JP2013221169A - Thermal sprayed member and method for manufacturing the same - Google Patents
Thermal sprayed member and method for manufacturing the same Download PDFInfo
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本発明は、基材と、当該基材の表面を被覆する溶射膜とを備えた溶射部材およびその製造方法、ならびに溶射部材を備えた製造装置部材に関する。 The present invention relates to a thermal spray member including a base material, a thermal spray film covering the surface of the base material, a manufacturing method thereof, and a manufacturing apparatus member including the thermal spray member.
半導体デバイス、液晶デバイスなどを製造する場合、Ｓｉウエハやガラス基板に形成された所定の膜をＦ２などのハロゲン系の腐食性ガスを用いプラズマ環境下で処理するドライエッチングなどの工程が存在する。そこで、近年、半導体デバイス、液晶デバイスなどの製造装置において、プラズマ環境下で腐食ガスに曝されるチャンバーや各種部材に、Ａｌなどの金属材料からなる基材の耐食を防止するために、基材表面に耐食性のあるセラミックス膜を設けることがある。たとえば、特許文献１には、Ｙ２Ｏ３からなるセラミックス膜を溶射で基材表面に設けることが記載されている。
When manufacturing semiconductor devices, liquid crystal devices, etc., there are processes such as dry etching in which a predetermined film formed on a Si wafer or a glass substrate is processed in a plasma environment using a halogen-based corrosive gas such as F 2. . Therefore, in recent years, in manufacturing apparatuses such as semiconductor devices and liquid crystal devices, in order to prevent the corrosion resistance of a base material made of a metal material such as Al on a chamber or various members exposed to a corrosive gas in a plasma environment, A corrosion-resistant ceramic film may be provided on the surface. For example,
しかし、ドライエッチング工程におけるプラズマ環境下でハロゲン系の腐食性ガスとセラミックス膜とが反応すると、ＹＦ３などのパーティクル固形物が生じ、これらが付着して、半導体デバイス、液晶デバイスなどの品質が低下するという問題があった。 However, when a halogen-based corrosive gas and a ceramic film react in a plasma environment in a dry etching process, solid particles such as YF 3 are generated and adhered to them, and the quality of semiconductor devices, liquid crystal devices, and the like deteriorates. There was a problem to do.
そこで、腐食ガスが曝されるチャンバーや各種部材に石英ガラスを用いる場合がある。この場合、Ｆ２などのハロゲン系の腐食性ガスで処理が行われても、石英ガラスと反応して生じるＳｉＦ４などは気体となるため、パーティクルの発生を防止することができる。しかしながら、半導体デバイス、液晶デバイスの大型化に伴い、耐食性部材を石英ガラスで製造することは、製造コスト面で非常に不利であった。 Thus, quartz glass may be used for chambers and various members exposed to corrosive gases. In this case, even if the treatment is performed with a halogen-based corrosive gas such as F 2 , the generation of particles can be prevented because SiF 4 and the like generated by reaction with quartz glass become a gas. However, with the increase in size of semiconductor devices and liquid crystal devices, it has been extremely disadvantageous in terms of manufacturing cost to manufacture the corrosion-resistant member with quartz glass.
そこで、金属材料からなる基材表面にＳｉ基材料からなる膜を設けることが考えられる。そして、このために、Ｓｉ基材料からなる焼結体またはＳｉ基金属セラミック複合材料を基材の表面に形成することが考えられる。しかし、この方法では、複雑な形状の基材表面にＳｉ基材料からなる膜を設けることができない。 Therefore, it is conceivable to provide a film made of a Si-based material on the surface of a base material made of a metal material. For this purpose, it is conceivable to form a sintered body made of a Si-based material or a Si-based metal ceramic composite material on the surface of the substrate. However, with this method, a film made of a Si-based material cannot be provided on the surface of a substrate having a complicated shape.
そこで、本発明は、複雑な形状の基材の表面にもＳｉ基材料からなる膜が設けられうる溶射部材、およびこれを製造する方法、ならびに溶射部材を備えた製造装置を提供することを目的とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide a thermal spray member that can be provided with a film made of an Si-based material on the surface of a substrate having a complicated shape, a method for manufacturing the thermal spray member, and a manufacturing apparatus including the thermal spray member. And
前記課題を解決するための本発明の溶射部材は、基材と、前記基材の表面を被覆する、金属Ｓｉ、または、金属ＳｉとＳｉＣ、Ｓｉ3Ｎ4もしくはＳｉＯ2のうちいずれかとの混合物を主成分とする溶射膜とを有する溶射部材であって、前記溶射膜の相対密度が９０〜９７［％］であることを特徴とする。 The thermal spray member of the present invention for solving the above problems is a base material and a mixture of metal Si or any one of metal Si and SiC, Si 3 N 4 or SiO 2 covering the surface of the base material. The thermal spraying member which has a thermal spraying film which has as a main component, Comprising: The relative density of the said thermal spraying film is 90-97 [%], It is characterized by the above-mentioned.
本発明の溶射部材は、Ｓｉ基材料からなる膜が溶射膜であるので、複雑な形状の基材の表面にもＳｉ基材料からなる膜が設けられうる。そして、この膜は空隙が少なく緻密である。 In the thermal spray member of the present invention, since the film made of the Si-based material is the sprayed film, the film made of the Si-based material can also be provided on the surface of the base material having a complicated shape. This film is dense with few voids.
前記課題を解決するための本発明の製造装置は、半導体デバイスまたは液晶デバイスの製造装置であり、前記溶射部材をプラズマ環境下で腐食ガスに曝される部材としたことを特徴とする。 The manufacturing apparatus of the present invention for solving the above problems is a manufacturing apparatus of a semiconductor device or a liquid crystal device, wherein the thermal spray member is a member exposed to a corrosive gas in a plasma environment.
本発明の製造装置は、空隙が少なく緻密な溶射膜を有する溶射部材を備えるので、真空雰囲気で用いられたとき、真空度を上げることが容易になる。また、プラズマ環境下で溶射膜が腐食ガスと反応してもパーティクル固形物が発生するおそれがない。 Since the manufacturing apparatus of the present invention includes a thermal spray member having a dense thermal spray film with few voids, it is easy to increase the degree of vacuum when used in a vacuum atmosphere. Moreover, there is no possibility of generating solid particles even if the sprayed film reacts with the corrosive gas in a plasma environment.
