predetermined pattern is deleted.
凹部内のガス導入孔の設置位置は凹部の底面又は壁面とすることができる。 The installation position of the gas introduction hole in the recess can be the bottom surface or the wall surface of the recess.
本発明の装置を使用して薄膜シリコン製膜を行う例では、プラズマ生成部（プラズマ生成領域）へ導入するＳｉＨ４又はＳｉＨ４／Ｈ２混合ガスの流量（及びＳｉＨ４／Ｈ２ガス混合比）と、それ以外の空間へ導入するＨ２ガス単体の流量との流量比には最適値が存在する。当該最適値は、気相反応、パウダー生成、膜成長表面における堆積種の表面反応に関係する堆積膜特性（結晶性その他）その他の要因で決まる。これ以外の応用についても当然同様な条件が存在する。 In an example in which thin film silicon film formation is performed using the apparatus of the present invention, the flow rate of SiH 4 or SiH 4 / H 2 gas mixture (and SiH 4 / H 2 gas mixture ratio) introduced into the plasma generation unit (plasma generation region). ) And the flow rate ratio of the flow rate of the H 2 gas alone introduced into the other space has an optimum value. The optimum value is determined by gas phase reaction, powder generation, deposited film characteristics (crystallinity, etc.) and other factors related to the surface reaction of the deposited species on the film growth surface. Of course, similar conditions exist for other applications.
また、気相反応を目的として導入するガス分子も、電子衝突による分解（解離）に要するエネルギー等にも依るが、ある割合で分解される場合が多い。薄膜シリコン製膜の場合を例に取れば、膜成長表面に飛来する製膜種と水素原子の数密度比が、微結晶の形成等、膜質に大きく影響するため、この観点からも流量比には最適値が存在する。 Further, gas molecules introduced for the purpose of gas phase reaction are often decomposed at a certain ratio, depending on energy required for decomposition (dissociation) by electron collision. Taking the case of thin-film silicon film as an example, the number density ratio between the film-forming species and hydrogen atoms flying on the film growth surface greatly affects the film quality, such as the formation of microcrystals. Has an optimal value.
一方、ＳｉＨ４／Ｈ２プラズマ中の支配的なイオンが軽量なＨ＋になると、両極性拡散により電子の消失係数が増加し、プラズマの電子温度が高くなるので、注意が必要である。つまり、プラズマの電子温度が高くなると、反応性の高いＳｉＨｘ（ｘ≦２）短寿命種の生成率が製膜種として望ましいＳｉＨ３の生成率に対して高くなり、好ましくない。しかし、プロセス圧力を高め（０．８Ｔｏｒｒ程度以上）に設定する場合には、気相反応による高次シラン及びパウダーの生成が活発になりやすいので、反応器内に導入するＳｉＨ４ガスのＨ２ガス希釈率が高い条件が好ましい。 On the other hand, when the dominant ions in the SiH 4 / H 2 plasma become light H + , the annihilation coefficient increases due to ambipolar diffusion, and the electron temperature of the plasma increases, so care must be taken. That is, when the electron temperature of plasma becomes high, the production rate of highly reactive SiH x (x ≦ 2) short-lived species becomes higher than the production rate of SiH 3 desirable as a film-forming species, which is not preferable. However, when the process pressure is set high (about 0.8 Torr or more), the production of higher order silane and powder by the gas phase reaction tends to become active, so that H 2 of the SiH 4 gas introduced into the reactor. Conditions with a high gas dilution rate are preferred.
例えばプロセスガス圧力が高い条件の場合、純ＳｉＨ４ガスをプラズマ生成部へ導入すると、プラズマ生成部で局所的にＳｉＨ４密度が高くなりすぎ、高次シラン種及びパウダーの生成が活発になる。このため、条件にもよるが、ガス圧力が０．８Ｔｏｒｒ程度以上の場合は、プラズマ生成部へのガス導入は、純ＳｉＨ４ガスではなく、ＳｉＨ４／Ｈ２混合ガスとすることが好ましい。 For example, when the process gas pressure is high, when pure SiH 4 gas is introduced into the plasma generation unit, the SiH 4 density becomes too high locally in the plasma generation unit, and generation of higher order silane species and powder becomes active. For this reason, although depending on the conditions, when the gas pressure is about 0.8 Torr or more, it is preferable that the gas introduction into the plasma generation unit is not a pure SiH 4 gas but a SiH 4 / H 2 mixed gas.
プラズマ生成部にＳｉＨ４又はＳｉＨ４／Ｈ２ガスを導入する薄膜シリコン作製の場合、導入するＳｉＨ４が枯渇条件（大部分が分解され、ＳｉＨ４分子として残っているものが少ない状態）となっていることが好ましい。 In the case of thin-film silicon production in which SiH 4 or SiH 4 / H 2 gas is introduced into the plasma generation unit, the introduced SiH 4 is in a depletion condition (a state in which most of the SiH 4 molecules are decomposed and there are few remaining SiH 4 molecules). It is preferable.
特許文献３に開示された電極構成（第１電極が複数の排気孔を有する）への適用も可能である。アモルファスシリコン製膜の場合、本発明の気相反応用途のガス独立導入による気相反応による高次シラン種の生成抑制効果、及びラジカル分離効果による高次シラン種の消失促進効果に、特許文献３のガス流による高次シラン種消失促進効果が組み合わされ、光安定性に優れた膜のより高速での成長が可能となる。 Application to the electrode configuration disclosed in Patent Document 3 (the first electrode has a plurality of exhaust holes) is also possible. In the case of an amorphous silicon film, Patent Document 3 discloses the effect of suppressing the generation of higher order silane species by the gas phase reaction by the independent gas introduction for the gas phase reaction of the present invention and the effect of promoting disappearance of the higher order silane species by the radical separation effect. Combined with the effect of promoting the disappearance of higher-order silane species by this gas flow, it becomes possible to grow a film having excellent light stability at a higher speed.
