JP2006118053A - Member for semiconductor fabrication equipment - Google Patents
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- JP2006118053A JP2006118053A JP2005362629A JP2005362629A JP2006118053A JP 2006118053 A JP2006118053 A JP 2006118053A JP 2005362629 A JP2005362629 A JP 2005362629A JP 2005362629 A JP2005362629 A JP 2005362629A JP 2006118053 A JP2006118053 A JP 2006118053A
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- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000004065 semiconductor Substances 0.000 title claims description 23
- 238000000576 coating method Methods 0.000 claims abstract description 155
- 239000011248 coating agent Substances 0.000 claims abstract description 148
- 238000010894 electron beam technology Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 26
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- 239000002184 metal Substances 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 4
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- 230000002093 peripheral effect Effects 0.000 claims description 2
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- 239000000843 powder Substances 0.000 abstract description 21
- 239000012298 atmosphere Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002844 melting Methods 0.000 abstract description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Drying Of Semiconductors (AREA)
Abstract
Description
本発明は、基材表面に、黒色化したY2O3の溶射皮膜を被成することにより、皮膜の熱放射性および耐損傷性を改善してなる半導体製造装置用部材に関するものである。 The present invention relates to a member for a semiconductor manufacturing apparatus in which the thermal radiation property and damage resistance of a coating are improved by depositing a blackened Y 2 O 3 thermal spray coating on the surface of a substrate.
溶射法は、金属、セラミックス、サーメットなどの粉末をプラズマや燃焼炎によって、溶融しつつ加速させ、被溶射体(基材)の表面に吹き付けることによって、皮膜を形成させることができるため、多くの産業分野において広く採用されている表面処理技術の一つである。ただし、溶融状態の微粒子を積層することによって得られる溶射皮膜は、皮膜を構成する粒子の結合力の強弱や未結合状態の有無によって、皮膜の機械的強度や耐食性に大きな差が生じることが知られている。このため、従来の溶射技術開発の目標は、高温の熱源、例えば、プラズマを熱源とする溶射粒子の完全溶融の実現を目指す装置や高速の燃焼炎を用いて、溶射粒子に大きな運動エネルギーを与え、被溶射体の表面に強い衝突エネルギーを発生させることによって、粒子間結合力を高めるとともに気孔率を最小に抑制しようとするものであった。 Thermal spraying can accelerate the process of melting metal, ceramics, cermet powder, etc. with plasma or combustion flame, and spray it onto the surface of the sprayed body (base material). This is one of the surface treatment techniques widely used in the industrial field. However, it is known that the thermal spray coating obtained by laminating fine particles in the molten state has a large difference in the mechanical strength and corrosion resistance of the coating depending on the strength of the particles constituting the coating and the presence or absence of the unbonded state. It has been. For this reason, the goal of conventional thermal spraying technology development is to apply a large kinetic energy to the thermal spray particles using a high-temperature heat source, for example, a device aiming at complete melting of the thermal spray particles using plasma as a heat source or a high-speed combustion flame. Thus, by generating a strong collision energy on the surface of the sprayed object, an attempt was made to increase the bonding force between particles and minimize the porosity.
例えば、特許文献1では、50〜200hPaのアルゴン雰囲気中でプラズマ溶射する減圧プラズマ溶射法の採用によって、粒子間結合力を向上させたり、気孔発生原因の一つである粒子表面に生成する酸化膜を低減させる方法を提案している。
For example, in
このような技術開発によって、近年、溶射皮膜の性能は向上してきたが、同一の溶射材料を用いて形成する皮膜表面の色調の変化についてまで検討した例はあまりない。しかしながら、セラミック溶射皮膜は、その色を観察すると、溶射材料としての酸化クロム(Cr2O3)粉末は、黒色に近い濃緑色であるが、これをプラズマ溶射した場合、黒色の皮膜となる。一方、酸化アルミニウム(Al2O3)粉末は純白であり、これをプラズマ溶射して得られる皮膜は白色である。ただし、酸化チタン(TiO2)粉末は白色系であるが、これをプラズマ溶射すると黒色系の皮膜になる。こうした色の変化の原因は、溶射熱源中において、例えば、TiO2を構成する酸素の一部が消失して、TinO2n−1で表示可能な酸化物となるためではないかと考えられている(特許文献2参照)。 Although the performance of the thermal spray coating has improved in recent years due to such technological development, there are not many examples that have examined the change in the color tone of the coating surface formed using the same thermal spray material. However, when the color of the ceramic sprayed coating is observed, the chromium oxide (Cr 2 O 3 ) powder as the sprayed material is dark green close to black, but when this is plasma sprayed, it becomes a black coating. On the other hand, aluminum oxide (Al 2 O 3 ) powder is pure white, and a coating obtained by plasma spraying this powder is white. However, titanium oxide (TiO 2 ) powder is white, but when it is plasma sprayed, it becomes a black film. The cause of such a color change is considered to be because, for example, a part of oxygen constituting TiO 2 disappears in the thermal spray heat source, and becomes an oxide that can be displayed by Ti n O 2n-1. (See Patent Document 2).
以上、説明したように、酸化物系セラミックス溶射皮膜の色は、一般に溶射用粉末材料自体の色がそのまま皮膜の色として再現されるものが普通である。例えば、酸化イットリウム(Y2O3)は、通常、Al2O3と同じように、粉末材料の状態はもとより、この粉末材料を溶射して得られる溶射皮膜もまた白色系であり、たとえプラズマ熱源中で溶射しても、Y2O3の結合状態に変化はないように思われる。それは、金属元素としてのAlやYは、ともに酸素との化学親和力が極めて強く、高温のプラズマ環境中においても酸素を消失することなく、溶射皮膜となった後でも、粉末材料時のAl2O3、Y2O3の特性を維持しているためと考えられるからである。 As described above, the color of the oxide-based ceramic sprayed coating is generally one in which the color of the thermal spray powder material itself is reproduced as it is. For example, in the case of yttrium oxide (Y 2 O 3 ), as in the case of Al 2 O 3 , not only the state of the powder material but also the sprayed coating obtained by spraying this powder material is also white, It seems that the Y 2 O 3 bonding state does not change even when sprayed in a heat source. It, Al and Y as the metal element, both chemical affinity is very strongly with oxygen, without loss of oxygen even during the high temperature plasma environment, even after a thermal spray coating, Al 2 O during powder material 3 because it is considered that the characteristics of Y 2 O 3 are maintained.
上記Y2O3溶射皮膜は、耐熱性や耐高温酸化性、耐食性に優れるとともに、半導体製造装置やその加工工程で使用されるプラズマ雰囲気中にあっても、卓越した抵抗性(耐プラズマエロージョン性)を発揮することから、多くの産業分野で使用されているセラミック皮膜である(特許文献3〜7)。 The Y 2 O 3 sprayed coating has excellent heat resistance, high-temperature oxidation resistance, and corrosion resistance, and excellent resistance (plasma erosion resistance) even in a plasma atmosphere used in semiconductor manufacturing equipment and its processing steps. This is a ceramic film used in many industrial fields (Patent Documents 3 to 7).