前記課題を解決するための本発明の溶射部材の製造方法は、基材と、前記基材の表面を被覆する金属Ｓｉを含有する溶射膜とを有する溶射部材の製造方法であって、金属Ｓｉ粉末、または、金属Ｓｉ粉末と、ＳｉＣ粉末、Ｓｉ3Ｎ4粉末もしくはＳｉＯ2粉末のうちいずれかとの混合粉末を主成分とする原料粉末の加速エネルギーｘ［ｇ／ｍｉｎ／ｍｍ２］および熱エネルギーｙ［ｋＪ／ｋｇ］の組み合わせを、ｘ−ｙ平面において（１）ｘ＝３．０（２０．０≦ｙ≦７５．０）、（２）ｙ＝−４．１７ｘ＋８７．５（３．０≦ｘ≦１５．０）、（３）ｘ＝１５．０（１０．０≦ｙ≦２５．０）および（４）ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦１５．０）により近似される線分によって囲まれた第１領域に収まるように調節しながら、前記基材に対して前記原料粉末を溶射することにより、前記溶射膜を形成することを特徴とする。 The manufacturing method of the thermal spray member of the present invention for solving the above-mentioned problem is a manufacturing method of a thermal spray member having a base material and a thermal spray film containing metal Si covering the surface of the base material, Acceleration energy x [g / min / mm 2 ] and thermal energy of powder, or raw material powder mainly composed of mixed powder of SiC powder, Si 3 N 4 powder or SiO 2 powder The combination of y [kJ / kg] is expressed as (1) x = 3.0 (20.0 ≦ y ≦ 75.0), (2) y = −4.17x + 87.5 (3.0 ≦ x ≦ 15.0), (3) x = 15.0 (10.0 ≦ y ≦ 25.0) and (4) y = −0.83x + 22.5 (3.0 ≦ x ≦ 15.0) While adjusting to fit within the first region surrounded by the line segment approximated by By spraying the raw material powder to the base material, and forming the sprayed film.
前記原料粉末の加速エネルギーｘおよび熱エネルギーｙの組み合わせを、ｘ−ｙ平面において（１’）ｘ＝３．０（２０．０≦ｙ≦６０．０）、（２’）ｙ＝−２．９２ｘ＋６８．８（３．０≦ｘ≦１５．０）、（３’）ｘ＝１５．０（１５．０≦ｙ≦２５．０）、（４’）ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦９．０）および（５’）ｙ＝１５．０（９．０≦ｘ≦１５．０）により近似される線分によって囲まれた第２領域に収まるように調節することが好ましい。 The combination of the acceleration energy x and the thermal energy y of the raw material powder is expressed as (1 ′) x = 3.0 (20.0 ≦ y ≦ 60.0), (2 ′) y = −2. 92x + 68.8 (3.0 ≦ x ≦ 15.0), (3 ′) x = 15.0 (15.0 ≦ y ≦ 25.0), (4 ′) y = −0.83x + 22.5 (3 0.0 ≦ x ≦ 9.0) and (5 ′) y = 15.0 (9.0 ≦ x ≦ 15.0) to adjust to fit in the second region surrounded by the line segment Is preferred.
本発明の方法によれば、Ｓｉ基材料からなる膜を溶射膜として形成するので、複雑な形状の基材の表面にもＳｉ基材料からなる膜が設けることが可能となる。そして、この膜は空隙が少なく緻密である。 According to the method of the present invention, since a film made of a Si-based material is formed as a sprayed film, a film made of a Si-based material can be provided on the surface of a substrate having a complicated shape. This film is dense with few voids.
複雑な形状の基材の表面にもＳｉ基材料からなる溶射膜を設けることができる。そして、この膜は空隙が少なく緻密である。 A sprayed film made of a Si-based material can also be provided on the surface of a substrate having a complicated shape. This film is dense with few voids.
発明者は、溶射によってＳｉ基材料からなる膜を設けることを考えた。しかし、液滴化された溶射材が高速ガス流などによって処理対象である基材表面に吹き付けられるので、基材表面で凝固した溶射材間に空隙が生じる場合があることがわかった。半導体デバイス、液晶デバイスなどの製造装置は真空雰囲気で用いられ、空隙が多いと真空度を上げることが困難になる。 The inventor considered providing a film made of a Si-based material by thermal spraying. However, since the sprayed spray material is sprayed onto the surface of the substrate to be processed by a high-speed gas flow or the like, it has been found that voids may be generated between the sprayed materials solidified on the surface of the substrate. Manufacturing apparatuses such as semiconductor devices and liquid crystal devices are used in a vacuum atmosphere. If there are many voids, it is difficult to increase the degree of vacuum.
そこで、空隙が少ない緻密な溶射膜を備えた溶射部材、およびこれを製造する方法を鋭意研究した。以下、これらについて説明する。 In view of this, the inventors have intensively studied a thermal spray member having a dense thermal spray film with few voids and a method for manufacturing the thermal spray member. Hereinafter, these will be described.
（製造方法）
ステンレス、アルミニウム合金、アルミニウムまたは銅などの金属製基材の表面が砥粒を用いたサンドブラストにより表面粗さＲａが２．０［μｍ］以上になるような粗面状態に加工される。基材の表面は、各種溶射膜の熱膨張差の緩衝層となるアンダーコート（Ｎｉ−Ｃｒ−Ａｌなど）は被覆されていても、被覆されていなくても構わない。基材は平板状のものであっても複雑形状であっても構わない。
(Production method)
The surface of a metal base material such as stainless steel, aluminum alloy, aluminum or copper is processed into a rough surface state such that the surface roughness Ra becomes 2.0 [μm] or more by sandblasting using abrasive grains. The surface of the base material may or may not be coated with an undercoat (Ni-Cr-Al or the like) serving as a buffer layer for the difference in thermal expansion of various sprayed films. The substrate may be a flat plate or a complicated shape.
溶射原料粉末としては、金属Ｓｉ粉末、または、金属Ｓｉ粉末とＳｉＣ粉末、Ｓｉ3Ｎ4粉末もしくはＳｉＯ2粉末のうちいずれかとの混合粉末を主成分とする粉末が用いることができる。溶射原料粉末として、アルコールなどで湿式混合したものにポリビニルアルコールなどの結合材を混合したものをスプレードライヤーにより造粒したもの、こうした造粒粉末をさらに焼結したもの、混合物を溶融粉砕したものなどを用いることができる。 As the thermal spray raw material powder, metal Si powder, or powder mainly composed of mixed powder of metal Si powder and SiC powder, Si 3 N 4 powder or SiO 2 powder can be used. Thermal spraying raw material powder that is wet-mixed with alcohol etc. mixed with a binder such as polyvinyl alcohol, granulated with a spray dryer, further sintered with such granulated powder, melt-pulverized mixture, etc. Can be used.
