WO2015076162A1 - プラズマ電極、プラズマ処理電極、cvd電極、プラズマcvd装置及び薄膜付基材の製造方法 - Google Patents
プラズマ電極、プラズマ処理電極、cvd電極、プラズマcvd装置及び薄膜付基材の製造方法 Download PDFInfo
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- WO2015076162A1 WO2015076162A1 PCT/JP2014/079940 JP2014079940W WO2015076162A1 WO 2015076162 A1 WO2015076162 A1 WO 2015076162A1 JP 2014079940 W JP2014079940 W JP 2014079940W WO 2015076162 A1 WO2015076162 A1 WO 2015076162A1
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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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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- 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
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
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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
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
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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
- H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
Definitions
- This technology relates to a plasma electrode, a plasma processing electrode, and a CVD electrode used for surface treatment and film formation of a substrate.
- Patent Document 1 discloses an electrode in which two magnetic circuits are arranged back to back, and plasma can be generated on both surfaces of the electrodes, whereby two surfaces can be sputtered simultaneously. According to the present invention, it is possible to perform sputtering film formation on both surfaces of the integrated cathode by arranging the two cathodes back to back, and efficiently form the film by running the substrate in each film formation zone. be able to.
- Patent Document 2 discloses an electrode structure that generates a magnetic field capable of performing magnetron discharge on both surfaces of an electrode by configuring a magnetic circuit without using a yoke.
- a magnetic circuit without using a yoke.
- the magnetic flux density on the opposite side of the discharge surface that has been conventionally induced by using the yoke is made to have the same magnetic flux density distribution as that on the discharge surface side by using a configuration that does not use the yoke.
- the target surface on the opposite side of the discharge surface it is possible to perform the sputter film formation on both surfaces, so that one electrode can perform the sputter film formation for two passes.
- Patent Document 3 discloses an electrode structure capable of performing sputter film formation on both sides of a cathode by generating a magnetic field capable of performing magnetron discharge on two surfaces using one magnet unit.
- This technology is an electrode that can be formed by sputtering on both sides of the cathode as in Patent Document 2, but the magnetic circuit is configured to actively induce magnetic flux using a yoke and to optimize the magnetic flux density distribution. it is conceivable that.
- JP 2004-27272 A JP 2006-233240 A JP2009-127109A
- the sputter electrode As the sputter electrode, an electrode structure has been proposed in which plasma is generated on both sides of the cathode so that sputtering can be efficiently formed as in the techniques of Patent Documents 1 to 3.
- an efficient plasma source that can be suitably used for applications other than sputtering film formation, such as plasma processing and plasma CVD, has not yet been proposed.
- plasmas with different intensities are generated on both sides of the cathode, or plasma is generated only on one side, It is difficult to discharge stably and evenly on both sides.
- This problem is not a big problem in a sputtering apparatus that forms a single layer on one discharge surface, but the controllability deteriorates as a plasma process or a plasma CVD electrode that performs one process by combining two plasmas. Therefore, it becomes a problem.
- the plasma electrode of the present invention that solves the above problems is An electrode body having a discharge surface on the outer peripheral surface, and a magnet for forming a tunnel-like magnetic field on the discharge surface;
- the discharge surface surrounds the outer periphery of the electrode body without or with a gap;
- a grounding member facing at least a part of the discharge surface with a gap and facing the electrode body.
- the plasma-treated electrode of the present invention that solves the above problems is as follows.
- the CVD electrode of the present invention includes the plasma processing electrode of the present invention, A source gas nozzle for introducing a CVD source in the vicinity of the electrode body, It is an electrode for film-forming on the base material installed in the place downstream from the electrode main body in the flow direction downstream of the gas discharge
- the plasma CVD apparatus of the present invention includes a vacuum vessel, a support mechanism for the base material, and the CVD electrode of the present invention in the vacuum vessel.
- the manufacturing method of the base material with a thin film of this invention which solves the said subject is as follows.