現在、使用されている上記Y2O3溶射皮膜は、そのすべてが白色系であり、それなりの効果が認められているが、Y2O3溶射皮膜の特性を変化させることなく、この皮膜の色を変化させるような技術についての提案はない。例えば、もしY2O3溶射皮膜の黒色化が可能になれば、表面研削のような機械的加工を行ったとしても所定の光沢(いわゆる黒光り)を付与することができ、商品価値を上げることができるようになる。しかも、黒色系の皮膜は、白色系の皮膜に比較して汚れが目立つようなことがなく、生産性の低下を招く皮膜被覆部材の洗浄回数を低減するのに役立つ。また、黒色系皮膜は、熱吸収能力や遠赤外線放射能力に優れ、加熱受熱などの熱交換部材の性能の向上と耐環境性の付与を与えるのに有力であるなどの工業的利用が期待できるにも拘わらず、Y2O3溶射皮膜の黒色化技術は現在のところ開発されていないのが実情である。
次に、基材の表面を改質する技術としては、上掲の溶射皮膜を被覆形成するものの他、電子ビーム照射やレーザビーム照射を利用する技術がある。例えば、電子ビーム照射に関しては、特許文献8において、金属皮膜に電子ビームを照射してこの皮膜を溶融して消滅させる技術、また、特許文献9には、炭化物サーメット皮膜や金属皮膜に対して電子ビームを照射して、皮膜の性能を向上させる技術などがある。 Next, as a technique for modifying the surface of the substrate, there is a technique using electron beam irradiation or laser beam irradiation in addition to the above-mentioned coating formation of the sprayed coating. For example, with respect to electron beam irradiation, Patent Document 8 discloses a technique for irradiating a metal film with an electron beam to melt and extinguish the film, and Patent Document 9 discloses an electron beam for a carbide cermet film or a metal film. There is a technique for improving the performance of a film by irradiating a beam.
しかし、これらの先行技術は、何れも炭化物サーメットや金属皮膜を対象とし、皮膜の消滅や密着性の向上を目的とした技術であり、しかも本発明が対象とするようなセラミックス、特にY2O3溶射皮膜の色彩調整を行う技術ではない。
これらの先行技術は、特許文献9の[0011]段落に説明しているように、溶射材料を電子ビーム処理で行うには、電気伝導性皮膜が必要であるとの固定した観念があることに起因しているものと考えられる。一方、溶射皮膜に対してレーザビームを照射する技術に関しては、特許文献10、11などを例示することができる。ただし、これらの例示技術は、金属皮膜のみならず炭化物サーメットなどのセラミック皮膜に対する照射例が多い。しかし、これらの技術は、下地がセラミック皮膜の場合であったとしても、その処理の目的は、皮膜の気孔を消滅させることや皮膜を再溶融現象に伴う縦割れの発生を促進させることにあり、対象とするセラミック皮膜はZrO2系のものである。
As described in paragraph [0011] of Patent Document 9, these prior arts have a fixed idea that an electrically conductive coating is necessary to perform a thermal spray material by electron beam treatment. It is thought that it is caused. On the other hand, Patent Documents 10 and 11 can be exemplified for the technique of irradiating the thermal spray coating with a laser beam. However, in these exemplary techniques, there are many examples of irradiation not only on metal films but also on ceramic films such as carbide cermets. However, even if the base is a ceramic film, the purpose of the treatment is to eliminate the pores of the film and to promote the occurrence of vertical cracks associated with the remelting phenomenon of the film. The target ceramic film is a ZrO 2 type.
本発明の目的は、従来技術が抱えている上述した問題を解決することができるようにすることにある。即ち、従来のY2O3溶射皮膜はその全てが白色に限定されていることに鑑み、この現実を打破して、基材表面に、Y2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜を形成してなる半導体製造装置用部材を提案することにある。 An object of the present invention is to make it possible to solve the above-described problems of the prior art. That is, in view of the fact that all of the conventional Y 2 O 3 sprayed coatings are limited to white, this reality is overcome, and Y 2 O 3 laser beam processing or electron beam processing black spraying is applied to the substrate surface. The object is to propose a member for a semiconductor manufacturing apparatus formed with a film.
それは、部材の表面にY2O3の黒色溶射皮膜を形成することによって、Y2O3の白色溶射皮膜では解決できない次のような技術的課題を解消することができるようになるからである。
(1)Y2O3の白色溶射皮膜を、この皮膜が有している特性を阻害することなく、黒色化したものであり、白色皮膜と同じような用途に使用することができる(良用途性)。
(2)皮膜の色が黒色になるため、皮膜製品に汚れが目立ち難く、必要以上に洗浄を繰返す必要がない(耐環境劣化性)。
(3)皮膜の色が黒色を示すため、この皮膜を放熱面や受熱面に形成すると、これらの部材を環境から保護するとともに、熱放射率や受熱効率を向上させ、装置全体の性能向上に寄与することができる(良熱放射特性)。
(4)Y2O3の黒色溶射皮膜は、白色皮膜に比較すると硬度が高いため、耐摩耗性の向上にも寄与することができる(耐損傷性)。
This is because by forming a Y 2 O 3 black sprayed coating on the surface of the member, the following technical problems that cannot be solved by the Y 2 O 3 white sprayed coating can be solved. .
(1) Y 2 O 3 white sprayed coating is blackened without impairing the properties of this coating, and can be used for the same applications as white coating (good use) sex).
(2) Since the color of the film is black, the film product is hardly contaminated, and it is not necessary to repeat washing more than necessary (environmental deterioration resistance).
(3) Since the color of the film is black, forming this film on the heat-dissipating surface and heat-receiving surface protects these members from the environment and improves the thermal emissivity and heat-receiving efficiency, thereby improving the overall performance of the device. Can contribute (good heat radiation characteristics).
(4) Since the black sprayed coating of Y 2 O 3 has higher hardness than the white coating, it can contribute to the improvement of wear resistance (damage resistance).
そこで、本発明では、色の変化によって上述した諸特性を示すY2O3溶射皮膜を被覆した部材を得るために、該基材の表面に形成する溶射皮膜として、Y2O3の黒色溶射皮膜を形成した点に特徴がある。即ち、本発明で特徴とする技術的事項を整理すると下記のとおりである。
(1)基材の表面が、Y2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜によって被覆されていることを特徴とする半導体製造装置用部材。
(2)基材と、Y2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜との間に、金属皮膜からなるアンダーコートが設られていることを特徴とする半導体製造装置用部材。
(3)前記アンダーコートとY2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜との間に、中間層を有することを特徴とする半導体製造装置用部材。
(4)上記アンダーコートは、Niおよびその合金、Wおよびその合金、Moおよびその合金、Tiおよびその合金、Alおよびその合金、Mg合金のうちから選ばれるいずれか1種以上の金属もしくはその合金を50〜500μmの厚さに形成した金属皮膜であることを特徴とする半導体製造装置用部材。
(5)上記中間層は、Al2O3もしくはY2O3との固溶体または混合物の皮膜にて形成されていることを特徴とする半導体製造装置用部材。
(6)上記レーザビーム処理もしくは電子ビーム処理黒色溶射皮膜は、Y2O3の白色溶射皮膜が、その表面から30μm未満の厚さで黒色化したY2O3層として形成されたものであることを特徴とする半導体製造装置用部材。
(7)上記レーザビーム処理もしくは電子ビーム処理黒色溶射皮膜は、この皮膜を構成している各Y2O3粒子の外周部のみ、または粒子の中心部までが黒色変化したY2O3粒子の積層体によって、膜厚50〜2000μm程度の厚さに構成されたものであることを特徴とする半導体製造装置用部材。
(8)上記のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜は、Y2O3の黒色溶射皮膜の表面が、30μm未満の厚さで、溶射粒子どうしが加熱融着した層になっていることを特徴とする半導体製造装置用部材。
Therefore, in the present invention, in order to obtain a member coated with the Y 2 O 3 sprayed coating exhibiting the above-mentioned characteristics by color change, Y 2 O 3 black sprayed coating is formed as the sprayed coating formed on the surface of the substrate. It is characterized in that a film is formed. That is, technical matters characterized by the present invention are summarized as follows.
