200936504 九、發明說明 【發明所屬之技術領域】 本發明係有關耐蝕性構件，有關具有適用於如：半導 體製造裝置內、平面顯示器製造裝置內、太陽電池製造裝 置內之氧化物被膜之耐蝕性構件的發明。 【先前技術】 Φ 於半導體製造裝置內、平面顯示器製造裝置內、太陽 電池製造裝置內時，爲於鹵素系腐蝕氣體或鹵素系氣體電 漿等之環境下，進行製造，而使用具耐鈾性之構件。近年 來，稀土類化合物之耐蝕性被確定，特別以 Υ2〇3受矚 目，如：特開20(Π-1 643 54號公報所載之基材表面上施予 含有Υ2〇3之耐蝕性被膜之構件被使用之。 惟，Υ3〇3爲高熔點者，因此不易熔融，於半熔融狀 態下形成氧化物被膜。因此，半導體製造裝置內、平面顯 φ 示器製造裝置內、太陽電池製造裝置內，若曝露於鹵素系 腐蝕氣體或鹵素系氣體電漿等則將藉由蝕刻由被膜表面使 結晶粒子脫粒，產生微粒。而且所產生之微粒附著於晶圓 上，導致降低收率之問題存在。 【發明內容】 本發明之目的係爲提供一種對於鹵素系腐蝕氣體或鹵 素系氣體電漿等，具有良好的耐蝕性之氧化物被膜所形成 之耐蝕性構件。 -5- 200936504 本發明鑑於上述現狀，爲解決上述課題，而提供一種 可充份確保對於鹵素系腐蝕氣體或鹵素系氣體電漿等之耐 蝕性之耐蝕性構件者爲其目的，因此爲達成該目的，而具 備如以下之構成。 亦即，以基材上形成含有Gd之氧化物被膜所成者爲 其特徵之耐蝕性構件，或以基材上形成含有Yb之氧化物 被膜所成者爲其特徵之耐蝕性構件。如：該氧化物被膜 φ 中’鐵族金屬化合物以氧化物換算下含有多於5ppm者爲 其特徵。或該氧化物被膜中，鐵族金屬化合物以氧化物換 算下含有少於50ppm者爲其特徵。而且，如：該氧化物 被膜藉由噴塗法所形成者爲其特徵。本發明之耐蝕性構件 更以於半導體製造裝置內、平面顯示器製造裝置內、太陽 電池製造裝置內所使用之構件者爲其特徵。具體而言，可 適用於爲靜電吸盤、加熱器、氣體擴散板、擋板、擋環、 簇射極板、以及棚室、鐘罩、圓頂及其內壁材料、以及高 〇 頻透窗、透紅外線窗、監視窗、基座、鎖緊圈、焦距環、 shadow ring、絕緣環、仿真晶圓、半導體晶圓之升降針、 伸縮護蓋、冷卻板、上部電極、下部電極。 本發明可提供一種可適用於利用鹵素系腐蝕氣體或鹵 素系氣體電漿等之半導體製造裝置內、平面顯示器製造裝 置內、太陽電池製造裝置內之良好耐蝕性之耐蝕性構件， 可減少微粒的產生。 又’本發明係藉由，於氧化物被膜中含有以氧化物換 算下爲多於5ppm之鐵族金屬化合物，可形成良好耐蝕性 200936504 之氧化物被膜。 【實施方式】 [發明實施之最佳形態] 本發明者爲達成該目的’進行精密硏討後結果，發 現，含有Gd或Yb之氧化物被膜即使曝露於鹵素系腐蝕 氣體或鹵素系氣體電漿等仍具良好耐蝕性，極少出現微粒 0 產生。且發現，該氧化物被膜中藉由以氧化物換算下含有 多於5ppm之鐵族金屬化合物，可降低Gd或Yb之熔點， 形成良好耐蝕性之氧化物被膜。 以下，參考圖面等，詳細說明本發明實施之形態例。 以下說明之本實施之形態例的耐蝕性構件係形成一種含有 Gd(§L : Gadolinium)或 Yb(鏡：Ytterbium)，且以氧化物換 算下含有多於5ppm之鐵族金屬化合物之氧化物被膜所成。 本實施之形態例之耐蝕性構件係適用於半導體製造裝 ❿ 置內、平面顯示器製造裝置內、太陽電池製造裝置內之構 件、至少於表面對於鹵素系腐蝕氣體或鹵素系氣體電漿等， 具有具耐鈾性之氧化物被膜。耐蝕性構件之基材材質並未特 別限定，一般可使用如：玻璃、石英、鋁、不鏽鋼等之金 屬、氧化鋁等之陶瓷等。又，必要時，亦可進行噴鍍處理， 使基材表面變粗後，形成氧化物被膜。 本實施之形態例之氧化物被膜之純度爲99.9%以上者 宜。藉由使純度作成99.9%以上，即使曝露於鹵素系腐鈾氣 體或鹵素系氣體電漿等，仍可抑制氧化物被膜腐蝕之進行。 200936504 含於本實施形態例之耐鈾性構件表面所形成之氧化物 被膜中之鐵族金屬化合物係爲用於Fe、Co、Ni等者宜，更 爲降低Gd或Yb之熔點之使用。而且，使作爲原料之Gd或 Yb進行氧化作成粉末化之同時，氧化鐵族金屬化合物，粉 末化後，混合此等後，於基材表面以後述之方法形成氧化物 被膜。鐵族金屬化合物之混合比例係以氧化物換算下含有多 於5ppm者即可。當鐵族金屬化合物以氧化物換算下含有少 φ 於5ppm時，則將減少降低Gd或Yb之熔點效果。又，當鐵 族金屬化合物以氧化物換算下含有多於50ppm時，則含有 Gd或Yb之氧化物被膜曝露於鹵素系腐蝕氣體或鹵素系氣 體電漿等時，將活化蝕刻，產生過剩之微粒。因此，以氧化 物換算下含有鐵族金屬化合物爲多於5 ppm、少於50ppm者 宜。 本實施之形態例中氧化物被膜之形成方法並未特別限 定，一般可以如：火焰噴塗、高速火焰噴塗（HVOF)、電漿 G 噴塗、爆炸火焰噴塗、冷噴霧、氣熔膠法等形成之。其中又 以噴塗輸出功率高、適於高溶點材料之噴塗之電漿噴塗所形 成者較佳。 電漿噴塗時之電漿產生時所使用之氣體並未特別限 定，一般可使用如：氬氣、氦氣、氮氣、氫氣、氧氣等。 本實施形態例中氧化物被膜之氣孔率爲5 %〜1 5 %者 宜。5%以上之氧化物被膜於被膜步驟中不易產生龜裂。 又’ 15 %以下之氧化物被膜即使曝露於鹵素系腐蝕氣體或鹵 素系氣體電漿等時，仍可維持氧化物被膜之強度，可防止缺 200936504 陷、剝離。更於未透過氧化物被膜之基材上使鹵素系腐鈾氣 體或鹵素系氣體電漿等不易受損。 爲形成本實施形態例之氧化物被膜所使用之噴塗粉末 藉由使平均粒徑爲20μιη〜60μηι、較佳者爲 30μιη〜50μηι 後，可於電漿火焰上流動、於熔融狀態下附著於構件。平均 粒徑爲20μιη以上，使噴塗粉末投入電漿火焰時，噴塗粉末 不會飛散，可流動於電漿火焰，於熔融狀態下附著於構件。 0 又，平均粒徑爲60μπι以下，使噴塗粉末投入電漿火焰時， 噴塗粉末不會經電漿火焰脫落，可流動於電漿火焰，於熔融 狀態下，附著於構件。 本實施形態例之氧化物被膜厚度爲ΙΟΟμηι〜ΙΟΟΟμιη者 宜。作成ΙΟΟμιη以上則即使曝露於鹵素系腐蝕氣體或鹵素 系氣體電漿等時，仍可預見耐蝕性之效果，甚至鹵素系腐蝕 氣體、或鹵素系氣體電漿等不易透過至基材爲止。又，作成 1 000 μπτ以下，則不易產生經由耐蝕性構件之基材與氧化物 〇 被膜之熱膨脹差的剝離。 本實施形態例之氧化物被膜之密合強度係以20MPa以 上形成於基材者宜。氧化物被膜與基材之密合強度作成 20MPa以上，可防止使用中、洗淨中之氧化物被膜之剝 離。氧化物被膜經剝離後則易由基材之露出部產生微粒，而 作成上述之密合強度則可防止。 [實施例] 以下’詳細說明本發明之一實施例。另外，本發明並 -9- 200936504 未受限於以下所說明之實施例。 實施例中Fe203値係使用ICP發光分析裝置所測定。實 施例中噴塗粉末之平均粒徑係使用雷射衍射·散射式之粒度 測定機所測定。 實施例中蝕刻率係使部份氧化物被膜以聚醯亞胺膠帶 進行標識，利用RIE裝置，於CF4電漿中進行照射10小 時，測定標識有無之個處的段差後求取之。 實施例中氣孔率係測定氧化物被膜之乾燥重量W 1、 水中重量W2、飽水重量W3，利用以下之阿基米德法求取 之。 