なお、ＳｉＣ粉末、Ｓｉ3Ｎ4もしくはＳｉＯ2粉末は、それぞれ単独では溶射原料粉末にすることはできない。たとえば、ＳｉＣ粉末及びＳｉ3Ｎ4粉末は加熱されると溶融せずに分解される。しかし、ＳｉＣ粉末、Ｓｉ3Ｎ4粉末もしくはＳｉＯ2粉末を金属Ｓｉ粉末と混合すると、ＳｉＣ、Ｓｉ3Ｎ4もしくはＳｉＯ2を元の粒子形状を保ったまま溶射することが可能となる。 Note that the SiC powder, Si 3 N 4 or SiO 2 powder cannot be used alone as a thermal spray raw material powder. For example, SiC powder and Si 3 N 4 powder are decomposed without melting when heated. However, when SiC powder, Si 3 N 4 powder or SiO 2 powder is mixed with metal Si powder, it is possible to spray SiC, Si 3 N 4 or SiO 2 while maintaining the original particle shape.
溶射原料粉末を、プラズマ溶射することにより、溶射膜が形成される。プラズマ溶射装置は、一般の大気プラズマ溶射装置、減圧プラズマ溶射装置が使用でき、プラズマガスとして、Ａｒ，Ａｒ＋Ｎ２，Ａｒ＋Ｈ２、Ａｒ＋ＣＯ２またはＡｒ＋Ｏ２などが用いられる。 A thermal spray film is formed by plasma spraying the thermal spray raw material powder. As the plasma spraying apparatus, a general atmospheric plasma spraying apparatus or a low pressure plasma spraying apparatus can be used, and Ar, Ar + N 2 , Ar + H 2 , Ar + CO 2, Ar + O 2 or the like is used as a plasma gas.
溶射ガンと基材との距離はたとえば１５０［ｍｍ］以下、好ましくは１００［ｍｍ］以下に設定される。溶射距離が１５０［ｍｍ］を超えると、溶射膜の密度が低下したり表面粗さが大きくなるため、パーティクルの発生原因になり好ましくない。 The distance between the spray gun and the substrate is set to, for example, 150 [mm] or less, preferably 100 [mm] or less. When the spraying distance exceeds 150 [mm], the density of the sprayed film decreases or the surface roughness increases, which is not preferable because it causes generation of particles.
また、溶射施工時には溶射膜が基材から剥離することを防止するため、基材はコンプレッサーエアなどの空冷方式により冷却される。なお、基材は水冷によって冷却されても構わない。水冷の場合、基材の中に水を流し、流出側の水温が１００［℃］以下となるように水量および水温が調節される。 Moreover, in order to prevent the sprayed film from being peeled off from the base material at the time of thermal spraying, the base material is cooled by an air cooling method such as compressor air. The substrate may be cooled by water cooling. In the case of water cooling, the amount of water and the water temperature are adjusted so that water flows through the substrate and the water temperature on the outflow side is 100 [° C.] or less.
プラズマ溶射に際して、使用するプラズマガスの流量、印加する電力を変更し、原料粉末の加速エネルギーｘ［ｇ／ｍｉｎ／ｍｍ２］および熱エネルギーｙ［ｋＪ／ｋｇ］の組み合わせがｘ−ｙ平面における「第１領域」に収まるように調節された。 At the time of plasma spraying, the flow rate of plasma gas to be used and the power to be applied are changed, and the combination of the acceleration energy x [g / min / mm 2 ] and the thermal energy y [kJ / kg] of the raw material powder is “ It was adjusted to fit in the “first region”.
加速エネルギーｘは、単位時間に投入したプラズマガス量（質量）を溶射ガン先端のプラズマガスを放出するノズルの穴の面積で除した値により表わされ、プラズマガスの流量の多少、プラズマガスの種類およびプラズマガスノズルの穴面積に応じて増減する。 The acceleration energy x is expressed by a value obtained by dividing the amount (mass) of plasma gas input per unit time by the area of the nozzle hole that discharges the plasma gas at the tip of the spray gun. Increase or decrease depending on the type and hole area of the plasma gas nozzle.
また、熱エネルギーｙはプラズマを発生させている電力を単位時間に投入したプラズマガス量（質量）で除した数値により表わされ、プラズマガスの種類、プラズマ出力に応じても増減する。 The thermal energy y is represented by a numerical value obtained by dividing the power generating plasma by the amount (mass) of plasma gas input per unit time, and increases or decreases depending on the type of plasma gas and the plasma output.
第１領域は、図１に実線で示され、式（１）〜（４）のそれぞれにより近似される４本の線分Ｌ１〜Ｌ４によって囲まれている。 The first region is indicated by a solid line in FIG. 1 and is surrounded by four line segments L1 to L4 that are approximated by equations (1) to (4), respectively.
ｘ＝３．０（２０．０≦ｙ≦７５．０）‥（１）
ｙ＝−４．１７ｘ＋８７．５（３．０≦ｘ≦１５．０） ‥（２）
ｘ＝１５．０（１０．０≦ｙ≦２５．０） ‥（３）
ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦１５．０） ‥（４）。
x = 3.0 (20.0 ≦ y ≦ 75.0) (1)
y = -4.17x + 87.5 (3.0 ≦ x ≦ 15.0) (2)
x = 15.0 (10.0 ≦ y ≦ 25.0) (3)
y = −0.83x + 22.5 (3.0 ≦ x ≦ 15.0) (4).
第１領域に代えて、第１領域の一部である「第２領域」に収まるように、原料粉末の加速エネルギーｘおよび熱エネルギーｙの組み合わせが採用されてもよい。第２領域は、図１に破線で示され、式（１’）〜（５’）によって近似される５本の線分Ｌ１’〜Ｌ５’により囲まれている。 Instead of the first region, a combination of the acceleration energy x and the thermal energy y of the raw material powder may be employed so as to fit in the “second region” which is a part of the first region. The second region is surrounded by five line segments L1 'to L5' approximated by the equations (1 ') to (5') shown by broken lines in FIG.
ｘ＝３．０（２０．０≦ｙ≦６０．０） ‥（１’）
ｙ＝−２．９２ｘ＋６８．８（３．０≦ｘ≦１５．０） ‥（２’）
ｘ＝１５．０（１５．０≦ｙ≦２５．０） ‥（３’）
ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦９．０） ‥（４’）
ｙ＝−１５．０（９．０≦ｘ≦１５．０） ‥（５’）。
x = 3.0 (20.0 ≦ y ≦ 60.0) (1 ′)
y = -2.92x + 68.8 (3.0 ≦ x ≦ 15.0) (2 ′)
x = 15.0 (15.0 ≦ y ≦ 25.0) (3 ′)
y = −0.83x + 22.5 (3.0 ≦ x ≦ 9.0) (4 ′)
y = -15.0 (9.0 ≦ x ≦ 15.0) (5 ′).
