JP6709005B2 - Film forming apparatus and film forming method using the same - Google Patents
Film forming apparatus and film forming method using the same Download PDFInfo
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- JP6709005B2 JP6709005B2 JP2016011537A JP2016011537A JP6709005B2 JP 6709005 B2 JP6709005 B2 JP 6709005B2 JP 2016011537 A JP2016011537 A JP 2016011537A JP 2016011537 A JP2016011537 A JP 2016011537A JP 6709005 B2 JP6709005 B2 JP 6709005B2
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Description
本発明は、大気圧非熱平衡プラズマを用いた成膜装置及び成膜方法に関する。 The present invention relates to a film forming apparatus and a film forming method using atmospheric pressure non-thermal equilibrium plasma.
太陽電池、トランジスタ、ディスプレーなどの電子デバイスの分野では無機材料や有機材料を用いた成膜技術が広く採用されている。
成膜方法は多種多様で、真空中でプラズマにより無機又は有機固体をガス化させて成膜するスパッタ法や有機材料を溶媒に溶かして基板に塗ることにより成膜する塗布法などがある。
前者は、緻密膜を再現よく成膜できる特長があるが真空装置等の特殊な装置が必要で、高コストとなる問題があり、後者は、印刷に近い技術のため装置が小型で製造コストが格段に安い特長があるが溶媒を用いているため成膜後の溶媒の回収処理が必要である問題があった。
In the field of electronic devices such as solar cells, transistors, and displays, film forming techniques using inorganic materials and organic materials are widely adopted.
There are various kinds of film forming methods, such as a sputtering method for gasifying an inorganic or organic solid by plasma in vacuum to form a film, and a coating method for forming a film by dissolving an organic material in a solvent and applying the solution to a substrate.
The former has the feature that a dense film can be formed with good reproducibility, but it requires a special device such as a vacuum device, which poses a problem of high cost.The latter is a technique similar to printing, so the device is small and the manufacturing cost is low. Although it is significantly cheaper, there is a problem that a solvent recovery process is required after film formation because a solvent is used.
本出願人は、先に誘電体バリア放電によるプラズマ生成装置を提案している（特許文献１）が、無機材料，有機材料あるいは、それらの複合膜の成膜を目的とするものではない。 The present applicant has previously proposed a plasma generation device by dielectric barrier discharge (Patent Document 1), but it is not intended to form an inorganic material, an organic material, or a composite film thereof.
本発明は、低コストで各種目的に応じた成膜が可能な成膜装置及び方法の提供を目的とする。 An object of the present invention is to provide a film forming apparatus and method capable of forming a film according to various purposes at low cost.
本発明に係る成膜装置は、大気圧非熱平衡のプラズマ流発生装置と、前記プラズマ流発生装置にて発生したプラズマ流の流路途中に成膜原材料との接触供給部とを備え、前記接触供給部にて発生した成膜材料ガスとプラズマ流との混合ガス流を被成膜基材上に到達させることを特徴とする。
ここで、プラズマは電離した気体であり大気圧非熱平衡のプラズマ流とは、大気圧下でガス温度よりも電子温度が高いプラズマ流をいう。
また、被成膜基材上に到達させると表現したのは、発生した混合ガス流をノズルから噴射させる形態や、帯状に噴射あるいは成膜原材料にスリット孔を設け、このスリット孔にプラズマ流を通過させることで混合ガス流を発生させ、そのまま成膜したい部材等の表面に吹き付ける形態、また例えば濾紙，繊維基材，メッシュ基材等のプラズマ流通過性の各種基材に成膜原材料を担持させておき、プラズマ流を通過させる形態等、何らかの手段にて前記混合ガス流が被成膜基材上に到達し、接触することをいう。
A film forming apparatus according to the present invention includes an atmospheric pressure non-thermal equilibrium plasma flow generating device and a contact supply unit for contacting a film forming raw material in the middle of a flow path of a plasma flow generated by the plasma flow generating device. It is characterized in that a mixed gas flow of a film forming material gas generated in a supply unit and a plasma flow is made to reach the film formation substrate.
Here, the plasma is an ionized gas, and the plasma flow in the atmospheric pressure non-thermal equilibrium refers to a plasma flow in which the electron temperature is higher than the gas temperature under the atmospheric pressure.
In addition, the expression of reaching the film-forming substrate means that the generated mixed gas flow is jetted from the nozzle, jetted in a strip shape or provided with slit holes in the film-forming raw material, and the plasma flow is provided in the slit holes. A mixed gas flow is generated by passing it, and the film is directly sprayed onto the surface of the member on which the film is to be formed, or the film forming raw material is supported on various types of plasma flow permeable substrates such as filter paper, fiber substrates, mesh substrates, etc. That is, it means that the mixed gas flow reaches and contacts the film formation substrate by some means such as a mode in which the plasma flow is passed.