χΐ 0 0 氣孔率（％)= (W3 - W1) (W3-W27 (實施例 1、2、3、4、5) 使平均粒徑爲 30μιη〜40μπι之分別含有 8ppm、BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a corrosion-resistant member, and a corrosion-resistant member having an oxide film suitable for use in, for example, a semiconductor manufacturing apparatus, a flat display manufacturing apparatus, or a solar cell manufacturing apparatus. Invention. [Prior Art] Φ is manufactured in an environment of a halogen-based corrosive gas or a halogen-based gas plasma in a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell manufacturing apparatus, and is resistant to uranium. The components. In recent years, the corrosion resistance of rare earth compounds has been determined, and in particular, the corrosion resistance film containing ruthenium 2〇3 is applied to the surface of the substrate as disclosed in JP-A-6-64354. However, since Υ3〇3 is a high melting point, it is difficult to melt and forms an oxide film in a semi-molten state. Therefore, in a semiconductor manufacturing apparatus, a flat display device manufacturing apparatus, and a solar cell manufacturing apparatus are provided. When exposed to a halogen-based corrosive gas or a halogen-based gas plasma, the crystal particles are degranulated by etching on the surface of the film to generate fine particles, and the generated particles adhere to the wafer, resulting in a problem of lowering the yield. SUMMARY OF THE INVENTION An object of the present invention is to provide a corrosion-resistant member formed of an oxide film having good corrosion resistance for a halogen-based etching gas or a halogen-based gas plasma, etc. - 5 - 200936504 In order to solve the above problems, a corrosion-resistant member capable of sufficiently ensuring corrosion resistance to a halogen-based corrosive gas or a halogen-based gas plasma is provided. In order to achieve the object, the object of the present invention is to provide a corrosion-resistant member characterized by forming an oxide film containing Gd on a substrate, or to form Yb-containing material on a substrate. A corrosion-resistant member characterized by an oxide film, such as: in the oxide film φ, the 'iron group metal compound is characterized by containing more than 5 ppm in terms of oxide. Or in the oxide film, the iron group The metal compound is characterized by containing less than 50 ppm in terms of oxide. Moreover, the oxide film is characterized by being formed by a spray coating method. The corrosion-resistant member of the present invention is more suitable for use in a semiconductor manufacturing apparatus and a plane. It is characterized by components used in the display manufacturing apparatus and in the solar cell manufacturing apparatus. Specifically, it can be applied to an electrostatic chuck, a heater, a gas diffusion plate, a baffle, a retaining ring, a shower plate, and a shed. Room, bell jar, dome and inner wall material, and sorghum frequency transmissive window, infrared window, monitor window, base, locking ring, focal length ring, shadow ring, insulating ring, simulation crystal The present invention provides a lifting device for a semiconductor wafer, a telescopic cover, a cooling plate, an upper electrode, and a lower electrode. The present invention can provide a semiconductor display device that can be applied to a semiconductor manufacturing device using a halogen-based etching gas or a halogen-based gas plasma. The corrosion-resistant member having good corrosion resistance in the device and the solar cell manufacturing device can reduce the generation of fine particles. The