(1) A member for a semiconductor manufacturing apparatus, wherein the surface of the substrate is coated with a Y 2 O 3 laser beam treatment or electron beam treatment black spray coating.
(2) A member for a semiconductor manufacturing apparatus, wherein an undercoat made of a metal film is provided between a base material and a Y 2 O 3 laser beam-treated or electron beam-treated black sprayed coating.
(3) A member for a semiconductor manufacturing apparatus, comprising an intermediate layer between the undercoat and a Y 2 O 3 laser beam-treated or electron beam-treated black sprayed coating.
(4) The undercoat is made of Ni and its alloy, W and its alloy, Mo and its alloy, Ti and its alloy, Al and its alloy, Mg alloy or one of its metals or its alloy A member for a semiconductor manufacturing apparatus, which is a metal film formed with a thickness of 50 to 500 μm.
(5) The member for a semiconductor manufacturing apparatus, wherein the intermediate layer is formed of a film of a solid solution or a mixture with Al 2 O 3 or Y 2 O 3 .
(6) The laser beam treatment or electron beam treatment black sprayed coating, Y white spray coating 2 O 3 is one formed as a blackened Y 2 O 3 layer with a thickness of less than 30μm from the surface A member for a semiconductor manufacturing apparatus.
(7) the laser beam treatment or electron beam treatment black sprayed coating, the outer peripheral portion of each of Y 2 O 3 particles constituting the coating only or to the center portion of the particles of black altered Y 2 O 3 particles, A member for a semiconductor manufacturing apparatus, wherein the member is configured to have a thickness of about 50 to 2000 μm by a laminate.
(8) The laser beam-treated or electron-beam-treated black sprayed coating described above has a Y 2 O 3 black sprayed coating surface having a thickness of less than 30 μm and a layer in which the sprayed particles are heat-sealed. A member for a semiconductor manufacturing apparatus.
上記の黒・白Y2O3溶射皮膜または黒色化したY2O3溶射皮膜は、下記に述べるような方法によって製造することができる。
(1)基材の表面に、直接または該基材の表面に施されたアンダーコートの上に、白色のY2O3粉末材料を、実質的に酸素を含まない不活性ガス雰囲気中でプラズマ溶射することにより、Y2O3の黒色溶射皮膜を形成する方法。
(2)基材の表面に、まず、Y2O3の白色溶射皮膜を形成し、その後、レーザビーム照射することによって、前記Y2O3の白色溶射皮膜の表面に黒色化したY2O3層を形成する方法。
(3)基材の表面に、直接または該基材の表面に施されたアンダーコートの上にまず、Y2O3の白色溶射皮膜を形成し、その後、減圧下の不活性ガス雰囲気中で電子ビーム照射することによって、前記Y2O3の白色溶射皮膜の表面に黒色化したY2O3層を形成する方法。
The black / white Y 2 O 3 sprayed coating or the blackened Y 2 O 3 sprayed coating can be produced by the method described below.
(1) Plasma is applied to a white Y 2 O 3 powder material directly or on an undercoat applied to the surface of the substrate in an inert gas atmosphere substantially free of oxygen. A method of forming a black sprayed coating of Y 2 O 3 by spraying.
(2) to the surface of the substrate, first, Y 2 O 3 white a thermal spray coating formed of, then the laser beam by irradiating, the Y 2 O 3 in the surface blackened Y 2 O white sprayed coating A method of forming three layers.
(3) A white sprayed coating of Y 2 O 3 is first formed on the surface of the substrate directly or on the undercoat applied to the surface of the substrate, and then in an inert gas atmosphere under reduced pressure. A method of forming a blackened Y 2 O 3 layer on the surface of the Y 2 O 3 white sprayed coating by electron beam irradiation.
上述したように、本発明にかかる半導体製造装置用部材に特有の構成であるY2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜は、基本的に従来のY2O3の白色溶射皮膜が有する諸特性をそのまま具えるものである。従って、この溶射皮膜の主要な用途であるハロゲンまたはハロゲン化合物を含む雰囲気中でのプラズマ処理のような環境下においても白色Y2O3溶射皮膜と全く同等の性能を示すものである。しかも、伝熱面や受熱面にY2O3の黒色溶射皮膜を形成すると、白色Y2O3溶射皮膜に比較すると、熱放射および受熱効率ともに優れた特性を発揮して、プラズマエッチング処理などの作業効率を一段と向上させる。 As described above, the Y 2 O 3 laser beam-treated or electron beam-treated black sprayed coating, which is unique to the semiconductor manufacturing apparatus member according to the present invention, is basically a conventional Y 2 O 3 white sprayed coating. It has various characteristics as it is. Therefore, even in an environment such as plasma treatment in an atmosphere containing a halogen or a halogen compound, which is the main application of this thermal spray coating, it exhibits the same performance as the white Y 2 O 3 thermal spray coating. Moreover, when a black sprayed coating of Y 2 O 3 is formed on the heat transfer surface or the heat receiving surface, it exhibits superior characteristics in both heat radiation and heat receiving efficiency compared with the white Y 2 O 3 sprayed coating, such as plasma etching treatment. Work efficiency will be further improved.
また、表面が黒色の皮膜(層)であるため、取扱い過程や環境から飛来するパーティクル類の付着に伴う汚染が目立ち難く、必要以上に繰返されている現行の洗浄回数を軽減できるので、装置の保守点検量の削減に加え、生産効率の向上、製品のコストダウン、腐食性の強い薬品による洗浄に伴う装置部材の寿命延長などに対しても貢献することができる。 In addition, since the surface is a black film (layer), contamination due to adhesion of particles flying from the handling process and the environment is not noticeable, and the current number of cleanings that are repeated more than necessary can be reduced. In addition to reducing the amount of maintenance and inspection, it can also contribute to improving production efficiency, reducing product costs, and extending the service life of equipment members associated with cleaning with highly corrosive chemicals.