- the CVD electrode of the present invention plasma is generated by the plasma electrode, the gas introduced from the gas nozzle is decomposed into radicals through this plasma and supplied onto the substrate, and the CVD source introduced from the source gas nozzle is supplied onto the substrate. To form a thin film on the substrate.
- an efficient plasma source can be provided in terms of installation space or from the viewpoint of production efficiency, whereby plasma processing or plasma CVD film formation can be performed at a higher speed than in the past.
- FIG. 4b is a schematic diagram of a cross section taken along the arrow II of the plasma processing electrode shown in FIG. 4a.
- FIG. 1 is a schematic sectional view showing an example of the plasma electrode of the present invention.
- a magnet 101, a yoke 102 and a cathode 103 constitute an electrode body.
- the magnetic flux generated by the magnet 101 is induced by the yoke 102 and emitted onto the cathode 103, whereby the surface of the cathode 103 becomes a discharge surface, and a magnetron magnetic field is formed on this discharge surface.
- the cathode 103 is disposed so as to surround the magnet 101 with its surface facing outward.
- the magnet 101 may be surrounded by one cathode 103, (ii) the plurality of cathodes 103 may surround the magnet 101 without being spaced from each other, or (iii) the plurality of cathodes 103 may be surrounded.
- the magnets 101 may be surrounded at intervals.
- the form (i) is also one of the forms in which the cathode 103 is arranged around the magnet 103 without any interval. Since the cathode 103 is arranged so as to surround the magnet 101 as described above, the magnetron magnetic field formed on the discharge surface of the cathode 103 is connected to surround the electrode body.
- the plasma electrode includes a grounding member (not shown) facing the cathode 103 with a space therebetween.
- a grounding member (not shown) facing the cathode 103 with a space therebetween.
- the ground member does not need to be installed facing all of the cathodes 103, and may be installed facing a part of the cathode 103 if there is a part facing the electrode body. However, it is preferable that the ground member is installed so as to surround the electrode body because plasma generated by surrounding the electrode body is more stable.
- a space surrounded by the magnetic field generating means 101, the yoke 102, and the cathode 103 may be used as the refrigerant flow path 104.
- the coolant can be flowed through the coolant channel 104 to be cooled.
- the type and shape of the magnet 101 are appropriately selected so that a tunnel-like magnetic flux can be expressed with sufficient strength on the surface of the cathode 103.
- a ferrite magnet, a samarium cobalt magnet, a neodymium magnet or the like is preferably used as the type of the magnet 101.
- the shape of the magnet 101 may be appropriately determined according to the electrode shape. If it is a small circular electrode, a circular magnet can be preferably used.
- a rectangular magnet is generally used for the rectangular electrode. The magnet itself increases in size to be used for a wide electrode, but a large magnet has a strong magnetic force, so that handling such as assembly work becomes difficult. In such a case, a magnet group in which a plurality of rectangular magnets are arranged in a row is generally handled as one magnet.
- the arrangement of the magnet 101 and the yoke 102 can be appropriately determined depending on the configuration of the magnetic circuit. As shown in the schematic cross-sectional view of FIG. 1, when the magnetic circuit is configured to guide the magnetic flux emitted from one magnet 101 to the surfaces of the cathodes 103 on both sides using the yoke 102, as shown in the figure. In addition, a configuration in which one magnet 101 is arranged at the center is preferably used. 2 and 3 are schematic cross-sectional views showing another example of the plasma electrode of the present invention. As shown in the schematic cross-sectional view of FIG.
- the material of the cathode 103 can be appropriately determined depending on the use of the electrode.
- the cathode 103 is preferably configured so that the material used as a sputtering target is at least on the outermost surface on the discharge surface side.
- the cathode 103 is made of a material having a low sputtering rate, for example, a material such as aluminum or titanium so that the cathode 103 is less susceptible to erosion due to plasma. preferable.
- the cathode 103 is preferably cooled by some cooling means, and more preferably the cathode 103 itself is directly cooled by the refrigerant.
- an auxiliary magnetic pole can be formed by projecting the outer end of the yoke 102 outward from the surface of the cathode 103, that is, from the discharge surface of the electrode body.