線分Ｌ１〜Ｌ４または線分Ｌ１’〜Ｌ５’は、第１領域または第２領域を次のような領域Ｓ１〜Ｓ４から区分するために定義される。 The line segments L1 to L4 or the line segments L1 'to L5' are defined to divide the first region or the second region from the following regions S1 to S4.
熱エネルギーｙが高い一方、加速エネルギーｘが低い領域Ｓ１では、原料粉末が揮発または昇華しやすくなり、塗着率の低下を招くことがある。また、加速エネルギーが低いため、基材に衝突する溶射粒子または液滴が溶射膜表面に形成されている細かい凹部に入り込むことができず、気孔が多い低密度の溶射膜が形成されてしまう。また、この領域Ｓ１では、熱エネルギーｙに比較してプラズマガス流量が少ないため、プラズマが発生しても失火しやすく、安定な成膜が困難である。 In the region S1 where the thermal energy y is high but the acceleration energy x is low, the raw material powder is likely to volatilize or sublimate, and the coating rate may be reduced. Further, since the acceleration energy is low, the sprayed particles or droplets that collide with the base material cannot enter the fine recesses formed on the surface of the sprayed film, and a low-density sprayed film with many pores is formed. Further, in this region S1, since the plasma gas flow rate is small as compared with the thermal energy y, it is easy to misfire even if plasma is generated, and stable film formation is difficult.
加速エネルギーｘおよび熱エネルギーｙがともに高い領域Ｓ２では、きわめて短時間であれば緻密な膜（溶射膜）が成形されうるものの、溶射ノズルの先端の損傷等、プラズマ溶射装置の損傷が発生する可能性が高く、実製品を安定した膜質で製造することが困難である。溶射ノズルの先端の損傷等が生じずに、所望の厚さ（たとえば０．１［ｍｍ］以上）の溶射膜が得られるという観点から、領域Ｓ２から第１領域および第２領域を区分するための、式（２）（２’）により表わされる境界線分が適宜変更されてもよい。 In the region S2 where the acceleration energy x and the thermal energy y are both high, a dense film (sprayed film) can be formed for a very short time, but damage to the plasma spraying device such as damage to the tip of the spray nozzle can occur. It is difficult to manufacture an actual product with a stable film quality. In order to distinguish the first region and the second region from the region S2 from the viewpoint that a sprayed film having a desired thickness (for example, 0.1 [mm] or more) can be obtained without causing damage to the tip of the spray nozzle. The boundary line segments represented by the equations (2) and (2 ′) may be changed as appropriate.
加速エネルギーｘが高い一方で熱エネルギーｙが低い領域Ｓ３では、原料粉末の溶融が不十分である。このため、基材に対する原料の付着率が著しく低く、付着したとしても著しく多孔質な溶射膜しか形成されえない。また、この領域Ｓ３では、プラズマが発生しにくく、Ｓ１と同様プラズマが発生しても失火しやすく、安定な成膜が困難である。 In the region S3 where the acceleration energy x is high but the thermal energy y is low, the raw material powder is not sufficiently melted. For this reason, the adhesion rate of the raw material with respect to a base material is remarkably low, and even if it adheres, only a remarkably porous sprayed film can be formed. Further, in this region S3, it is difficult for plasma to be generated, and even if plasma is generated as in S1, misfire is likely to occur, and stable film formation is difficult.
加速エネルギーｘおよび熱エネルギーｙがともに低い領域Ｓ４では、原料粉末の溶融がより不十分である。このため、基材に対する原料の付着率が著しく低く、付着したとしても著しく多孔質な溶射膜しか形成されえない。また、この領域では、プラズマが不安定になりやすく、長時間にわたるプラズマ溶射の継続は困難である。 In the region S4 where both the acceleration energy x and the thermal energy y are low, the raw material powder is more insufficiently melted. For this reason, the adhesion rate of the raw material with respect to a base material is remarkably low, and even if it adheres, only a remarkably porous sprayed film can be formed. In this region, the plasma tends to become unstable, and it is difficult to continue plasma spraying for a long time.
溶射膜のＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２の平均粒径は０．１〜１０μｍであり、ＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２の焼結体にＳｉを含浸させて作製したＳｉＣ／Ｓｉ複合材料体、Ｓｉ３Ｎ４／Ｓｉ複合材料体、またはＳｉＯ２／Ｓｉ複合材料体中のＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２の平均粒径１０〜１００μｍに比較して小さくなっている。ＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２の粒径が細かいと、溶射膜の相対密度が高くなるため、好ましい。一方、粒径が粗くなり過ぎると、溶射膜の密度低下や粒子の脱落が生じやすくなるため、好ましくない。 The average particle diameter of SiC, Si 3 N 4 or SiO 2 in the sprayed film is 0.1 to 10 μm, and the SiC / Si composite produced by impregnating Si into a sintered body of SiC, Si 3 N 4 or SiO 2 The average particle size of SiC, Si 3 N 4 or SiO 2 in the material body, Si 3 N 4 / Si composite body, or SiO 2 / Si composite body is smaller than that of 10 to 100 μm. It is preferable that the particle size of SiC, Si 3 N 4 or SiO 2 is small because the relative density of the sprayed film is increased. On the other hand, if the particle size becomes too coarse, it is not preferable because the density of the sprayed film is reduced and the particles are likely to fall off.
溶射膜の相対密度は９０％以上であることが好ましい。相対密度が９０％に満たないと、溶射膜の粒子の結合が弱くパーティクルが発生するおそれが大きくなり、また製造装置の真空度を保持することが困難になるため、好ましくない。 The relative density of the sprayed film is preferably 90% or more. If the relative density is less than 90%, bonding of particles in the sprayed film is weak and the possibility of generating particles increases, and it is difficult to maintain the degree of vacuum in the manufacturing apparatus, which is not preferable.
溶射膜の同素材の焼結体に対するビッカース硬度の比は０．５以上であることが好ましい。この比が０．５に満たないと、溶射膜を形成する粒子の結合が弱く、パーティクルが発生するおそれが大きくなるため、好ましくない。 The ratio of the Vickers hardness to the sintered body of the same material of the sprayed film is preferably 0.5 or more. If this ratio is less than 0.5, the bonding of the particles forming the sprayed film is weak and the possibility of generating particles is increased, which is not preferable.