(1)黒色化したY2O3溶射皮膜(Y2O3の黒色溶射皮膜)の性状と特性
本発明に特有の構成であるY2O3の黒色溶射皮膜は、Y2O3の白色溶射皮膜とは少なくとも外観が明らかに異なるものの、この黒色化したY2O3溶射皮膜をX線回折しても、Y2O3の白色溶射皮膜とのX線回折の明確な相違は認められないので、結晶構造は同じと考えられる。しかし、外観は、図1(写真)示すように、明瞭な差が見られるので、本発明では“黒色化したY2O3溶射皮膜”をY2O3の黒色溶射皮膜と言うことにした。発明者らが行った実験によると、Y2O3溶射皮膜の黒色化現象は、酸素分圧の低い環境で短時間の間融点以上に高温加熱(急速加熱)された場合に顕在化してくることから、Y2O3を構成する酸素の一部が失われた結果であろうと推定されるので、化合物の形態がY2O3−xの状態になったものと考えられるものである。
(1) Properties and Characteristics of Blackened Y 2 O 3 Sprayed Coating (Y 2 O 3 Black Sprayed Coating) The black sprayed coating of Y 2 O 3 , which is a structure unique to the present invention, is white in Y 2 O 3 Although at least the appearance is clearly different from the sprayed coating, X-ray diffraction of this blackened Y 2 O 3 sprayed coating reveals a clear difference in X-ray diffraction from the Y 2 O 3 white sprayed coating. The crystal structure is considered to be the same. However, as shown in FIG. 1 (photograph), there is a clear difference in appearance, and in the present invention, “blackened Y 2 O 3 sprayed coating” is referred to as a Y 2 O 3 black sprayed coating. . According to the experiments conducted by the inventors, the blackening phenomenon of the Y 2 O 3 sprayed coating becomes apparent when heated to a temperature higher than the melting point (rapid heating) for a short time in an environment with a low oxygen partial pressure. From this, it is presumed that a part of oxygen constituting Y 2 O 3 is lost, and therefore, it is considered that the form of the compound is in a Y 2 O 3-x state.
黒色化したY2O3すなわちY2O3−xの形をとるY2O3の黒色溶射皮膜というのは、大気プラズマ溶射法で形成したY2O3の白色溶射皮膜の性状を比較すると、次のような相違が認められる。
(i)Y2O3の黒色溶射皮膜(黒色化したY2O3−x溶射皮膜のことであり、以下の表記も同様である)の表面は非常に平滑であり、光沢性が良好で皮膜の商品価値が向上する。
(ii)Y2O3の黒色溶射皮膜は、白色系の溶射皮膜に比べて汚れ(例えば、指紋、微細な黒色系の粉じんなど)が目立たないので、保守管理が容易であり、生産性が向上する。
(iii)Y2O3の黒色溶射皮膜の表面は、緻密であるため、腐食性ガス成分の皮膜内部への侵入を抑制し、基材に対する防食性が向上する。
(iv)Y2O3の黒色溶射皮膜の表面は、皮膜を構成する各Y2O3−x粒子が溶融することによって、大気プラズマ溶射によって形成されるY2O3の白色溶射皮膜に比べて粒子の相互結合力が格段に向上するため、硬さや耐摩耗性などが向上する。
(v)上記(iii)および(iv)の現象は、Y2O3の黒色溶射皮膜のうち少なくとも表層から30μmの深さが黒色化したY2O3−x溶射皮膜となっている。この場合、それ以外の、いわゆるY2O3の白色溶射皮膜の部分はプラズマ溶射皮膜特有の多孔質な状態を維持しているものである。従って、Y2O3の黒色溶射皮膜(層)は環境の急激な温度変化、すなわち熱衝撃を受けても溶射皮膜が破壊されたり、剥離するようなことがない。
(vi)発熱体の表面にY2O3の黒色溶射皮膜を形成すると、顕著な遠赤外線放射作用を発揮するので、減圧雰囲気中に配設すると、輻射型熱源皮膜として有用である。なお、この用途の場合には、皮膜厚さが薄いほど効果を発揮する。
(vii)Y2O3の黒色溶射皮膜の物理化学的性質は、色調の変化(黒変化)を除けば、従来のY2O3の白色溶射皮膜と変わることはないので、その用途も従来通りの用途に使用することができる。例えば、Y2O3の白色溶射皮膜の主要な用途の一つに、半導体製造装置関連のプラズマ処理容器内に配設される部材がある。一般に、Y2O3溶射皮膜は各種のハロゲンガスを含む雰囲気中でプラズマ処理されるような環境下において優れた耐プラズマエロージョン性を発揮することが知られているが、本発明で用いるY2O3の黒色溶射皮膜も卓越した性能を示す。
The black sprayed coating of Y 2 O 3 in the form of blackened Y 2 O 3, that is, Y 2 O 3 -x , is a comparison of the properties of the Y 2 O 3 white sprayed coating formed by the atmospheric plasma spraying method. The following differences are observed.
(I) The surface of the Y 2 O 3 black sprayed coating (which is a blackened Y 2 O 3-x sprayed coating, and the following notation is the same) has a very smooth surface and good gloss. The commercial value of the film is improved.
(Ii) The Y 2 O 3 black sprayed coating is less noticeable of dirt (for example, fingerprints, fine black dust, etc.) than the white sprayed coating, so that maintenance management is easy and productivity is improved. improves.
(Iii) Since the surface of the Y 2 O 3 black sprayed coating is dense, the invasion of corrosive gas components into the coating is suppressed, and the corrosion resistance to the substrate is improved.
(Iv) The surface of the Y 2 O 3 black sprayed coating is compared to the Y 2 O 3 white sprayed coating formed by atmospheric plasma spraying by melting each Y 2 O 3-x particle constituting the coating. Thus, the mutual bonding force of the particles is remarkably improved, so that the hardness and wear resistance are improved.
(V) The phenomenon of (iii) and (iv) is a Y 2 O 3-x sprayed coating in which the depth of at least 30 μm from the surface layer is blackened among the Y 2 O 3 black sprayed coating. In this case, other portions of the so-called Y 2 O 3 white sprayed coating maintain a porous state peculiar to the plasma sprayed coating. Therefore, the Y 2 O 3 black sprayed coating (layer) does not break or peel off even when the environment undergoes a rapid temperature change, that is, a thermal shock.
(Vi) When a black sprayed coating of Y 2 O 3 is formed on the surface of the heating element, a remarkable far-infrared radiation effect is exerted. Therefore, when it is disposed in a reduced-pressure atmosphere, it is useful as a radiation heat source coating. In the case of this application, the effect is exhibited as the film thickness is thinner.
(Vii) The physicochemical properties of the Y 2 O 3 black sprayed coating are the same as the conventional Y 2 O 3 white sprayed coating except for the change in color tone (black change). Can be used for street applications. For example, one of the main uses of the Y 2 O 3 white sprayed coating is a member disposed in a plasma processing vessel related to a semiconductor manufacturing apparatus. In general, Y 2 O 3 sprayed coating is known to exhibit excellent plasma erosion resistance in an environment in which plasma treatment is performed in an atmosphere containing various halogen gases, but Y 2 used in the present invention. The black sprayed coating of O 3 also shows outstanding performance.