- Use of such an auxiliary magnetic pole is more preferable because the controllability of the magnetic field on the cathode 103 can be improved.
- the auxiliary magnetic pole is designed so as to generate a magnetic field that rises sharply in a narrow range between the magnetic poles, high-density plasma concentrated in a narrow area can be obtained.
- the auxiliary magnetic pole is designed so as to generate a magnetic field with little fluctuation in the magnetic field strength over a wide range between the magnetic poles, a wide range of plasma can be obtained.
- FIG. 4 a is a schematic cross-sectional view showing an example of a plasma processing electrode using the plasma electrode of the present invention.
- FIG. 5 is a schematic diagram of a cross section taken along the line II of the plasma processing electrode of FIG. 4a.
- This plasma processing electrode uses the plasma electrode configuration illustrated in the schematic cross-sectional view of FIG. 1 as an electrode 201, and an earth member 202 is disposed so as to be sandwiched with a certain gap with respect to the electrode 201. Further, a gas nozzle 204 for introducing gas from a direction parallel to the discharge surface is disposed between the discharge surface on the surface of the cathode 103 and the ground member 202.
- a base material 203 supported by a support mechanism (not shown) is arranged at a position distant from the electrode 201 on an extension line in the gas introduction direction (downstream in the gas flow direction) introduced by the gas nozzle 204, and the surface of the base material 203 Is plasma treated.
- the support mechanism for the base material may be in a form that is fixed and does not move, or may be in the form of a cylindrical drum that moves so as to convey the base material 203.
- the gas nozzle 204 is arranged so that the gas can be directly introduced into the ionization space generated by the electrode 201, the introduced gas can be efficiently ionized. Moreover, since directionality can be imparted to the introduction of gas, ions, radicals, and the like generated in the ionization space can be used efficiently. From such characteristics, it is preferably used as a plasma processing apparatus such as an ion source or a radical source, and more preferably used as a plasma CVD electrode.
- FIG. 4b is a schematic sectional view showing another example of the plasma processing electrode using the plasma electrode of the present invention.
- the electrode 201 having the plasma electrode configuration shown in the schematic cross-sectional view of FIG. 1 is used as a basic unit, and two basic units are arranged side by side in the gas flow direction introduced from the gas nozzle 204.
- the two basic units side by side By arranging the two basic units side by side in this way, the introduced gas is exposed to a longer and stronger plasma to promote decomposition. Therefore, the amount of ions and radicals generated is increased, which is effective for improving the processing capability of the plasma processing apparatus and improving the film forming speed of the plasma CVD apparatus.
- the plasma processing electrode of FIG. 4 b is configured by arranging two basic units, it may be configured by arranging three or more.
- FIG. 6a is a schematic sectional view showing an example of a plasma CVD electrode using the plasma processing electrode of the present invention.
- a source gas nozzle 205 for introducing a CVD source is disposed on the opposite side of the gas nozzle 204 across the discharge space.
- plasma is generated in the discharge space by the plasma electrode.
- gas is introduce
- FIG. 6 b is a schematic cross-sectional view showing another example of a plasma CVD electrode using the plasma processing electrode of the present invention.
- a source gas nozzle 205 for introducing a CVD source is installed in the space between the electrode body 201 and the base 203 using the structure of the plasma processing electrode exemplified in the schematic cross-sectional view of FIG. Using this plasma processing electrode, plasma is generated in the discharge space by the plasma electrode. And gas is introduce
- the ionized gas is supplied to the space between the electrode body 201 and the base material 203, and the CVD source gas is supplied from the source gas nozzle 205 to the same space, whereby the CVD source gas is decomposed and a thin film is formed on the base material 203.
- Both the plasma CVD electrodes of FIGS. 6a and 6b are characterized in that the source gas nozzle 205 is located downstream of the discharge space with respect to the basic gas flow, so that the film-forming species are less likely to flow backward and the electrode 201 is less likely to be contaminated. There is. Further, the base material 203 can be moved away from the discharge space, and film formation can be performed with low damage by suppressing thermal damage and ion bombardment caused by plasma.