溶射膜の表面粗さＲａは７μｍ以下であることが好ましい。表面粗さＲａが７μｍより大きくなると、溶射膜表面を構成する粒子の結合が弱く、パーティクルの発生を招くため、好ましくない。 The surface roughness Ra of the sprayed film is preferably 7 μm or less. When the surface roughness Ra is larger than 7 μm, the bonding of the particles constituting the sprayed film surface is weak and causes the generation of particles, which is not preferable.
なお、溶射材の組成を変更することによって、溶射膜の性能を傾斜的に変化させることが可能となる。たとえば、溶射膜の基材表面に近い部分の硬度を低くして基材と溶射膜との密着性を図るとともに、溶射膜の表面部分の硬度を高くして傷付防止を図ることができる。また、溶射膜の基材表面に近い部分の熱膨張率を基材と近いものとして、基材と溶射膜との剥離防止を図ることもできる。 In addition, it becomes possible to change the performance of the sprayed coating in an inclined manner by changing the composition of the sprayed material. For example, the hardness of the portion near the substrate surface of the sprayed film can be lowered to improve the adhesion between the substrate and the sprayed film, and the hardness of the surface portion of the sprayed film can be increased to prevent damage. Moreover, the thermal expansion coefficient of the part near the base material surface of the sprayed film can be made close to the base material to prevent the base material and the sprayed film from peeling off.
（製造装置）
本発明の溶射部材は、半導体デバイスまたは液晶デバイスの製造装置において、プラズマ環境下で腐食ガスに曝されるチャンバーなどの各種部材として使用されることに適している。これは、空隙が少なく緻密な溶射膜を溶射部材が備えるため、真空雰囲気で使用したときに、真空度を上げることが容易になるからである。また、プラズマ環境下で溶射膜が腐食ガスと反応してもパーティクル固形物が発生するおそれがないからである。
(manufacturing device)
The thermal spray member of the present invention is suitable for use as various members such as a chamber exposed to a corrosive gas in a plasma environment in a semiconductor device or liquid crystal device manufacturing apparatus. This is because the thermal spray member has a dense thermal spray film with few voids, so that it is easy to increase the degree of vacuum when used in a vacuum atmosphere. Moreover, even if the sprayed film reacts with the corrosive gas in the plasma environment, there is no possibility that particle solids are generated.
（実施例）
前記方法により、溶射膜を有する溶射部材が製造された。原料粉末として（１）ＳｉＣ粉末（７５体積％）と金属Ｓｉ粉末（２５体積％）、（２）金属Ｓｉ粉末（１００体積％）、（３）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（４）ＳｉＯ2粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（５）ＳｉＣ粉末（９０体積％）と金属Ｓｉ粉末（１０体積％）、（６）金属Ｓｉ粉末（１００体積％）、（７）Ｓｉ3Ｎ4粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（８）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（９）ＳｉＣ粉末（１０体積％）と金属Ｓｉ粉末（９０体積％）、（１０）金属Ｓｉ粉末（１００体積％）、（１１）金属Ｓｉ粉末（１００体積％）、（１２）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（１３）金属Ｓｉ粉末（１００体積％）、（１４）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（１５）Ｓｉ3Ｎ4粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（１６）ＳｉＣ粉末（２５体積％）と金属Ｓｉ粉末（７５体積％）、（１７）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）のそれぞれが用いられ、実施例１〜１７の溶射部材が製造された。
(Example)
By the above method, a thermal spray member having a thermal spray film was manufactured. (1) SiC powder (75% by volume) and metal Si powder (25% by volume), (2) Metal Si powder (100% by volume), (3) SiC powder (50% by volume) and metal Si powder ( 50 volume%), (4) SiO 2 powder (50 volume%) and metal Si powder (50 volume%), (5) SiC powder (90 volume%) and metal Si powder (10 volume%), (6) metal Si powder (100% by volume), (7) Si 3 N 4 powder (50% by volume) and metal Si powder (50% by volume), (8) SiC powder (50% by volume) and metal Si powder (50% by volume) (9) SiC powder (10% by volume) and metal Si powder (90% by volume), (10) Metal Si powder (100% by volume), (11) Metal Si powder (100% by volume), (12) SiC powder (50% by volume) and metal Si powder (50% by volume), (13) metal Si powder Powder (100% by volume), (14) SiC powder (50% by volume) and metal Si powder (50% by volume), (15) Si 3 N 4 powder (50% by volume) and metal Si powder (50% by volume), (16) SiC powder (25% by volume) and metallic Si powder (75% by volume), (17) SiC powder (50% by volume) and metallic Si powder (50% by volume), respectively, Examples 1 to 17 The thermal spraying member was manufactured.
実施例１〜１７のそれぞれの溶射部材の製造条件としての溶射の加速エネルギーｘおよび熱エネルギーｙの組み合わせが、第１領域または第２領域に収まるように調節された。加速エネルギーｘおよび熱エネルギーｙの組み合わせを示すプロットが、図１において丸付き数字により示されている。丸の中の数字は実施例の番数を表わしている。図１から実施例１〜１７のうち、実施例１〜５、８〜１７が第２領域に含まれていることがわかる。 The combination of thermal acceleration energy x and thermal energy y as production conditions for each of the thermal spray members of Examples 1 to 17 was adjusted to be in the first region or the second region. A plot showing the combination of acceleration energy x and thermal energy y is indicated by the circled numbers in FIG. The number in the circle represents the number of the example. It can be seen from FIG. 1 that Examples 1 to 5 and Examples 8 to 17 of Examples 1 to 17 are included in the second region.
各実施例において、溶射膜の相対密度、原料粉末の基材に対する塗着率、溶射膜の同素材の焼結体に対するビッカース硬度の比、溶射膜の表面粗さＲａ、およびテープ試験での脱粒数のそれぞれが測定された。また、溶射膜がＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２を含む場合、これらの平均粒径が測定された。表１には測定結果がまとめて示されている。なお、実施例２、６、１０、１１、１３では、溶射膜中に、マイクロクラックやポアが存在してＳｉ粒子の形状が不明瞭であるので、Ｓｉ粒子の粒径を測定することはできなかった。 In each example, the relative density of the sprayed film, the coating ratio of the raw material powder to the base material, the ratio of the Vickers hardness to the sintered body of the same material of the sprayed film, the surface roughness Ra of the sprayed film, and the degranulation in the tape test Each of the numbers was measured. Further, when the sprayed film contains SiC, Si 3 N 4 or SiO 2 , the average particle diameter of these was measured. Table 1 summarizes the measurement results. In Examples 2, 6, 10, 11, and 13, since the shape of the Si particles is unclear due to the presence of microcracks and pores in the sprayed film, the particle size of the Si particles cannot be measured. There wasn't.