具体的には、CF4 100cm3−Ar1000cm3−O210cm3の混合ガス中で、プラズマ照射出力1300Wの条件下において、20時間照射実験を行ったところ、
白色Y2O3溶射皮膜表面のエロージョン損失深さ:6.1〜7.6μm
黒色Y2O3溶射皮膜表面のエロージョン損失深さ:5.8〜6.5μm
のような結果となり、本発明において特有のものであるY2O3の黒色溶射皮膜の方が耐プラズマ照射性能に優れていることがわかった。
また、白色と黒色のY2O3溶射皮膜を2NのNaOH水溶液(40℃)に浸漬しても、両皮膜とも全く浸食されず、優れた耐アルカリ性を発揮した。
Specifically, CF 4 100cm 3 -Ar1000cm 3 -O 2 10cm mixed gas of 3, where under the conditions of the plasma irradiation output 1300 W, was 20 hours irradiation experiments,
Erosion loss depth on the surface of white Y 2 O 3 sprayed coating: 6.1 to 7.6 μm
Black Y 2 O 3 erosion loss of the thermal spray coating surface depth: 5.8~6.5Myuemu
As a result, it was found that the Y 2 O 3 black sprayed coating, which is peculiar to the present invention, is superior in the resistance to plasma irradiation.
Further, even when the white and black Y 2 O 3 sprayed coatings were immersed in a 2N NaOH aqueous solution (40 ° C.), both coatings were not eroded at all and exhibited excellent alkali resistance.
本発明において、基材表面に上記Y2O3の黒色溶射皮膜の形成に当って、まずその基材表面に、アンダーコートを形成しておいてもよい。この場合、アンダーコートの材料としては、Niおよびその合金、Wおよびその合金、Moおよびその合金、Tiおよびその合金、Alおよびその合金、Mg合金などから選ばれるいずれか1種以上の金属、合金を用いて、厚さ50〜500μm程度に施工することが好ましい。この場合において、アンダーコートの溶射皮膜が50μmより薄いとアンダーコートとしての作用効果が弱く、一方、その厚さが500μmを超えると被覆効果が飽和し、積層作業による制作費の向上を招くので得策でない。 In the present invention, in forming the Y 2 O 3 black sprayed coating on the substrate surface, first, an undercoat may be formed on the substrate surface. In this case, as an undercoat material, any one or more metals or alloys selected from Ni and its alloys, W and its alloys, Mo and its alloys, Ti and its alloys, Al and its alloys, Mg alloys, etc. It is preferable to apply a thickness of about 50 to 500 μm. In this case, if the sprayed coating of the undercoat is thinner than 50 μm, the effect as the undercoat is weak, while if the thickness exceeds 500 μm, the covering effect is saturated and the production cost is increased due to the laminating work. Not.
基材表面に直接もしくはアンダーコートや中間層を介してトップコートとして形成されるY2O3の黒色溶射皮膜は、無酸素プラズマ溶射によって形成したものの他、Y2O3の白色溶射皮膜を電子ビームやレーザビームで照射して黒色化したもの、あるいは黒色化層を含めて、50〜2000μm程度の厚さにするとよい、それは、その膜厚が50μm未満では、黒色皮膜としての熱放射性能は得られるとしても、セラミック皮膜としての本質的特性、例えば、耐熱性、断熱性、耐食性、耐摩耗性などを十分に発揮することができなからである。一方、その厚さが2000μmより大きな厚膜では、皮膜を構成するセラミック粒子の相互結合力が低下して、皮膜が機械的に破壊され易くなると共に、膜厚の形成に長時間を要して生産コストが上昇するので適切でない。従って、厚さは50〜2000μm程度とするのが好ましいと言える。 The Y 2 O 3 black sprayed coating formed directly on the surface of the substrate or as a top coat through an undercoat or intermediate layer is formed by oxygen-free plasma spraying, as well as the Y 2 O 3 white sprayed coating. It is good to make the film black by irradiation with a beam or a laser beam, or a thickness of about 50 to 2000 μm including the blackened layer. If the film thickness is less than 50 μm, the heat radiation performance as a black film is This is because even if it is obtained, essential characteristics as a ceramic film, for example, heat resistance, heat insulation, corrosion resistance, wear resistance, etc. cannot be sufficiently exhibited. On the other hand, when the thickness is larger than 2000 μm, the mutual bonding force of the ceramic particles constituting the coating is reduced, the coating is easily broken mechanically, and it takes a long time to form the thickness. It is not appropriate because the production cost increases. Therefore, it can be said that the thickness is preferably about 50 to 2000 μm.
上記Y2O3の黒色溶射皮膜の気孔率は、無酸素プラズマ溶射皮膜の場合、0.2〜5%程度である。この気孔率は従来の大気プラズマ溶射で得られるY2O3の白色溶射皮膜の気孔率8〜15%に比べると際立って小さいものである。また、Y2O3の白色溶射皮膜を電子ビーム照射やレーザビーム照射によって処理した黒色化したY2O3溶射皮膜の表面は、それぞれY2O3の融点(2683K)以上に加熱されているため、照射時には局部的には完全に溶融して、無気孔状態となる。しかし、その後の冷却によって凝固した際、体積の収縮現象によって亀裂が発生して、これが新しい気孔となる。この新しい気孔の存在は、初期の皮膜の気孔率に比較して、はるかに少なくなる特徴がある。しかし、トップコートとしてのY2O3の黒色溶射皮膜では、無気孔の皮膜では熱衝撃抵抗が著しく低下することが経験的に知られているので、本発明では照射後に発生する凝固割れに起因する気孔(0.1〜1%)を含めても5%程度以下である。 The porosity of the Y 2 O 3 black sprayed coating is about 0.2 to 5% in the case of the oxygen-free plasma sprayed coating. This porosity is remarkably small compared to the porosity of 8 to 15% of the Y 2 O 3 white spray coating obtained by conventional atmospheric plasma spraying. Further, the surface of the blackened Y 2 O 3 sprayed coating obtained by treating the Y 2 O 3 white sprayed coating by electron beam irradiation or laser beam irradiation is heated to the melting point (2683K) or more of Y 2 O 3 respectively. For this reason, it is completely melted locally at the time of irradiation and becomes a non-porous state. However, when solidified by subsequent cooling, cracks are generated due to the contraction phenomenon of the volume, and this becomes a new pore. The presence of this new pore is characterized by much less compared to the porosity of the initial film. However, it is empirically known that the thermal shock resistance is significantly reduced in the non-porous coating in the Y 2 O 3 black spray coating as the top coat. Even if pores (0.1 to 1%) are included, it is about 5% or less.
また、本発明において、トップコートとして形成するY2O3の黒色溶射皮膜の下には、前記アンダーコート(金属層)との間に、中間層を形成してもよい。その中間層としては、Al2O3単独またはAl2O3とY2O3との固溶体または混合物からなる溶射皮膜とすることができる。この中間層の厚さは50〜1000μm程度とすることが好適であり、それは50mより薄い場合は中間層としての機能が十分でなく、一方、1000μmより厚い場合は、皮膜の機械的強度が低下するので適当でない。 In the present invention, an intermediate layer may be formed between the undercoat (metal layer) and the Y 2 O 3 black spray coating formed as a top coat. The intermediate layer can be a sprayed coating made of Al 2 O 3 alone or a solid solution or mixture of Al 2 O 3 and Y 2 O 3 . The thickness of the intermediate layer is preferably about 50 to 1000 μm. When the thickness is less than 50 m, the function as the intermediate layer is not sufficient. On the other hand, when the thickness is greater than 1000 μm, the mechanical strength of the film decreases. This is not appropriate.