present invention is characterized in that the oxide film contains more than 5 ppm of iron group metal in terms of oxide. The compound can form an oxide film of good corrosion resistance of 200936504. [Embodiment] [Best Mode for Carrying Out the Invention] The inventors of the present invention found that an oxide film containing Gd or Yb was obtained after performing a precise beating. Even if it is exposed to a halogen-based corrosive gas or a halogen-based gas plasma, it has good corrosion resistance, and particle 0 is rarely generated. Further, it has been found that the oxide film contains an iron group metal compound of more than 5 ppm in terms of oxide, thereby lowering the melting point of Gd or Yb and forming an oxide film having good corrosion resistance. Hereinafter, a form of embodiment of the present invention will be described in detail with reference to the drawings and the like. The corrosion-resistant member of the embodiment of the present embodiment described below forms an oxide film containing Gd (§L: Gadolinium) or Yb (Ytterbium) and containing more than 5 ppm of an iron group metal compound in terms of oxide. Made into. The corrosion-resistant member according to the embodiment of the present invention is applied to a semiconductor manufacturing device, a flat display manufacturing device, a member in a solar cell manufacturing device, or at least a surface for a halogen-based etching gas or a halogen-based gas plasma. An oxide film with uranium resistance. The material of the substrate of the corrosion-resistant member is not particularly limited, and generally, a metal such as glass, quartz, aluminum, or stainless steel, or a ceramic such as alumina can be used. Further, if necessary, a thermal spraying treatment may be performed to form a surface of the substrate to form an oxide film. The purity of the oxide film of the embodiment of the present embodiment is preferably 99.9% or more. By making the purity 99.9% or more, it is possible to suppress the progress of the oxide film corrosion even when exposed to a halogen-based uranium gas or a halogen-based gas plasma. 200936504 The iron group metal compound contained in the oxide film formed on the surface of the uranium-resistant member of the present embodiment is preferably used for Fe, Co, Ni, etc., and further reduces the melting point of Gd or Yb. In addition, Gd or Yb as a raw material is oxidized and pulverized, and the iron oxide group metal compound is mixed, and after mixing, the oxide film is formed on the surface of the substrate to be described later. The mixing ratio of the iron group metal compound may be more than 5 ppm in terms of oxide. When the iron group metal compound contains less φ at 5 ppm in terms of oxide, the effect of lowering the melting point of Gd or Yb is reduced. In addition, when the iron group metal compound contains more than 50 ppm in terms of oxide, when the oxide film containing Gd or Yb is exposed to a halogen-based etching gas or a halogen-based gas plasma, it is activated and etched to generate excess particles. . Therefore, it is preferred that the iron group-containing metal compound is contained in an amount of more than 5 ppm and less than 50 ppm in terms of oxide. The method for forming the oxide film in the embodiment of the present embodiment is not