テープ試験は、カーボンテープ（ＳＨＩＮＴＯＰＡＩＮＴ製、Ｓｈｉｎｔｒｏｎｔａｐｅ）を用い、射放し面の溶射膜の表面にカーボンテープを貼った後、再びカーボンテープを剥し、溶射膜と接触したカーボンテープ表面をＳＥＭで観察して、溶射膜から脱落してカーボンテープ表面に接着した粒子の１ｍｍ２当りの個数を調べた。 In the tape test, a carbon tape (manufactured by SHINTTOPAINT, Shintrontape) was used. After the carbon tape was applied to the surface of the sprayed film, the carbon tape was peeled off again and the carbon tape surface in contact with the sprayed film was observed with an SEM Then, the number per 1 mm 2 of the particles dropped from the sprayed film and adhered to the carbon tape surface was examined.
Ａｌ６０６１製の基材（２５×７×２．５［ｍｍ］、表面積５．１［ｃｍ２］）の全面に各溶射膜が形成される。 Each sprayed film is formed on the entire surface of a substrate made of Al6061 (25 × 7 × 2.5 [mm], surface area 5.1 [cm 2 ]).
表１から、エネルギー組み合わせが第１領域に含まれるように溶射環境が調節されることにより、相対密度が９０〜９７［％］の範囲にある緻密な溶射膜を備えた溶射部材が製造されることがわかる。また、原料粉末の基材または溶射膜に対する塗着率が４５［％］以上であり、同素材の焼結体に対する溶射膜のビッカース硬度の比が０．５以上であり、溶射膜の表面粗さＲａが７．０［μｍ］以下であり、テープ試験による溶射膜の射放し面の脱粒が１ｍｍ2当り５０個以下であることがわかる（実施例１〜１７参照）。また、溶射膜がＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２を含む場合、これらの平均粒径が０．１〜１０μｍであることがわかる（実施例１、３〜５、７〜９、１２、１４〜１７参照）。 From Table 1, the thermal spraying environment is adjusted so that the energy combination is included in the first region, whereby a thermal spraying member including a dense thermal spraying film having a relative density in the range of 90 to 97 [%] is manufactured. I understand that. Further, the coating ratio of the raw material powder to the base material or the sprayed film is 45% or more, the ratio of the Vickers hardness of the sprayed film to the sintered body of the same material is 0.5 or more, and the surface roughness of the sprayed film The thickness Ra is 7.0 [μm] or less, and it can be seen that the sprayed surface of the sprayed film by the tape test has 50 grains or less per 1 mm 2 (see Examples 1 to 17). Further, if the sprayed coating comprises SiC, the Si 3 N 4 or SiO 2, it is understood that these average particle diameter of 0.1 to 10 [mu] m (Example 1,3～5,7～9,12,14 To 17).
さらに、エネルギー組み合わせが第２領域に含まれるように溶射環境が調節されることにより、溶射膜の表面粗さＲａが６．１［μｍ］以下に低減されることがわかる（実施例１〜５、８〜１７参照）。 Further, it is understood that the surface roughness Ra of the sprayed film is reduced to 6.1 [μm] or less by adjusting the spraying environment so that the energy combination is included in the second region (Examples 1 to 5). 8-17).
第１領域の境界線の近似式（１）〜（４）は、溶射ガンの損傷を生じずに溶射膜が十分な厚さ（たとえば０．１［ｍｍ］以上）を有し、溶射膜の相対密度が９０〜９７［％］の範囲にあり、原料粉末の基材または溶射膜に対する塗着率が４５［％］以上であり、溶射膜の同素材の焼結体に対するビッカース硬度の比が０．５以上であり、溶射膜の表面粗さＲａが７．０［μｍ］以下であり、テープ試験による溶射膜の射放し面の脱粒が５０［個／ｍｍ2］以下であり、溶射膜がＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２を含む場合にはこれらの平均粒径が０．１〜１０μｍである第１の実施例群のうち、最も外側に位置する測定データに基づいて求められる。 The approximate expressions (1) to (4) of the boundary line of the first region have a sufficient thickness (for example, 0.1 [mm] or more) without causing damage to the spray gun. The relative density is in the range of 90 to 97 [%], the coating ratio of the raw material powder to the base material or the sprayed film is 45 [%] or more, and the ratio of the Vickers hardness to the sintered body of the same material of the sprayed film is It is 0.5 or more, the surface roughness Ra of the sprayed film is 7.0 [μm] or less, the degranulation of the sprayed surface of the sprayed film by the tape test is 50 [pieces / mm 2 ] or less, and the sprayed film When SiC contains SiC, Si 3 N 4 or SiO 2 , it is obtained based on measurement data located on the outermost side in the first example group in which the average particle diameter is 0.1 to 10 μm.
近似式（１）は、実施例１０を基準とする１次式により表現されている。近似式（２）は、実施例６および実施例９のそれぞれを基準として定められ、当該実施例に相当する２点を結ぶ１次式により表現されてもよい。近似式（３）は、実施例１７を基準とする１次式により表現されている。近似式（４）は、実施例１および実施例７を基準として定められ、当該実施例のそれぞれに相当する２点を結ぶ１次式により表現されていてもよい。 The approximate expression (1) is expressed by a linear expression based on the tenth embodiment. The approximate expression (2) is determined based on each of the sixth embodiment and the ninth embodiment, and may be expressed by a linear expression connecting two points corresponding to the embodiment. The approximate expression (3) is expressed by a linear expression based on the seventeenth embodiment. The approximate expression (4) is determined with reference to the first embodiment and the seventh embodiment, and may be expressed by a linear expression connecting two points corresponding to the respective embodiments.
第２領域の境界線の近似式（１’）〜（５’）は、溶射ガンの損傷を生じずに溶射膜が十分な厚さ（たとえば０．１［ｍｍ］以上）を有し、溶射膜の相対密度が９０〜９７［％］の範囲にあり、原料粉末の基材または溶射膜に対する塗着率が４５［％］以上であり、溶射膜の同素材の焼結体に対するビッカース硬度の比が０．５以上であり、溶射膜の表面粗さＲａが６．１［μｍ］以下であり、テープ試験による溶射膜の射放し面の脱粒が５０［個／ｍｍ2］以下であり、溶射膜がＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２を含む場合にはこれらの平均粒径が０．１〜１０μｍである第２の実施例群のうち、最も外側に位置する測定データに基づいて求められる。 The approximation formulas (1 ′) to (5 ′) of the boundary line of the second region are such that the sprayed film has a sufficient thickness (for example, 0.1 [mm] or more) without causing damage to the spray gun. The relative density of the film is in the range of 90 to 97 [%], the coating ratio of the raw material powder to the substrate or the sprayed film is 45 [%] or more, and the Vickers hardness of the sintered material of the same material of the sprayed film is The ratio is 0.5 or more, the surface roughness Ra of the sprayed film is 6.1 [μm] or less, and the degranulation of the sprayed surface of the sprayed film by the tape test is 50 [pieces / mm 2 ] or less, When the sprayed film contains SiC, Si 3 N 4 or SiO 2 , it is obtained based on measurement data located on the outermost side in the second embodiment group in which the average particle diameter is 0.1 to 10 μm. It is done.