大気圧非熱平衡のプラズマ流発生装置はマイクロ波の発生器とプラズマ発生用ガスの供給部とを組み合せたり、誘電体バリア放電によるものであってもよく、またこれらに限定されない。
このようなプラズマ流を無機や有機材料等の成膜原材料に接触させると、このプラズマ流により、これらの成膜原材料がガス化し、混合ガス流となる。
The atmospheric pressure non-thermal equilibrium plasma flow generator may be a combination of a microwave generator and a plasma generation gas supply unit, or may be a dielectric barrier discharge, but is not limited thereto.
When such a plasma flow is brought into contact with a film-forming raw material such as an inorganic or organic material, the film-forming raw material is gasified by the plasma flow and becomes a mixed gas flow.
本発明に係る成膜方法は上記装置を用いて、大気圧非熱平衡プラズマ流と成膜原材料とを接触させることで前記成膜原材料がガス化し、生成された原材料との混合プラズマ流を被成膜基材上に到達させることを特徴とする。
ここで、成膜原材料が複数からなり、得られた成膜が前記複数の原材料成分が複合また反応した複合化膜とすることもできる。
In the film forming method according to the present invention, by using the above apparatus, the film formation raw material is gasified by bringing the atmospheric pressure non-thermal equilibrium plasma flow into contact with the film formation raw material, and a mixed plasma flow with the generated raw material is formed. It is characterized in that it reaches the membrane substrate.
Here, the film-forming raw material may be composed of a plurality of films, and the obtained film may be a composite film in which the plurality of raw material components are composited or reacted.
本発明に係る成膜装置は、大気圧下で発生させた非熱平衡のプラズマ（ジェット）流を成膜のための原材料に接触させ、この原材料をガス化した混合ガス流を得ることができる。
この混合ガス流を各種被成膜基材に到達するように輸送することで、この基材上に薄膜を成膜することができる。
これにより、従来のような大がかりな真空装置が不要で簡単な装置となる。
また、スピンコート法のような溶媒が不要となり、環境負荷を低減することができる。
The film forming apparatus according to the present invention can bring a non-thermal equilibrium plasma (jet) flow generated under atmospheric pressure into contact with a raw material for film formation, and obtain a mixed gas flow obtained by gasifying the raw material.
By transporting this mixed gas flow so as to reach various film-forming substrates, a thin film can be formed on this substrate.
As a result, a large vacuum device as in the prior art is not required and the device becomes simple.
Further, a solvent such as the spin coating method is not required, and the environmental load can be reduced.
本発明に係る成膜装置は、大気圧非熱平衡プラスのジェット流を成膜原材料に接触させると、この成膜原材料がガス化し、プラズマジェット流とともに被成膜基材上に噴きつけられ、薄膜が形成される。
このプラズマジェット流と成膜原材料との接触方法には制限がない。
成膜原材料としては、無機物、有機物の固体、液体等その形態に制限はない。
また、このプラズマジエット流を異なる複数の成膜原材料と接触させることで、複合化成膜の形成も可能である。
無機質（無機薄膜）の例としては、二酸化ケイ素膜、ＴｉＯｘ，ＭＯＯｘ等の金属酸化物、有機物（有機薄膜）の例としてはフタロシアニン，フラーレン等の有機半導体膜、また、無機有機の複合膜としては、ペロブスカイト膜等が例として挙げられる。
なお、本発明に係る成膜装置の応用例として複合成分からなる物質を、このプラズマジェット流に接触させることで複合成分がガス化した際に各成分に分離させ、分別するのに応用できる。
In the film forming apparatus according to the present invention, when a jet flow of atmospheric pressure non-thermal equilibrium plus is brought into contact with a film forming raw material, the film forming raw material is gasified and jetted onto a film-forming substrate together with a plasma jet flow to form a thin film. Is formed.
There is no limitation on the method of contacting the plasma jet stream with the film-forming raw material.
The film forming raw material is not limited in its form such as an inorganic substance, an organic solid, or a liquid.
Further, it is possible to form a composite film by bringing the plasma jet flow into contact with a plurality of different film forming raw materials.
Examples of the inorganic (inorganic thin film) are silicon dioxide film, T i Ox, M O metal oxide such as Ox, organic phthalocyanine Examples of (organic thin film), an organic semiconductor film of fullerene, also, the inorganic-organic Examples of the composite film include a perovskite film and the like.
In addition, as an application example of the film forming apparatus according to the present invention, a substance composed of a composite component is brought into contact with the plasma jet flow, so that when the composite component is gasified, it can be separated into each component and applied.