particularly limited, and may be generally formed by flame spraying, high-speed flame spraying (HVOF), plasma G spraying, explosion flame spraying, cold spraying, gas melting method, or the like. . Among them, it is preferably formed by plasma spraying with high spray output power and suitable for spraying of high melting point materials. The gas used in the plasma generation during plasma spraying is not particularly limited, and generally, for example, argon gas, helium gas, nitrogen gas, hydrogen gas, oxygen gas or the like can be used. In the present embodiment, the porosity of the oxide film is preferably from 5% to 15%. More than 5% of the oxide film is less likely to be cracked in the film step. Further, when the oxide film of 15% or less is exposed to a halogen-based corrosive gas or a halogen-based gas plasma, the strength of the oxide film can be maintained, and the fall and tear of the 200936504 can be prevented. Further, the halogen-based uranium gas or the halogen-based gas plasma is less likely to be damaged on the substrate which is not permeable to the oxide film. The spray powder used for forming the oxide film of the present embodiment can be attached to the member in a molten state by flowing the film to an average particle diameter of 20 μm to 60 μm, preferably 30 μm to 50 μm. . When the average particle diameter is 20 μm or more, when the spray powder is put into the plasma flame, the spray powder does not scatter, and it can flow to the plasma flame and adhere to the member in a molten state. 0 Further, when the average particle diameter is 60 μm or less, when the spray powder is put into the plasma flame, the spray powder does not fall off by the plasma flame, and can flow in the plasma flame and adhere to the member in a molten state. The thickness of the oxide film of the present embodiment is preferably ΙΟΟμηι~ΙΟΟΟμιη. When it is ΙΟΟμιη or more, even when it is exposed to a halogen-based corrosive gas or a halogen-based gas plasma, the effect of corrosion resistance can be expected, and even a halogen-based corrosive gas or a halogen-based gas plasma is hardly transmitted to the substrate. Further, when it is made to be 1 000 μπτ or less, peeling of the difference in thermal expansion between the substrate passing through the corrosion-resistant member and the oxide ruthenium film is less likely to occur. The adhesion strength of the oxide film of the present embodiment is preferably 20 MPa or more. The adhesion strength between the oxide film and the substrate is 20 MPa or more, and peeling of the oxide film during use and during cleaning can be prevented. When the oxide film is peeled off, fine particles are easily generated from the exposed portion of the substrate, and the above-described adhesion strength can be prevented. [Examples] Hereinafter, an embodiment of the present invention will be described in detail. Further, the present invention and -9-200936504 are not limited to the embodiments described below. In the examples, Fe203 was measured using an ICP emission spectrometer. The average particle diameter of the sprayed powder in the examples was measured using a laser diffraction/scattering type particle size measuring machine. In the examples, the etching rate was such that a part of the oxide film was marked with a polyimide tape, and the film was irradiated for 10 hours in a CF4 plasma by an RIE apparatus, and the difference in the presence or absence of the mark was measured. In the examples, the porosity was determined by measuring the dry weight W 1 of the oxide film, the weight W2 in water, and the weight W3 of the water, using the following Archimedes method. Χΐ 0 0 Porosity (%) = (W3 - W1) (W3-W27 (Examples 1, 2, 3, 4, 5) The average particle diameter is 30 μm to 40 μm, respectively, containing 8 ppm.