以上の膜厚を整理すると次のようになる。但し、この皮膜の厚みは本発明の効果を得る点において不可欠のものと言うわけではなく、好ましい例示の範囲である。
アンダーコート(金属・合金) 50〜500μm
中間層(Al2O3、Al2O3+Y2O3) 50〜1000μm
トップコート(黒色Y2O3) 50〜2000μm
The above film thickness is arranged as follows. However, the thickness of the film is not indispensable in obtaining the effects of the present invention, and is a preferable exemplary range.
Undercoat (metal / alloy) 50-500μm
Intermediate layer (Al 2 O 3 , Al 2 O 3 + Y 2 O 3 ) 50 to 1000 μm
Top coat (black Y 2 O 3 ) 50-2000 μm
(2)Y2O3の黒色溶射皮膜を被成する基材
本発明において、上記のY2O3の黒色溶射皮膜を形成する対象、即ち基材は、Alおよびその合金、ステンレス鋼、Tiおよびその合金、セラミックの焼結体(例えば、酸化物、窒化物、硼化物、珪化物およびこれらの混合物)をはじめ、石英、ガラス、プラスチックなど如何なる素材も使用が可能である。また、これらの素材の上に、各種の蒸着膜やめっき膜を施したものを使用することができ、これらの素材の表面に直接またはアンダーコートや中間層を介して成膜してもよい。
(2) In the
(3)Y2O3の黒色溶射皮膜の構造
発明者らは、上記Y2O3の黒色溶射皮膜構造は、次のような構成をとるものと考えている。即ち、基材を被覆する最表層にY2O3の黒色溶射皮膜を形成したもの(Y2O3の黒色溶射皮膜単層)、Y2O3の黒色溶射皮膜の基材との密着性を向上させるため、基材の表面に金属系のアンダーコートを施工した後、その上にY2O3の黒色溶射皮膜を形成したもの(2層構造皮膜)、さらに、前記アンダーコートの上に、Al2O3やAl2O3とY2O3との固溶体または混合物の皮膜からなる中間層を形成し、その上に、Y2O3の黒色溶射皮膜を形成したもの(3層構造皮膜)などである。また必要に応じ、3層構造皮膜におけるAl2O3とY2O3中間層において、両セラミックの配合割合をアンダーコート側ほどAl2O3含有量を高くし、そして、トップコート側ほどY2O3含有量が多くなるようにセラミックス質の含有量を意識的に傾斜させるものとすることも可能である。
(3) Structure of black sprayed coating of Y 2 O 3 The inventors consider that the black sprayed coating structure of Y 2 O 3 takes the following configuration. That is, (black sprayed coating monolayer of Y 2 O 3) the outermost layer to that form black spray coating Y 2 O 3 coating the substrate, adhesion to a substrate of a black spray coating Y 2 O 3 In order to improve the surface, a metal-based undercoat is applied to the surface of the base material, and then a Y 2 O 3 black sprayed coating is formed thereon (two-layer structure coating). An intermediate layer made of a coating of a solid solution or a mixture of Al 2 O 3 or Al 2 O 3 and Y 2 O 3 is formed, and a black sprayed coating of Y 2 O 3 is formed thereon (three-layer structure) Film). Further, if necessary, in the Al 2 O 3 and Y 2 O 3 intermediate layer in the three-layer structure film, the mixing ratio of both ceramics is set such that the Al 2 O 3 content is increased toward the undercoat side, and the Y is increased toward the topcoat side. It is also possible to intentionally incline the ceramic content so that the 2 O 3 content is increased.
(4)Y2O3の黒色溶射皮膜を形成するための溶射法
Y2O3の黒色溶射皮膜は、下記に示す溶射法によって形成することができる。
(a)アンダーコート(金属・合金)は、電気アーク溶射法、フレーム溶射法、高速フレーム溶射法、大気プラズマ溶射法、減圧プラズマ溶射法、爆発溶射法を用いることが好ましい。
(b)トップコート(白色Y2O3、黒色Y2O3)は、白色皮膜は大気プラズマ溶射法、黒色皮膜は無酸素プラズマ溶射法を用いることが好ましい。
(c)中間層(Al2O3、Al2O3+Y2O3)は、大気プラズマ溶射法、無酸素プラズマ溶射法、爆発溶射法を用いることが好ましい。
(4) Thermal spraying method for forming a black sprayed coating of Y 2 O 3 The black sprayed coating of Y 2 O 3 can be formed by the thermal spraying method shown below.
(A) For the undercoat (metal / alloy), it is preferable to use an electric arc spraying method, a flame spraying method, a high-speed flame spraying method, an atmospheric plasma spraying method, a low pressure plasma spraying method, or an explosion spraying method.
(B) For the top coat (white Y 2 O 3 , black Y 2 O 3 ), it is preferable to use an air plasma spraying method for the white coating and an oxygen-free plasma spraying method for the black coating.
(C) For the intermediate layer (Al 2 O 3 , Al 2 O 3 + Y 2 O 3 ), it is preferable to use an atmospheric plasma spraying method, an oxygen-free plasma spraying method, or an explosion spraying method.
(5)白色系のY2O3溶射皮膜を黒色化させる方法
一般的な溶射用Y2O3粉末材料は、粒径5〜80μmの範囲に調整された白色の粉末である。この白色粉末を用いて通常の大気プラズマ溶射を行うと、形成される溶射皮膜もまた白色になる。これに対し本発明では、外観上、即ち、少なくとも皮膜表面が一定の厚みで、図1に示すような黒色化したY2O3溶射皮膜(Y2O3−x溶射皮膜)を作製するため、以下に示すような方法を採用する。
(a)実質的に空気(酸素)を含まない雰囲気中で、白色のY2O3粉末を用いてプラズマ溶射する(以下、「無酸素プラズマ溶射」という)。
例えば、ArやHeなどの不活性雰囲気中で白色のY2O3溶射材料粉末を用いてプラズマ溶射することにより、黒変化した溶射皮膜が得られる。この方法では、溶射皮膜を構成している各Y2O3溶射粒子の表層部のみが黒色に変化し、その粒子の中心部は未だ白色の状態にあることが多い。特に、粒径の大きいY2O3溶射材料粉末において、このような現象が見られ、粒径の小さい粒子(5μm未満)では、粒子の中心部まで黒色変化するので、Y2O3溶射材料粉末の黒色変化は表面から発生し、処理時間(溶射時間)の経過に伴って、内部に伝播しているように考えられる。
なお、ArやHeのような不活性ガス雰囲気では、それが大気圧であっても50hPaのような減圧下でも黒変化したY2O3溶射皮膜が得られる。
(5) Method of Blackening White Y 2 O 3 Thermal Spray Coating A general Y 2 O 3 powder material for thermal spraying is a white powder adjusted to a particle size in the range of 5 to 80 μm. When ordinary air plasma spraying is performed using this white powder, the formed sprayed coating also becomes white. On the other hand, in the present invention, in order to produce a blackened Y 2 O 3 sprayed coating (Y 2 O 3-x sprayed coating) as shown in FIG. The following method is adopted.