図１に実験に用いた成膜装置構成例を示す。
２．４５ＧＨＺのマイクロ波発生器を用い、非熱平衡となるように出力調整したマイクロ波にＧａｓ供給部からＡｒガスを供給し、プラズマジェット流を発生させた。
ノズル先端部のクォーツ管（Ｑｕａｒｔｚ）内側に、前駆体物質ＣＨ３ＮＨ３ＩとＰｂＩ２との混合液を塗布及び乾燥させ、上記プラズマジェット流と接触させ、そのままノズルから基板上に噴射した。
これにより形成された成膜のＡＦＭ（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ）像を図３（ａ），（ｂ）に示し、ペロブスカイト（ＣＨ３ＮＨ３ＰｂＩ３）膜が形成されていることが確認できた。
このことから、プラズマジェット流に無機物と有機物とを接触させることで反応生成したペロブスカイト膜が得られることが明らかになった。
そこで、図２に示すようにクォーツ内部にＭａｔｅｒｉａｌ（１）とＭａｔｅｒｉａｌ（２）との異なる材料の接触供給部を連続形成しても、複合膜が得られる。
また、プラズマジェット流の発生には本出願人が、先に提案した特許文献１の誘電体バリア放電を用いてもよい。
本実施例は、ノズル先端部のクォーツ管内で成膜原材料と接触させたが、成膜原材料に孔やスリット孔，異形状の孔を形成し、その内側にプラズマ流を通過させてもよい。
また、上記成膜原材料を被成膜基材の表面に沿って移動させながら、混合ガスを吹き付けてもよい。
図４は、成膜原材料を濾紙，繊維基材等のプラズマ流が通過できる基材に担持させた例を示す。
被成膜基材３の上に直接又は所定の間隔ｄ２を隔てて、上記基材に担持させた成膜原材料２を配置する。
この上に所定の高さｄ１に配置したノズルからプラズマ流１を吹き付ける。
プラズマ流は、基材を通過する際に成膜原材料と接触し、混合ガスとなる。
このように、混合ガスが被成膜基材上に到達すれば、どのようなプラズマ流と成膜原材料との接触方法でもよい。
FIG. 1 shows a configuration example of a film forming apparatus used in the experiment.
Using a microwave generator of 2.45 GHZ, Ar gas was supplied from the Gas supply unit to the microwave whose output was adjusted so as to be in non-thermal equilibrium, and a plasma jet flow was generated.
A mixed liquid of the precursor substances CH 3 NH 3 I and PbI 2 was applied and dried on the inner side of the quartz tube (Quartz) at the tip of the nozzle, brought into contact with the plasma jet stream, and sprayed directly from the nozzle onto the substrate.
The AFM (Atomic Force Microscope) images of the film thus formed are shown in FIGS. 3A and 3B, and it was confirmed that a perovskite (CH 3 NH 3 PbI 3 ) film was formed.
From this, it became clear that a perovskite film produced by reaction was obtained by bringing an inorganic substance and an organic substance into contact with the plasma jet flow.
Therefore, as shown in FIG. 2, a composite film can be obtained by continuously forming a contact supply part of different materials of Material (1) and Material (2) inside the quartz.
Further, the dielectric barrier discharge of Patent Document 1 previously proposed by the present applicant may be used to generate the plasma jet flow.
In this embodiment, the film-forming raw material was brought into contact with the inside of the quartz tube at the tip of the nozzle, but holes, slit holes, or irregular shaped holes may be formed in the film-forming raw material, and the plasma flow may be passed inside thereof.
Further, the mixed gas may be sprayed while moving the film-forming raw material along the surface of the film-forming substrate.
FIG. 4 shows an example in which the film-forming raw material is carried on a base material such as a filter paper or a fiber base material through which a plasma flow can pass.
The film-forming raw material 2 supported on the base material 3 is placed directly or at a predetermined distance d 2 on the base material 3.
A plasma stream 1 is blown onto this from a nozzle arranged at a predetermined height d 1 .
The plasma flow comes into contact with the film-forming raw material as it passes through the substrate, and becomes a mixed gas.
As described above, any method of contacting the plasma flow with the film-forming raw material may be used as long as the mixed gas reaches the film-forming substrate.
１ プラズマ流
２ 成膜原材料（基材に担持）
３ 被成膜基材
1 Plasma flow 2 Raw material for film formation (supported on substrate)
3 Substrates for film formation
Claims (2)
前記プラズマジェット流に前記固体の成膜原材料を接触させることで、前記固体の成膜原材料がガス化し混合したプラズマジェット流との混合プラズマ流が被成膜基材上に到達し、成膜されることを特徴とする成膜方法。 An atmospheric pressure non-thermal equilibrium plasma flow generator, and a contact supply unit with a solid film forming raw material in the middle of the flow path of the plasma jet flow generated by the plasma flow generator,
By bringing the solid film-forming raw material into contact with the plasma jet stream, a mixed plasma stream with the plasma jet stream in which the solid film-forming raw material is gasified and mixed reaches the substrate for film formation. A film forming method comprising:
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