Q lOppm、20ppm、30ppm、40ppm Fe203 之 Gd 氧化物的 Gd203之噴塗粉末利用空氣電漿公司製ASP 7100電漿噴 塗機，於電壓275V、電流110A、氬氣流量25L/min、氧 氣流量40L/min之噴塗條件下，於噴鍍處理之lOOxlOOx 5t(mm)之鋁基材上進行噴塗，形成200μιη〜300μπι之氧化 物被膜。接著進行所形成氧化物被膜之蝕刻率及氣孔率之 評定。 (實施例 6、7、8、9、10) -10- 200936504 使平均粒徑爲 30μιη〜40μιη之分別含有 8ppm、 lOppm、20ppm、30ppm、40ppm Fe2〇3 之 Yb 氧化物的 Yb203之噴塗粉末利用空氣電漿公司製ASp 7100電漿噴 塗機，於電壓275V、電流110A、氬氣流量25L/min、氧 氣流量40L/min之噴塗條件下，於噴鍍處理之ΙΟΟχΙΟΟχ 5t(mm)之鋁基材上進行噴塗，形成200μηι〜300μιη之氧化 物被膜。接著，進行所形成氧化物被膜之蝕刻率及氣孔率 φ 之評定。 (比較例 1、2 ' 3、4、5) 使平均粒徑爲 30μιη〜40μιη之分別含有 lppm、 3ppm、4ppm ' 70ppm、80ppm Fβ203 之 Gd 氧化物的 Gd203噴塗粉末，利用空氣電漿公司製ASP 7100電漿噴 塗機，於電壓2 75V、電流110A、氬氣流量25L/min、氧 氣流量40L/min之噴塗條件下，於噴鍍處理之ΙΟΟχΙΟΟχ Φ 5t(mm)之鋁基材上進行噴塗，形成200μιη〜300μιη之氧化 物被膜。接著，進行所形成之氧化物被膜之蝕刻率及氣孔 率之評定。 (比較例 6、7、8、9、1 0) 使平均粒徑爲 30μπι〜40μιη之分別含有 lppm、 3ppm、4ppm、70ppm、80ppm Fe2〇3 之 Yb 氧化物的 Yb203噴塗粉末，使用空氣電漿公司製ASP 7100電漿噴 塗機，於電壓275V、電流110A、氬氣流量25L/min、氧 -11 - 200936504 氣流量40L/min之噴塗條件下，於噴鍍處理之ιοοχΙΟΟχ 5t(mm)之銘基材上進行噴塗，形成200μιη〜300μιη之氧化 物被膜。接著，進行評定所形成氧化物被膜之蝕刻率及氣 孔率。 (比較例U) 使平均粒徑爲30μιη〜40μηι之含有l〇ppm Fe203之Υ 0 的氧化物之 Y2〇3噴塗粉末，利用空氣電漿公司製 ASP 7100電漿噴塗機，以電壓275V、電流1 i〇A、氬氣流量 25L/min、氧氣流量40L/min之噴塗條件下，於噴鍍處理 之10〇xl00x5t(mm)之銘基材上進行噴塗、形成200μιη〜 3 00 μιη之氧化物被膜。接著’進行評定所形成氧化物被膜 之蝕刻率及氣孔率。 表1顯示，針對實施例與比較例所測定之蝕刻率及氣 孔率之結果。另外，比較例5、1 〇被確定局部性蝕刻，故 Q 於表1顯示其部份蝕刻率。 -12- 200936504 表1 Ο Ο 種類 F e2 〇 3 (ppm) 蝕刻率 (nm/min) 氣孔率 (%) 實施例1 G d 2 0 3 8 0.9 14.1 實施例2 實施例3 10 0.8 12.3 20 0.6 10.4 實施例4 30 0.6 9.5 實施例5 40 0.7 8.9 實施例6 Y b 2 〇 3 8 0.9 14.5 實施例7 10 0.9 12.1 實施例8 實施例9 實施例1 0 20 0.6 10.8 30 0.7 8.7 40 0.7 7.9 比較例1 G d 2 0 3 1 5.7 21.5 比較例2 比較例3 3 2.8 18.4 4 1.7 17.5 比較例4 70 11 8.6 比較例5 80 55 8.2 比較例6 Yb2〇3 1 5.6 2 1.1 比較例7 3 3.0 18.7 比較例8 4 1.9 16.8 比較例9 70 15 7.4 比較例1 0 80 86 7.2 比較例1 1 Y2〇3 10 1.9 9.8 由表1得知，Fe203爲少於5ppm之Gd2〇3及Yb203 其氣孔率爲15 %以上，因此氧化物被膜曝露於鹵素系腐蝕 氣體或鹵素系氣體電漿等，則氧化物被膜因強度不足容易 被蝕刻，進而產生微粒。故不適於作爲利用鹵素系腐蝕氣 體或鹵素系氣體電漿等之半導體製造裝置內、平面顯示器 裝置內、太陽電池製造裝置內之耐蝕性構件。反之， -13- 200936504Q lOppm, 20ppm, 30ppm, 40ppm Fe203 Gd oxide Gd203 spray powder using air plasma company ASP 7100 plasma sprayer, at 275V, current 110A, argon flow 25L / min, oxygen flow 40L / min Under the spraying conditions, the aluminum substrate of 100 μlOOx 5 t (mm) of the sputtering treatment was sprayed to form an oxide film of 200 μm to 300 μm. Next, the etching rate and the porosity of the formed oxide film were evaluated. (Examples 6, 7, 8, 9, 10) -10-200936504 A spray powder of Yb203 containing Yb oxides of 8 ppm, 10 ppm, 20 ppm, 30 ppm, and 40 ppm Fe2〇3, respectively, having an average particle diameter of 30 μm to 40 μm was used. Air slurry company ASp 7100 plasma spraying machine, under the spraying conditions of voltage 275V, current 110A, argon flow rate 25L/min, oxygen flow rate 40L/min, spray coating ΙΟΟχΙΟΟχ 5t (mm) aluminum substrate Spraying was performed to form an oxide film of 200 μm to 300 μm. Next, the etching rate and the porosity φ of the formed