たとえば、近似式（２’）は、実施例９および実施例１０を基準とする１次式により表現されている。近似式（５’）は、実施例１７を基準とする１次式により表現されている。 For example, the approximate expression (2 ′) is expressed by a linear expression based on the ninth and tenth embodiments. The approximate expression (5 ′) is expressed by a linear expression based on the seventeenth embodiment.
近似式は、複数の実施例のそれぞれに相当する複数の点に基づき、最小二乗法等にしたがって求められる２次以上の高次式により表わされてもよい。たとえば、近似式（２’）が実施例５、９、１０および１５のそれぞれに相当する４点に基づき、最小二乗法等にしたがって求められる２次以上の高次式により表わされてもよい。測定結果が良好であったプロットがすべて第１領域または第２領域に含まれるように、最小二乗法等により求められた境界線分がｙ方向およびｘ方向のうち少なくとも一方にずらされてもよい。 The approximate expression may be expressed by a higher-order expression of the second or higher order obtained according to the least square method or the like based on a plurality of points corresponding to each of the plurality of embodiments. For example, the approximate expression (2 ′) may be expressed by a higher-order expression of the second or higher order obtained according to the least square method or the like based on the four points corresponding to the fifth, ninth, tenth and fifteenth embodiments. . The boundary line segment obtained by the least square method or the like may be shifted to at least one of the y direction and the x direction so that all plots with good measurement results are included in the first region or the second region. .
（比較例）
原料粉末として（１）金属Ｓｉ粉末（１００体積％）、（２）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（３）金属Ｓｉ粉末（１００体積％）、（４）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（５）ＳｉＣ粉末（５０体積％）と金属Ｓｉ粉末（５０体積％）、（６）ＳｉＣ粉末（２５体積％）と金属Ｓｉ粉末（７５体積％）、（７）金属Ｓｉ粉末（１００体積％）のそれぞれが用いられ、比較例１〜７の溶射部材が製造された。
(Comparative example)
(1) Metal Si powder (100% by volume), (2) SiC powder (50% by volume) and metal Si powder (50% by volume), (3) Metal Si powder (100% by volume), (4) SiC powder (50% by volume) and metal Si powder (50% by volume), (5) SiC powder (50% by volume) and metal Si powder (50% by volume), (6) SiC powder (25% by volume) and metal Si Each of powder (75 volume%) and (7) metal Si powder (100 volume%) was used, and the thermal spray member of Comparative Examples 1-7 was manufactured.
比較例１〜１０のそれぞれの溶射部材の製造条件としての溶射の加速エネルギーｘおよび熱エネルギーｙの組み合わせが、第１範囲から外れるように調節された。加速エネルギーｘおよび熱エネルギーｙの組み合わせを示すプロットが、図１において三角付き数字により示されている。三角の中の数字は実施例の番数を表わしている。 The combination of thermal spray acceleration energy x and thermal energy y as the production conditions of each thermal spray member of Comparative Examples 1 to 10 was adjusted to be out of the first range. A plot showing the combination of acceleration energy x and thermal energy y is shown in FIG. The number in the triangle represents the number of the embodiment.
各比較例において、溶射膜の相対密度、原料粉末の基材に対する塗着率、溶射膜の同素材の焼結体に対するビッカース硬度の比、および溶射膜の表面粗さＲａのそれぞれが測定された。また、溶射膜がＳｉＣ、Ｓｉ３Ｎ４またはＳｉＯ２を含む場合、これらの平均粒径が測定された。表２には測定結果がまとめて示されている。 In each comparative example, the relative density of the sprayed film, the coating ratio of the raw material powder to the base material, the ratio of the Vickers hardness to the sintered body of the same material of the sprayed film, and the surface roughness Ra of the sprayed film were measured. . Further, when the sprayed film contains SiC, Si 3 N 4 or SiO 2 , the average particle diameter of these was measured. Table 2 summarizes the measurement results.
ただし、比較例８によれば、プラズマは点火させることはできたが、出力が安定しないために溶射を行うことができなった。比較例９によれば、プラズマを点火させることができなかった。比較例１０はプラズマを発生させることはできたが、出力が高すぎたため１ｍｉｎ弱でプラズマトーチが焼損し、製膜はできなかった。 However, according to Comparative Example 8, the plasma could be ignited, but the thermal spraying could not be performed because the output was not stable. According to Comparative Example 9, the plasma could not be ignited. In Comparative Example 10, plasma could be generated, but since the output was too high, the plasma torch was burned out in less than 1 min and film formation was not possible.
表２から、エネルギー組み合わせが第１領域から外れるように溶射環境が調節されることにより、実施例と比較して、相対密度が８４〜８９［％］という低い範囲になることがわかる。また、実施例と比較した場合に、原料粉末の基材または溶射膜に対する塗着率が１３〜３０［％］に低下し、溶射膜の同素材の焼結体に対するビッカース硬度の比が０．３５〜０．４７という低い範囲にあり、溶射膜の表面粗さＲａが７．１〜８．６［μｍ］という高い範囲にあり、テープ試験による溶射膜の射放し面の脱粒が５７〜１５０［個／ｍｍ2］という高い範囲にあり、溶射膜中のＳｉＣの平均粒径が１１．９と大きな溶射膜を備えた溶射部材が製造される場合があることがわかる（比較例１〜７参照）。 From Table 2, it can be seen that the relative density is in the low range of 84 to 89 [%] as compared with the example by adjusting the thermal spraying environment so that the energy combination deviates from the first region. Further, when compared with the examples, the coating ratio of the raw material powder to the base material or the sprayed film is reduced to 13 to 30 [%], and the ratio of the Vickers hardness to the sintered body of the same material of the sprayed film is 0. It is in the low range of 35 to 0.47, the surface roughness Ra of the sprayed film is in the high range of 7.1 to 8.6 [μm], and the degranulation of the sprayed surface of the sprayed film by the tape test is 57 to 150. It can be seen that there is a case where a sprayed member having a large sprayed film with a mean SiC particle size of 11.9 in the sprayed film is produced in a high range of [pieces / mm 2 ] (Comparative Examples 1 to 7). reference).