(A) Plasma spraying using white Y 2 O 3 powder in an atmosphere substantially free of air (oxygen) (hereinafter referred to as “oxygen-free plasma spraying”).
For example, a black sprayed coating can be obtained by plasma spraying using a white Y 2 O 3 spray material powder in an inert atmosphere such as Ar or He. In this method, only the surface layer portion of each Y 2 O 3 sprayed particle constituting the sprayed coating changes to black, and the central portion of the particle is still in a white state in many cases. In particular, the larger Y 2 O 3 spray material powder having a particle size, observed such a phenomenon, the small particle size particles (less than 5 [mu] m), because the black changes to the center of the particles, Y 2 O 3 spray material The black color change of the powder occurs from the surface and seems to propagate to the inside as the processing time (spraying time) elapses.
In an inert gas atmosphere such as Ar or He, a Y 2 O 3 sprayed coating that has changed to black can be obtained even at atmospheric pressure or under reduced pressure such as 50 hPa.
(b)大気プラズマ溶射法で形成されたY2O3の白色溶射皮膜を、減圧下の不活性ガス雰囲気中で電子ビーム照射を行う。
例えば、通常の大気プラズマ溶射して得られたY2O3の白色溶射皮膜を10−1〜10−3MPa、Arガス中で電子ビームを照射すると、該溶射皮膜の表層部のみが黒色に変化する。この方法では、黒色変化したY2O3の粒子の表層部が電子ビームによって局部的に溶融状態になるため、皮膜全体にわたって平滑化する傾向がある。また、この溶射皮膜の黒色変化部は、電子ビームの照射回数を重ねることによって、次第に内部層にも及んでいくが、実用的には30μm程度の深さがあれば、本発明の目的に適するものができる。
(b) The Y 2 O 3 white sprayed coating formed by the atmospheric plasma spraying method is irradiated with an electron beam in an inert gas atmosphere under reduced pressure.
For example, when a white sprayed coating of Y 2 O 3 obtained by normal atmospheric plasma spraying is irradiated with an electron beam in 10 −1 to 10 −3 MPa and Ar gas, only the surface layer portion of the sprayed coating becomes black. Change. In this method, since the surface layer portion of the Y 2 O 3 particles changed to black is locally melted by the electron beam, it tends to be smoothed over the entire film. Further, the black change portion of the thermal spray coating gradually reaches the inner layer by repeating the number of times of electron beam irradiation. However, if the depth is practically about 30 μm, it is suitable for the purpose of the present invention. I can do things.
なお、電子ビーム照射の条件としては、下記のようなものが推奨される。
照射雰囲気:1×10−1〜5×10−3MPa
照射出力 :10〜30Kev
照射速度 :1〜20mm/s
照射回数 :1〜100回(連続または不連続)
The following conditions are recommended as the conditions for electron beam irradiation.
Irradiation atmosphere: 1 × 10 −1 to 5 × 10 −3 MPa
Irradiation output: 10-30Kev
Irradiation speed: 1 to 20 mm / s
Number of irradiations: 1 to 100 times (continuous or discontinuous)
(c)大気プラズマ溶射法で形成されたY2O3の白色溶射皮膜をレーザ照射する。例えば、通常の大気プラズマ溶射して得たY2O3の白色溶射皮膜に対し、大気中もしくは真空中で、レーザビームを照射することによっても黒色変化させることができる。この方法では、広い面積の溶射皮膜全体を黒色化させるには長時間を要するが、溶射皮膜の局部のみを黒色化するのには好適な方法である。 (C) A white sprayed coating of Y 2 O 3 formed by the atmospheric plasma spraying method is irradiated with a laser. For example, black color can be changed by irradiating a white spray coating of Y 2 O 3 obtained by normal atmospheric plasma spraying with a laser beam in the air or in vacuum. In this method, it takes a long time to blacken the entire sprayed coating having a large area, but this method is suitable for blackening only the local part of the sprayed coating.
なお、レーザビーム照射条件としては、下記のようなものが推奨される。
レーザ出力 :2〜4kW
ビーム面積 :5〜10mm2
ビーム走査速度:5〜20mm/s
As the laser beam irradiation conditions, the following are recommended.
Laser output: 2 to 4 kW
Beam area: 5 to 10 mm 2
Beam scanning speed: 5 to 20 mm / s
本発明は、例示した上記のY2O3の黒色溶射皮膜の形成方法を適宜組合わせることによっても、望ましいY2O3の黒色溶射皮膜を得ることができる(例えば、(a)の方法と(b)の方法の組合せ、(a)の方法と(c)の方法の組合わせなど)である。 The present invention, by combining the method of forming the illustrated black spray coating the above Y 2 O 3 as appropriate, it is possible to obtain a black thermal spray coating of the desired Y 2 O 3 (for example, a method of (a) (B) method combination, (a) method and (c) method combination, etc.).
(実施例1)
この実施例では、電熱線を内蔵した石英ガラス製の保護管の表面に、従来技術によるY2O3の白色溶射皮膜と本発明において特有のY2O3の黒色溶射皮膜(50μm厚)を形成した後、電熱線に電流を通し、それぞれの皮膜の表面から放出される波長を調査した。その結果、Y2O3の白色溶射皮膜では0.2〜1μm程度であったが、Y2O3の黒色溶射皮膜では0.3〜5μmとなり、赤外線の放出が認められ、加熱ヒータとしての効率に差が認められた。
また、石英ガラス製のヒータに替えて、ハロゲンランプ(高輝度ランプ)の表面にY2O3の黒色溶射皮膜(50μm厚)を施工すると、皮膜のない状態のランプの波長は0.2〜3μmの範囲であったのに対し、Y2O3の黒色溶射皮膜を施したものでは、0.3〜10μm超となり、遠赤外線領域での利用となり、加熱ヒータとしての効率の向上が明らかとなった。なお、従来技術によるY2O3の白色溶射皮膜では、溶射皮膜の施工がない状態と同一か、またそれ以下の波長の範囲内であった。
Example 1
In this example, a white spray coating of Y 2 O 3 according to the prior art and a black spray coating (50 μm thickness) of Y 2 O 3 specific to the present invention are applied to the surface of a protective tube made of quartz glass with a built-in heating wire. After forming, an electric current was passed through the heating wire, and the wavelength emitted from the surface of each film was examined. As a result, the Y 2 O 3 white sprayed coating was about 0.2 to 1 μm, but the Y 2 O 3 black sprayed coating was 0.3 to 5 μm, and infrared emission was observed. Differences in efficiency were observed.
When a black spray coating (50 μm thickness) of Y 2 O 3 is applied on the surface of a halogen lamp (high brightness lamp) instead of the quartz glass heater, the wavelength of the lamp without the coating is 0.2 to In contrast to the range of 3 μm, when Y 2 O 3 black sprayed coating was applied, it was over 0.3 to 10 μm, and it was used in the far-infrared region, which clearly improved the efficiency of the heater. became. It should be noted that the Y 2 O 3 white sprayed coating according to the prior art was in the same wavelength range as when no thermal spray coating was applied, or within a wavelength range of less than that.