oxide film were evaluated. (Comparative Example 1, 2 '3, 4, 5) Gd203 spray powder containing Gd oxides of 1 ppm, 3 ppm, 4 ppm '70 ppm, and 80 ppm of Fβ203, respectively, having an average particle diameter of 30 μm to 40 μm, using ASP manufactured by Air Plasma Co., Ltd. The 7100 plasma spraying machine is sprayed on the aluminum substrate of Φ 5t (mm) under the spraying process under the spraying conditions of voltage 2 75V, current 110A, argon flow rate 25L/min and oxygen flow rate 40L/min. An oxide film of 200 μm to 300 μm is formed. Next, the etching rate and the porosity of the formed oxide film were evaluated. (Comparative Examples 6, 7, 8, 9, 10) Yb203 spray powder containing Yb oxides of 1 ppm, 3 ppm, 4 ppm, 70 ppm, and 80 ppm Fe2〇3, respectively, having an average particle diameter of 30 μm to 40 μm, using air plasma The company's ASP 7100 plasma spraying machine is immersed in the spraying condition of ιοοχΙΟΟχ 5t(mm) under the spraying conditions of voltage 275V, current 110A, argon flow rate 25L/min, oxygen-11 - 200936504 air flow 40L/min. The substrate was sprayed to form an oxide film of 200 μm to 300 μm. Next, the etching rate and the porosity of the oxide film formed were evaluated. (Comparative Example U) A Y2〇3 spray powder having an average particle diameter of 30 μm to 40 μηι containing an oxide of 〇0 ppm of 〇ppm Fe203, using an ASP 7100 plasma sprayer manufactured by Air Plasma Co., Ltd., with a voltage of 275 V, a current 1 i〇A, argon flow rate 25L/min, oxygen flow rate 40L/min under spraying conditions, spraying on the substrate of 10〇xl00x5t (mm) of the spray treatment to form oxide of 200μηη~3 00 μηη Membrane. Next, the etching rate and the porosity of the oxide film formed were evaluated. Table 1 shows the results of the etching rate and the porosity measured for the examples and the comparative examples. Further, Comparative Examples 5 and 1 were determined to be partially etched, so Q shows a partial etching rate thereof in Table 1. -12- 200936504 Table 1 Ο Ο Type F e2 〇 3 (ppm) Etch rate (nm/min) Porosity (%) Example 1 G d 2 0 3 8 0.9 14.1 Example 2 Example 3 10 0.8 12.3 20 0.6 10.4 Example 4 30 0.6 9.5 Example 5 40 0.7 8.9 Example 6 Y b 2 〇 3 8 0.9 14.5 Example 7 10 0.9 12.1 Example 8 Example 9 Example 1 0 20 0.6 10.8 30 0.7 8.7 40 0.7 7.9 Comparison Example 1 G d 2 0 3 1 5.7 21.5 Comparative Example 2 Comparative Example 3 3 2.8 18.4 4 1.7 17.5 Comparative Example 4 70 11 8.6 Comparative Example 5 80 55 8.2 Comparative Example 6 Yb2〇3 1 5.6 2 1.1 Comparative Example 7 3 3.0 18.7 Comparative Example 8 4 1.9 16.8 Comparative Example 9 70 15 7.4 Comparative Example 1 0 80 86 7.2 Comparative Example 1 1 Y2〇3 10 1.9 9.8 It is known from Table 1 that Fe203 is less than 5 ppm of Gd2〇3 and Yb203. When the oxide film is exposed to a halogen-based corrosive gas or a halogen-based gas plasma or the like, the oxide film is easily etched due to insufficient strength, and fine particles are generated. Therefore, it is not suitable as a corrosion-resistant member in a semiconductor manufacturing apparatus using a halogen-based etching gas or a halogen-based gas plasma, in a flat display device, or in a solar cell manufacturing apparatus. Conversely, -13- 200936504