以上説明したように、本発明によれば、特性の光劣化が更に低減されたアモルファスシリコン膜を製膜することができるなど、プラズマ生成部からもたらされる分解種成分構成を積極的に改質し、プロセス反応種の制御性・選択性を向上して製膜性能を向上させることができるので、プラズマプロセス装置を使用した製膜一般に広く利用することができる。 As described above, according to the present invention, it is possible to form an amorphous silicon film in which the photodegradation of characteristics is further reduced, for example, to positively modify the decomposition species component structure brought about from the plasma generation unit. Since the film-forming performance can be improved by improving the controllability and selectivity of the process reaction species, it can be widely used for film-forming using a plasma process apparatus in general.
１・・反応容器
２・・第１電極
３・・第２電極
４・・ガス導入管
５・・ガス導入管
６・・ガス導入管
７・・ガス排気管
８・・プロセス基板
９・・電源
１０・・ヒーター
１１・・アースシールド
１２ａ・・ガス導入用小孔（ガス導入孔）
１２ｂ・・ガス導入用小孔（ガス導入孔）
１３・・スポット型凹部
１４・・溝部（溝型凹部）
１５・・貫通孔
１６・・ガス通路
1 .... Reaction vessel 2 .... First electrode 3 .... Second electrode 4 .... Gas introduction pipe 5 .... Gas introduction pipe 6 .... Gas introduction pipe 7 .... Gas exhaust pipe 8 .... Process substrate 9 .... Power supply 10. Heater 11 Earth shield 12a Gas introduction hole (gas introduction hole)
12b .. Small hole for gas introduction (gas introduction hole)
13. ・ Spot type concave part 14 ・ ・ Groove part (groove type concave part)
15. ・ Through hole 16 ・ ・ Gas passage
Claims (11)
前記反応容器内に収容された放電用の第１電極と前記第１電極に対向して置かれた第２電極を含む電極体と、
前記第１電極の前記第２電極に対向する側に掘り込まれた凹部で画定されるプラズマ生成領域と、
前記第１電極の前記凹部内に設けられた、分解して膜堆積種を生成する第１のガスを導入する第１のガス導入部と、
前記反応容器内の前記プラズマ生成領域と異なる箇所であって、前記第１のガス導入部よりも第２電極側に設けられた、前記第１のガスが前記プラズマ生成領域中で分解して生成する分解種の少なくとも一部と気相反応する第２のガスを導入する第２のガス導入部と
を設け、
前記反応容器中に入れた部材を処理するプラズマプロセス装置。 A reaction vessel;
An electrode body including a first electrode for discharge housed in the reaction vessel and a second electrode placed opposite to the first electrode;
A plasma generation region defined by a recess dug in the side of the first electrode facing the second electrode;
A first gas introduction part that introduces a first gas that decomposes and generates a film deposition species provided in the recess of the first electrode;
The first gas, which is different from the plasma generation region in the reaction vessel and is closer to the second electrode than the first gas introduction part, is decomposed and generated in the plasma generation region. Providing a second gas introduction part for introducing a second gas that undergoes a gas phase reaction with at least a part of the decomposition species
The plasma processing apparatus which processes the member put in the said reaction container.
前記第１のガスを輸送する少なくとも１本の第１のガス導入管路と、
前記第１のガス導入管路に連通して前記第１のガスを前記プラズマ生成領域に導入する少なくとも１つの第１の導入孔と
を有し、
前記第２のガス導入部は
前記第２のガスを輸送する少なくとも１本の第２のガス導入管路と、
前記第２のガス導入管路に連通して前記第２のガスを前記反応容器内に導入する少なくとも１つの第２の導入孔と
を有する
請求項１又は２に記載のプラズマプロセス装置。 The first gas introduction unit includes at least one first gas introduction line for transporting the first gas;
Having at least one first introduction hole communicating with the first gas introduction pipe and introducing the first gas into the plasma generation region;
The second gas introduction unit includes at least one second gas introduction line for transporting the second gas;
3. The plasma processing apparatus according to claim 1, further comprising at least one second introduction hole that communicates with the second gas introduction pipe and introduces the second gas into the reaction vessel. 4.
前記第２電極は前記第１電極側から前記第３電極側に貫通する複数の貫通孔を有し、
前記第２電極は更に前記第２の導入孔を開口し、
前記第３の電極の前記第２の電極に対向する表面に置かれた部材を処理する、
請求項７から９の何れかに記載のプラズマプロセス装置。 The electrode body further includes a third electrode on a side of the second electrode that is not on the first electrode side,
The second electrode has a plurality of through holes penetrating from the first electrode side to the third electrode side,
The second electrode further opens the second introduction hole,
Treating a member placed on a surface of the third electrode facing the second electrode;
The plasma processing apparatus according to claim 7.
前記第２電極は前記第１電極側から前記第３電極側に貫通するとともに前記第１電極上の前記スポット型凹部に整列した複数の貫通孔を有し、
前記第２電極は更に前記第２の導入孔を開口し、
前記第３の電極の前記第２の電極に対向する表面に置かれた部材を処理する、
請求項８または９に記載のプラズマプロセス装置。 The electrode body further includes a third electrode on a side of the second electrode that is not on the first electrode side,
The second electrode has a plurality of through holes penetrating from the first electrode side to the third electrode side and aligned with the spot-type recesses on the first electrode;
The second electrode further opens the second introduction hole,
Treating a member placed on a surface of the third electrode facing the second electrode;
The plasma processing apparatus according to claim 8 or 9.
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