JP2017133048A - Film deposition apparatus, and film deposition method using the same - Google Patents
Film deposition apparatus, and film deposition method using the same Download PDFInfo
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- 238000000151 deposition Methods 0.000 title abstract description 12
- 230000008021 deposition Effects 0.000 title abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000011368 organic material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- Plasma Technology (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
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 film forming methods, such as a sputtering method in which an inorganic or organic solid is gasified by plasma in vacuum and a coating method in which an organic material is dissolved in a solvent and applied to a substrate.
The former has the advantage that a dense film can be formed with good reproducibility, but a special device such as a vacuum device is required, and there is a problem that the cost is high. Although it is extremely cheap, there is a problem that a solvent recovery process after film formation is required 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 apparatus using dielectric barrier discharge (Patent Document 1), but 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 a 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 with a film forming raw material in the middle of the flow path of the plasma flow generated by the plasma flow generating device. A mixed gas flow of a film forming material gas and a plasma flow generated in the supply unit is made to reach the film forming substrate.
Here, the plasma is an ionized gas, and the atmospheric pressure non-thermal equilibrium plasma flow is a plasma flow having an electron temperature higher than the gas temperature under atmospheric pressure.
In addition, the expression of reaching the film-forming substrate means that the generated mixed gas flow is jetted from the nozzle, or a band-like jet or a film-forming raw material is provided with a slit hole, and a plasma flow is supplied to the slit hole. A mixed gas flow is generated by passing it and sprayed directly onto the surface of the member or the like to be deposited, and the deposition raw materials are supported on various plasma flow permeable substrates such as filter paper, fiber substrate, mesh substrate, etc. In other words, it means that the mixed gas flow reaches and contacts the deposition target substrate by some means such as a form 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 generating gas supply unit, or 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 to form 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。
The film forming method according to the present invention uses the above apparatus to bring the atmospheric pressure non-thermal equilibrium plasma flow into contact with the film forming raw material, thereby gasifying the film forming raw material and forming a mixed plasma flow with the generated raw material. It is made to reach | attain on a membrane base material.
Here, a plurality of film forming raw materials may be formed, and the obtained film may be a composite film in which the plurality of raw material components are combined 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 the mixed gas flow so as to reach various film formation substrates, a thin film can be formed on the substrate.
As a result, a large-scale vacuum apparatus as in the prior art is unnecessary and the apparatus is simple.
Further, a solvent such as a spin coating method is not necessary, 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 an atmospheric pressure non-thermal equilibrium plus jet flow is brought into contact with the film forming raw material, the film forming raw material is gasified and sprayed onto the film forming substrate together with the plasma jet flow. Is formed.
There is no limitation on the method of contacting the plasma jet flow with the film forming raw material.
The raw material for film formation is not limited in its form such as inorganic, organic solid, liquid and the like.
Further, a composite film can be formed by bringing this 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 An example of the composite film is a perovskite film.
Note that, as an application example of the film forming apparatus according to the present invention, a substance composed of a composite component can be applied to this plasma jet stream to separate and separate each component when the composite component is gasified.
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 2.45 GHZ microwave generator, Ar gas was supplied from the Gas supply unit to the microwave whose output was adjusted so as to achieve non-thermal equilibrium, thereby generating a plasma jet flow.
A liquid mixture of the precursor substances CH 3 NH 3 I and PbI 2 was applied and dried inside the quartz tube (Quartz) at the tip of the nozzle, brought into contact with the plasma jet flow, and sprayed directly from the nozzle onto the substrate.
3A and 3B show the AFM (Atomic Force Microscope) image of the film formed by this, 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 by bringing an inorganic substance and an organic substance into contact with a plasma jet stream can be obtained.
Therefore, as shown in FIG. 2, a composite film can be obtained by continuously forming contact supply portions of different materials of Material (1) and Material (2) in the quartz.
Moreover, the dielectric barrier discharge disclosed in Patent Document 1 previously proposed by the present applicant may be used for generation of the plasma jet flow.
In the present embodiment, the film forming raw material is brought into contact with the quartz tube at the tip of the nozzle, but a hole, a slit hole, or an irregularly shaped hole may be formed in the film forming raw material, and the plasma flow may be passed through the inside.
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 a film forming raw material is supported on a base material that can pass a plasma flow, such as a filter paper or a fiber base material.
Directly on the HiNarumakumotozai 3 or spaced predetermined intervals d 2, placing the film formation raw material 2 which is supported on the substrate.
Blowing a plasma stream 1 from a nozzle disposed at a predetermined height d 1 on this.
The plasma flow comes into contact with the film-forming raw material when passing through the substrate, and becomes a mixed gas.
As described above, any contact method between the plasma flow and 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 Deposition raw material (supported on substrate)
3 Deposition substrate
Claims (6)
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成膜装置。 An atmospheric pressure non-thermal equilibrium plasma flow generator, and a contact supply unit with a film forming raw material in the middle of the flow path of the plasma flow generated by the plasma flow generator,
A film forming apparatus characterized in that a mixed gas flow of a film forming material gas and a plasma flow generated in the contact supply unit reaches a film forming substrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110880550A (en) * | 2018-09-05 | 2020-03-13 | 杭州纤纳光电科技有限公司 | Coating equipment and method for precursor solution containing surfactant |
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| JP2012188701A (en) * | 2011-03-10 | 2012-10-04 | Kanagawa Acad Of Sci & Technol | Apparatus and method for forming coating film |
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| JP2002515639A (en) * | 1998-05-12 | 2002-05-28 | マサリコヴァ ユニヴェルツィタ | Method of forming a physically and chemically active environment by a plasma jet and related plasma jet |
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