Fe2〇3爲多於50pprn之Gd2〇3及Yb203其氧化物被膜局部 被蝕刻’產生過剩之微粒。因此，不適於作爲利用鹵素系 腐蝕氣體或鹵素系氣體電漿等之半導體製造裝置內、平面 顯示器製造裝置內、太陽電池製造裝置內之耐蝕性構件。 由表1得知，Fe203爲多於 5ppm之 Gd203及 Yb203 ’對於Y2〇3而言，其蝕刻率爲1/2〜1/3因此極少 產生微粒。故適於作爲利用鹵素系腐蝕氣體或鹵素系氣體 0 電漿等之半導體製造裝置內、平面顯示器製造裝置內、太 陽電池製造裝置內之耐蝕性構件。 由上述顯示，含有Gd或Yb之氧化物，且以氧化物 換算下含有多於5ppm鐵族金屬化合物之氧化物被膜所形 成之耐蝕性構件對於_素系腐蝕氣體或鹵素系氣體電漿等 具良好耐蝕性。因此，適於曝露於鹵素系腐蝕氣體或鹵素 系氣體電漿等之半導體製造裝置內、平面顯示器製造裝置 內、太陽電池製造裝置內之使用。 〇 (試料1、2) 使平均粒徑爲30μιη〜40μηι之含有8ppm Fe2〇3之Gd 及Yb氧化物之Gd203及Yb203噴塗粉末，利用空氣電漿 公司製 ASP 7100電漿噴塗機，以電壓 275V、電流 110A、氬氣流量25L/min、氧氣流量40L/min之噴塗條件 下，於噴鍍處理之棒狀鋁基材上（表面粗度Ra 5.1 Ιμιη)進 行噴塗，形成200μπι〜300μιη之氧化物被膜。之後，以黏 著劑黏接形成該氧化物被膜之基材與另一棒狀鋁基材，測 -14 - 200936504 定藉由拉延之剝離強度，亦即密合強度。（JIS Η 8666爲基 準之試驗方法）。 (試料3) 使平均粒徑爲30μιη〜40μιη之含有8ppm Fe203之Υ 氧化物的Y2〇3噴塗粉末，利用空氣電漿公司製ASP 7100 電漿噴塗機，以電壓 275V、電流 110A、氬氣流量 φ 25L/min、氧氣流量40L/min之噴塗條件下，於噴鍍處理 之棒狀鋁基材上（表面粗度Ra 5.02μηι)進行噴塗，形成 2 0(^111〜3 0(^111之氧化物被膜。之後，以黏著劑黏接形成 該氧化物被膜之基材與另一棒狀之鋁基材，測定藉由拉延 之剝離強度，亦即密合強度。（依JISH 8666爲基準之試 驗方法）。 表2顯示針對該試料1、2、3所測定之密合強度之結 果。 表2 種類 表面粗度Ra (μιη) 氣孔率 (%) 密合力 (MPa、 試料1 Gd2〇3 5.09 14.1 22 試料2 Yb203 5.09 14.5 21 試料3 Y2〇3 5.10 13.8 —14 依據表2，同等條件下，相較於Υ2〇3與基材之密合 強度14MPa、Gd；2〇3及 Yt»2〇3與基材之密合強度分別爲 22MPa、21MPa。因此，Gd2〇3 與 Yb2〇3 比 γ2〇3 較易密合 -15- 200936504 於基材，較不易產生剝離。 由以上顯示，Gd及Yb之氧化物的Gd203及Yb2〇3所 形成之耐蝕性構件適於半導體製造裝置內、平面顯示器製 造裝置內、太陽電池製造裝置內之使用、洗淨環境之使 用。 另外，作爲半導體製造裝置內、平面顯示器製造裝置 內、太陽電池製造裝置內所使用之構件者，可使用如：靜 φ 電吸盤、加熱器等、內部具有靜電電極、電阻發熱體者。 靜電電極多半使用耐蝕性低的金屬，因此，以本發明耐蝕 性構件被覆此等後，可大幅提昇耐蝕性，亦可長時間使用 之。 本發明之耐蝕性構件可採用爲使鹵素系腐蝕氣體導入 裝置內之氣體擴散板、擋板、擋環、簇射極板等。更亦可 適用導入氣體之處理容器的棚室、鐘罩、圓頂及其內壁材 料、以及高頻透窗、透紅外線窗、監視窗。進一步可適用 於爲支撐容器內所使用之基座、鎖緊圈、焦距環、shadow ring、絕緣環、仿真晶圓、半導體晶圓之升降針、伸縮護 蓋、冷卻板、上部電極、下部電極等、電漿雰圍下被曝 露’需要耐蝕性之各種構件。 【圖式簡單說明】 [圖1 ]圖1代表於實施例及比較例所得之蝕刻率及氣 孔率之圖。 -16-Fe2〇3 is more than 50 pprn of Gd2〇3 and Yb203 whose oxide film is partially etched to generate excess particles. Therefore, it is not suitable as a corrosion-resistant member in a semiconductor manufacturing apparatus using a halogen-based etching gas or a halogen-based gas plasma, in a flat-panel manufacturing apparatus, or in a solar cell manufacturing apparatus. As is apparent from Table 1, Fe203 is more than 5 ppm of Gd203 and Yb203'. For Y2〇3, the etching rate is 1/2 to 1/3, so that fine particles are rarely generated. Therefore, it is suitable as a corrosion-resistant member in a semiconductor manufacturing apparatus using a halogen-based etching gas or a halogen-based gas 0 plasma, or in a flat-panel manufacturing apparatus and a solar cell manufacturing apparatus. As described above, the corrosion-resistant member formed of an oxide film containing an oxide of Gd or Yb and containing more than 5 ppm of an iron group metal compound in terms of an oxide is provided for a sulphur-based corrosive gas or a halogen-based gas plasma. Good corrosion resistance. Therefore, it is suitable for use in a semiconductor manufacturing apparatus exposed to a halogen-based corrosive gas or a halogen-based gas plasma, in a flat-panel display manufacturing apparatus, or in a solar cell manufacturing apparatus. 