- the shortest distance between the center of the discharge space and the substrate 203 is preferably 30 mm or more in consideration of the ease of handling of the structure such as the source gas nozzle 205. If the gap between the center of the discharge space and the substrate 203 is longer than 300 mm, the film formation rate decreases, the occupied space becomes larger, and the efficiency is lowered. Therefore, the gap is preferably 300 mm or less.
- the mesh has an aperture ratio of 50% or more because it is possible to prevent the film forming ability from being lowered due to hindering the passage of products other than charged particles.
- the electrode body has the structure shown in FIG.
- As the magnet 101 it is assumed that a neodymium magnet having a magnetization direction (height direction) of 20 mm, a width of 10 mm, and a length of 40 mm is used side by side, and the magnet surface magnetic flux density is 300 mT.
- ferritic stainless steel SUS430 is used for the yoke 102
- the relative magnetic permeability was set to 500 (magnetic permeability 1.26 ⁇ 10 ⁇ 6 ⁇ 500 H / m). It was assumed that pure titanium was used for the cathode 103 and cooling water was allowed to flow through the coolant channel 104.
- the present invention can be applied not only to a plasma CVD electrode but also to a plasma processing electrode, a plasma electrode as an ion source or a radical source, etc., but the application range is not limited thereto.
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Abstract
Description
外周面に放電面を有し、この放電面にトンネル状の磁場を形成するためのマグネットが内部に設けられた電極本体と、
前記放電面は前記電極本体の外周を、間隔を置かずまたは間隔を置いて囲んでおり、
前記放電面の少なくとも一部と間隔を空けて対向し、前記電極本体を挟んで向かい合うアース部材と、を有している。
本発明のプラズマ電極と、
前記アース部材とこのアース部材に対向する前記放電面との間の放電空間へ、前記放電面と平行な方向からガスを導入するためのガスノズルと、を有している。
電極本体近傍にCVD原料を導入するための原料ガスノズルと、を有しており、
前記ガスノズルから放出されるガスの流れ方向下流側で、電極本体から離れたところに設置される基材に成膜するための電極である。
本発明のCVD電極を用い、プラズマ電極でプラズマ生成し、ガスノズルから導入されたガスをこのプラズマを通してラジカルに分解して基材上に供給すると共に、原料ガスノズルから導入されたCVD原料を基材上に供給することでこの基材に薄膜を形成する。
電極本体は図1に示す構造とした。マグネット101には着磁方向(高さ方向)20mm、幅10mm、長さ40mmのネオジウム磁石を並べて用いる想定とし、磁石表面磁束密度を300mTとした。ヨーク102にはフェライト系ステンレスSUS430を用いることと想定し、比透磁率を500(透磁率1.26×10-6×500H/m)と設定した。カソード103には純チタンを用い、冷媒流路104には冷却水を流す想定とした。以上の条件で図7に示す解析モデルを設定し、STAR-CCM+Ver.7.04.011を用いて解析を行った。解析の結果、カソードの周囲を取り囲むようにトンネル状の磁束が形成されることが分かった。参考までに、磁束密度分布の様子を図8の側面断面図および図9の正面図で示す。このカソードを用いれば、両直線部でのプラズマ強度が極端に違ったりしない、安定的なプラズマを生成することが出来る。
102 ヨーク
103 カソード
104 冷媒流路
105 ケーシング
201 電極
202 アース部材
203 基材
204 ガスノズル
205 原料ガスノズル
A 極間距離
B 冷媒流路幅
Claims (12)
- 外周面に放電面を有し、この放電面にトンネル状の磁場を形成するためのマグネットが内部に設けられた電極本体と、
前記放電面は前記電極本体の外周を、間隔を置かずまたは間隔を置いて囲んでおり、