(実施例2)
この実施例では、SUS304ステンレス鋼の基材(寸法 幅50mm×長さ50mm×厚さ3.5mm)の片面に、アンダーコートとして80mass%Ni−20mass%Cr合金の大気プラズマ溶射皮膜(厚さ100μm)を形成した後、市販の白色Y2O3溶射材料粉末を用いて、従来法に属する大気プラズマ溶射法によりY2O3の白色溶射皮膜および本発明に適合する無酸素プラズマ溶射法により、Y2O3の黒色溶射皮膜を、それぞれ250μm厚さに施工した溶射皮膜試験片を、1条件につき3枚づつ作製した。
その後、これらの試験片について、外観試験、皮膜断面のY2O3トップコート皮膜の気孔率を光学顕微鏡および画像解析装置で計測する一方、熱衝撃試験、トップコートの密着強さ試験およびトップコート表面のミクロビッカース硬さを測定し、白色と黒色のY2O3溶射皮膜の性状を比較した。
表1は、以上の試験結果を要約したものである。なお、表の下段には皮膜の製作条件および試験方法・条件を併記した。
(Example 2)
In this example, an atmospheric plasma sprayed coating of 80 mass% Ni-20 mass% Cr alloy (thickness 100 μm) as an undercoat on one side of a SUS304 stainless steel base material (size: width 50 mm × length 50 mm × thickness 3.5 mm). ), And using a commercially available white Y 2 O 3 spray material powder, a white spray coating of Y 2 O 3 by an atmospheric plasma spray method belonging to the conventional method and an oxygen-free plasma spray method suitable for the present invention, Three thermal spray coating specimens each having a Y 2 O 3 black thermal spray coating having a thickness of 250 μm were prepared for each condition.
Thereafter, for these test pieces, the appearance test, the porosity of the Y 2 O 3 topcoat film in the cross section of the film were measured with an optical microscope and an image analyzer, while the thermal shock test, the topcoat adhesion strength test, and the topcoat The surface micro Vickers hardness was measured and the properties of the white and black Y 2 O 3 sprayed coatings were compared.
Table 1 summarizes the above test results. In the lower part of the table, the film production conditions and test methods / conditions are also shown.
この表1に示す結果から明らかなように、本発明に適合する溶射皮膜(No2〜5)は何れも黒色を呈するとともに、皮膜の耐熱衝撃性、密着強さなどは、比較例のY2O3の白色溶射皮膜(No1)と同等の性能を有している。また、皮膜の気孔率は、本発明の皮膜の方が明らかに緻密であることが判明したが、この原因は、電子ビーム(No2)やレーザビーム(No3)による照射によって、皮膜表面のY2O3粒子が溶融したためと考えられる。しかし、皮膜の表面は完全に無気孔状態とはならず、Y2O3粒子が溶融後、冷却凝固する際に微細な新しい“ひび割れ”が発生する傾向が認められた。
なお、皮膜表面のミクロ硬さは、従来技術に係るY2O3の白色溶射皮膜に比較すると、明らかに硬度の上昇が見られ、耐ブラストエロージョン性が向上していることが窺われる。
As is clear from the results shown in Table 1, the thermal spray coatings (Nos. 2 to 5) suitable for the present invention are all black, and the thermal shock resistance, adhesion strength, etc. of the coatings are Y 2 O of the comparative example. 3 has the same performance as the white sprayed coating (No. 1). The porosity of the coating, although it towards the coating of the present invention are clearly dense turned out, this causes, by irradiation with an electron beam (No2) and laser beam (No3), the coating surface Y 2 This is probably because the O 3 particles were melted. However, the surface of the film was not completely non-porous, and it was recognized that fine new “cracks” were generated when the Y 2 O 3 particles were melted and then cooled and solidified.
The microhardness of the coating surface clearly shows an increase in hardness as compared with the Y 2 O 3 white sprayed coating according to the prior art, indicating that the blast erosion resistance is improved.
(実施例3)
この実施例では、実施例2の試験片を用いて、トップコートのY2O3の黒色溶射皮膜の耐摩耗性を調査した。供試した試験装置および試験条件は下記の通りである。
試験方法:JIS H8503 めっきの耐摩耗試験方法に規定されている往復運動摩耗
試験方法を採用した。
試験条件:荷重 3.5N、往復速度40回/分を10分(400回)と20分(800回)実施、摩耗面積30×12mm、摩耗試験紙 CC320
評価は、試験前後における試験片の重量測定を行い、その差から摩耗量を定量して比較した。
上記試験結果を表2に示した。この表2に示す結果から明らかなよう、皮膜表面の硬いY2O3の黒色溶射皮膜の摩耗量(No2〜5)は、比較例のY2O3の白色溶射皮膜(No1)の50〜60%に止まっており、優れた耐摩耗性が認められた。この結果には黒色処理による皮膜表面の平滑化も含まれている。
(Example 3)
In this example, the wear resistance of the Y 2 O 3 black sprayed coating of the top coat was examined using the test piece of Example 2. The test equipment and test conditions tested are as follows.
Test method: Reciprocating wear specified in JIS H8503 plating wear resistance test method
The test method was adopted.
Test conditions: Load 3.5N, reciprocating speed 40 times / minute, 10 minutes (400 times) and 20 minutes (800 times), wear area 30 × 12 mm, wear test paper CC320
The evaluation was performed by measuring the weight of the test piece before and after the test, and quantifying the amount of wear from the difference and comparing it.
The test results are shown in Table 2. As is apparent from the results shown in Table 2, the wear amount (No 2 to 5) of the Y 2 O 3 black sprayed coating having a hard coating surface is 50 to 50 of that of the Y 2 O 3 white spray coating (No 1) of the comparative example. It was only 60%, and excellent wear resistance was recognized. This result includes smoothing of the coating surface by black treatment.
本発明にかかる部材(Y2O3のレーザビーム処理もしくは電子ビーム処理黒色溶射皮膜つき部材)は、従来のY2O3の白色溶射皮膜製品の用途に適用した場合に、熱放射性や耐損傷性に優れるほか、汚れの目立ち難い皮膜になる。具体的には、半導体製造装置において、ハロゲンおよびその化合物を含む処理ガスを用いてプラズマ処理されるデポシールド、バッフルプレート、フォーカスリング、インシュレータリング、シールドリング、ベローズカバー、電極などに加え、耐溶融金属性を利用した金属溶解ルツボなどの部材の表面処理技術として適用が可能である。 The member according to the present invention (a member with a Y 2 O 3 laser beam treatment or electron beam treatment black sprayed coating) is applied to a conventional Y 2 O 3 white sprayed coating product for thermal radiation and damage resistance. In addition to excellent properties, the film is less noticeable. Specifically, in semiconductor manufacturing equipment, in addition to deposition shields, baffle plates, focus rings, insulator rings, shield rings, bellows covers, electrodes, etc. that are plasma-treated using a processing gas containing halogen and its compounds, resistance to melting It can be applied as a surface treatment technique for a member such as a metal melting crucible using metallicity.
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