なお、ＳｉＣの焼結体にＳｉを含浸させて作製した、ＳｉＣが５０体積％、Ｓｉが５０体積％のＳｉＣ／Ｓｉ複合材料体中におけるＳｉＣの平均粒径は３５μｍであった。 In addition, the average particle diameter of SiC in a SiC / Si composite material produced by impregnating Si into a SiC sintered body and containing 50% by volume of SiC and 50% by volume of Si was 35 μm.
Claims (4)
前記溶射膜の相対密度が９０〜９７［％］であることを特徴とする溶射部材。 A thermal spray member having a base material and a thermal spray film mainly comprising a metal Si or a mixture of metal Si and SiC, Si 3 N 4, or SiO 2 covering the surface of the base material. And
A thermal spray member having a relative density of 90 to 97 [%] of the thermal spray film.
金属Ｓｉ粉末、または、金属Ｓｉ粉末とＳｉＣ粉末、Ｓｉ3Ｎ4粉末もしくはＳｉＯ2粉末のうちいずれかとの混合粉末を主成分とする原料粉末の加速エネルギーｘ［ｇ／ｍｉｎ／ｍｍ２］および熱エネルギーｙ［ｋＪ／ｋｇ］の組み合わせを、ｘ−ｙ平面において（１）ｘ＝３．０（２０．０≦ｙ≦７５．０）、（２）ｙ＝−４．１７ｘ＋８７．５（３．０≦ｘ≦１５．０）、（３）ｘ＝１５．０（１０．０≦ｙ≦２５．０）および（４）ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦１５．０）により近似される線分によって囲まれた第１領域に収まるように調節しながら、前記基材に対して前記原料粉末を溶射することにより、前記溶射膜を形成することを特徴とする方法。 A method for producing a thermal spray member having a base material and a thermal spray film containing metal Si covering the surface of the base material,
Acceleration energy x [g / min / mm 2 ] and heat of raw material powder mainly composed of metal Si powder or mixed powder of metal Si powder and SiC powder, Si 3 N 4 powder or SiO 2 powder The combination of energy y [kJ / kg] is expressed by (1) x = 3.0 (20.0 ≦ y ≦ 75.0), (2) y = −4.17x + 87.5 (3. 0 ≦ x ≦ 15.0), (3) x = 15.0 (10.0 ≦ y ≦ 25.0) and (4) y = −0.83x + 22.5 (3.0 ≦ x ≦ 15.0) The sprayed film is formed by spraying the raw material powder on the base material while adjusting so that the first region surrounded by the line segment approximated by
前記原料粉末の加速エネルギーｘおよび熱エネルギーｙの組み合わせを、ｘ−ｙ平面において（１’）ｘ＝３．０（２０．０≦ｙ≦６０．０）、（２’）ｙ＝−２．９２ｘ＋６８．８（３．０≦ｘ≦１５．０）、（３’）ｘ＝１５．０（１５．０≦ｙ≦２５．０）、（４’）ｙ＝−０．８３ｘ＋２２．５（３．０≦ｘ≦９．０）および（５’）ｙ＝１５．０（９．０≦ｘ≦１５．０）により近似される線分によって囲まれた第２領域に収まるように調節することを特徴とする方法。 The method of claim 3, wherein
The combination of the acceleration energy x and the thermal energy y of the raw material powder is expressed as (1 ′) x = 3.0 (20.0 ≦ y ≦ 60.0), (2 ′) y = −2. 92x + 68.8 (3.0 ≦ x ≦ 15.0), (3 ′) x = 15.0 (15.0 ≦ y ≦ 25.0), (4 ′) y = −0.83x + 22.5 (3 0.0 ≦ x ≦ 9.0) and (5 ′) y = 15.0 (9.0 ≦ x ≦ 15.0) to adjust to fit in the second region surrounded by the line segment A method characterized by.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726373A (en) * | 1993-07-09 | 1995-01-27 | Asahi Glass Co Ltd | Rotating cathode target, its production and film formed by using this target |
| JPH0726370A (en) * | 1993-07-09 | 1995-01-27 | Asahi Glass Co Ltd | Target, its production and film formed by using the target |
| JPH10226869A (en) * | 1997-02-17 | 1998-08-25 | Mitsui Eng & Shipbuild Co Ltd | Plasma thermal spraying method |
| JP2002249864A (en) * | 2000-04-18 | 2002-09-06 | Ngk Insulators Ltd | Halogen gas plasma resistant member and production method therefor |
| JP2005350685A (en) * | 2004-06-08 | 2005-12-22 | Tosoh Corp | Parts of substrate treatment apparatus, and manufacturing method therefor |
| JP2006104496A (en) * | 2004-09-30 | 2006-04-20 | Toshiba Corp | Part for vacuum film-forming apparatus, and vacuum film-forming apparatus |
| JP2007250569A (en) * | 2006-03-13 | 2007-09-27 | Tokyo Electron Ltd | Plasma treatment apparatus and member to be exposed in plasma |
| JP2009267070A (en) * | 2008-04-25 | 2009-11-12 | Mitsubishi Materials Corp | Plasma etching apparatus |
-
2012
- 2012-04-13 JP JP2012092457A patent/JP6027712B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726373A (en) * | 1993-07-09 | 1995-01-27 | Asahi Glass Co Ltd | Rotating cathode target, its production and film formed by using this target |
| JPH0726370A (en) * | 1993-07-09 | 1995-01-27 | Asahi Glass Co Ltd | Target, its production and film formed by using the target |
| JPH10226869A (en) * | 1997-02-17 | 1998-08-25 | Mitsui Eng & Shipbuild Co Ltd | Plasma thermal spraying method |
| JP2002249864A (en) * | 2000-04-18 | 2002-09-06 | Ngk Insulators Ltd | Halogen gas plasma resistant member and production method therefor |
| JP2005350685A (en) * | 2004-06-08 | 2005-12-22 | Tosoh Corp | Parts of substrate treatment apparatus, and manufacturing method therefor |
| JP2006104496A (en) * | 2004-09-30 | 2006-04-20 | Toshiba Corp | Part for vacuum film-forming apparatus, and vacuum film-forming apparatus |
| JP2007250569A (en) * | 2006-03-13 | 2007-09-27 | Tokyo Electron Ltd | Plasma treatment apparatus and member to be exposed in plasma |
| JP2009267070A (en) * | 2008-04-25 | 2009-11-12 | Mitsubishi Materials Corp | Plasma etching apparatus |
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