前記放電面の少なくとも一部と間隔を空けて対向し、前記電極本体を挟んで向かい合うアース部材と、を有するプラズマ電極。 - 前記電極本体が補助磁極を有し、この補助磁極の外側端部は電極本体の前記放電面より外側に出ている、請求項1のプラズマ電極。
- 前記アース部材が前記電極本体を囲んでいる、請求項1または2のプラズマ電極。
- 請求項1~3のいずれかのプラズマ電極と、
前記アース部材とこのアース部材に対向する前記放電面との間の放電空間へ、放電面と平行な方向からガスを導入するためのガスノズルと、を有するプラズマ処理電極。 - 前記電極本体を複数有し、これら複数の電極本体が前記ガスノズルから導入されるガスの流れ方向に並べて配置された、請求項4のプラズマ処理電極。
- 請求項4または5のプラズマ処理電極と、
前記電極本体近傍にCVD原料を導入するための原料ガスノズルと、を有し、
前記ガスノズルから放出されるガスの流れ方向下流側で、前記電極本体から離れたところに設置される基材に成膜するためのCVD電極。 - 前記原料ガスノズルが、前記ガスノズルに対して前記放電空間を挟んだ反対側に設けられた、請求項6のCVD電極。
- 前記原料ガスノズルが、前記電極本体と前記基材が設置される位置との間の空間に設けられた、請求項6のCVD電極。
- 前記基材が設置される位置から前記電極本体までの最短距離が30mm以上300mm以下である、請求項6~8のいずれかのCVD電極。
- 前記電極本体と前記基材が設置される位置との間に、開口率50%以上のアース接続されたメッシュが設けられた、請求項6~9のいずれかのCVD電極。
- 真空容器と、この真空容器内に基材の支持機構と請求項6~10のいずれかのCVD電極とを備えたプラズマCVD装置。
- 請求項6~10のいずれかのCVD電極を用い、前記プラズマ電極でプラズマを生成し、前記ガスノズルから導入されたガスをこのプラズマを通してラジカルに分解して基材上に供給すると共に、前記原料ガスノズルから導入されたCVD原料を前記基材上に供給することでこの基材に薄膜を形成する、薄膜付基材の製造方法。
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US15/038,207 US20160298237A1 (en) | 2013-11-22 | 2014-11-12 | Plasma electrode, plasma processing electrode, cvd electrode, plasma cvd device, and method for manufacturing substrate with thin film |
KR1020167004073A KR102188988B1 (ko) | 2013-11-22 | 2014-11-12 | 플라즈마 전극, 플라즈마 처리 전극, cvd 전극, 플라즈마 cvd 장치 및 박막 부착 기재의 제조 방법 |
EP14863952.9A EP3073808B1 (en) | 2013-11-22 | 2014-11-12 | Plasma cvd device and method for manufacturing a substrate with a thin film |
CN201480058043.3A CN105659708B (zh) | 2013-11-22 | 2014-11-12 | 等离子体电极、等离子体处理电极、cvd电极、等离子体cvd装置及带薄膜的基材的制造方法 |
JP2014556848A JP6511813B2 (ja) | 2013-11-22 | 2014-11-12 | プラズマ処理電極およびcvd電極 |
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- 2014-11-12 KR KR1020167004073A patent/KR102188988B1/ko active IP Right Grant
- 2014-11-12 US US15/038,207 patent/US20160298237A1/en not_active Abandoned
- 2014-11-12 WO PCT/JP2014/079940 patent/WO2015076162A1/ja active Application Filing
- 2014-11-12 JP JP2014556848A patent/JP6511813B2/ja active Active
- 2014-11-12 EP EP14863952.9A patent/EP3073808B1/en active Active
- 2014-11-12 CN CN201480058043.3A patent/CN105659708B/zh active Active
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Also Published As
Publication number | Publication date |
---|---|
CN105659708A (zh) | 2016-06-08 |
KR102188988B1 (ko) | 2020-12-09 |
JPWO2015076162A1 (ja) | 2017-03-16 |
JP6511813B2 (ja) | 2019-05-15 |
CN105659708B (zh) | 2018-05-01 |
EP3073808A4 (en) | 2017-04-19 |
KR20160088854A (ko) | 2016-07-26 |
EP3073808A1 (en) | 2016-09-28 |
US20160298237A1 (en) | 2016-10-13 |
EP3073808B1 (en) | 2020-09-23 |
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