〇 (samples 1, 2) Gd203 and Yb203 spray powders containing 8 ppm Fe2〇3 of Gd and Yb oxides having an average particle diameter of 30 μm to 40 μm, using an ASP 7100 plasma sprayer manufactured by Air Plasma Co., Ltd., at a voltage of 275V Spraying on a rod-shaped aluminum substrate (surface roughness Ra 5.1 Ιμιη) under spray coating to form an oxide of 200 μm to 300 μm under spray conditions of a current of 110 A, an argon flow rate of 25 L/min, and an oxygen flow rate of 40 L/min. Membrane. Thereafter, the substrate of the oxide film and the other rod-shaped aluminum substrate are bonded by an adhesive, and the peel strength, that is, the adhesion strength, is determined by drawing. (JIS Η 8666 is the benchmark test method). (Sample 3) A Y2〇3 spray powder containing 8 ppm of Fe203 oxide of an average particle diameter of 30 μm to 40 μm was used, and an ASP 7100 plasma sprayer manufactured by Air Plasma Co., Ltd. was used, with a voltage of 275 V, a current of 110 A, and an argon flow rate. Under the spraying conditions of φ 25L/min and oxygen flow rate of 40L/min, spraying on the bar-shaped aluminum substrate (surface roughness Ra 5.02μηι) of the spray coating to form 20 (^111~3 0 (^111 After the oxide film is formed, the base material of the oxide film and the other aluminum alloy substrate are bonded by an adhesive, and the peel strength by drawing, that is, the adhesion strength is measured. (Based on JISH 8666) Test method) Table 2 shows the results of the adhesion strength measured for the samples 1, 2, and 3. Table 2 Type surface roughness Ra (μιη) Porosity (%) Adhesion (MPa, sample 1 Gd2〇3 5.09 14.1 22 Sample 2 Yb203 5.09 14.5 21 Sample 3 Y2〇3 5.10 13.8 —14 According to Table 2, under the same conditions, the adhesion strength to the substrate is 14 MPa, Gd; 2〇3 and Yt»2 compared to Υ2〇3 The adhesion strength between 〇3 and the substrate is 22 MPa and 21 MPa, respectively. Therefore, Gd2〇3 and Yb2〇3 are more than γ2. 3 Easier adhesion -15- 200936504 It is less prone to peeling on the substrate. From the above, the corrosion-resistant members formed by Gd203 and Yb2〇3 of Gd and Yb oxides are suitable for semiconductor manufacturing equipment and flat panel display manufacturing. Use in the inside of the device, in the solar cell manufacturing device, and in the cleaning environment. As a component used in the semiconductor manufacturing device, in the flat panel display manufacturing device, or in the solar cell manufacturing device, for example, a static φ electric chuck can be used. For example, a heater or the like has an electrostatic electrode or a resistance heating element. Most of the electrostatic electrode uses a metal having low corrosion resistance. Therefore, after the corrosion-resistant member of the present invention is coated, the corrosion resistance can be greatly improved, and the corrosion resistance can be greatly improved. The corrosion-resistant member of the present invention may be a gas diffusion plate, a baffle plate, a baffle plate, a shower plate or the like for introducing a halogen-based corrosive gas into the device, and may also be applied to a chamber or a bell jar for introducing a gas processing container. , the dome and its inner wall materials, as well as high-frequency transparent windows, infrared-transparent windows, and monitoring windows. Further suitable for use in supporting containers Seat, locking ring, focal length ring, shadow ring, insulating ring, dummy wafer, lifting pad of semiconductor wafer, telescopic cover, cooling plate, upper electrode, lower electrode, etc., exposed under plasma atmosphere 'requires corrosion resistance [Members of the drawings] [Fig. 1] Fig. 1 is a view showing the etching rate and the porosity of the examples and the comparative examples.