TW200815624A - Ceramic coating material for thermal spray on the parts of semiconductor processing devices and fabrication method and coating method thereof - Google Patents

Abstract

A thermal spray coating material for use in semiconductor equipment, its preparation method, and a coating method thereof are disclosed. The coating material may have a composition of (A1xY1-x)2O3 (x is within a range of 0.05 to 0.95), and be formed as a powder with a diameter of 1 [mu]m to 100 [mu]m. A coating film that is coated by using the powder according to the thermal spray method has an amorphous structure.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal spray 5 material for a component of a semiconductor manufacturing apparatus, a thermal spray material for a semiconductor manufacturing apparatus, a method of manufacturing the same, and a coating method . [Prior Art] Background of the Invention

Vacuum ionizer equipment is widely used in semiconductor components or other fields of engineering that realize ultra-fine construction. For example, a PECVD (plasma enhanced chemical vapor deposition) device in which a vapor deposited film is formed on a substrate by a chemical vapor deposition method using plasma, a vacuum film formed by a physical method, and a substrate in a desired pattern are prepared. A vacuum plasma apparatus is used for the dry etching apparatus or the like of the coated member on the substrate. 15 20 Ά Plasma S is prepared for high-temperature plasma (10) j semiconductor components ^ Realize ultra-fine structure. Therefore, the inside of the vacuum (four) sub-parent will produce: the warm plasma 'damages from the chamber and internal components 1 and the specific elements and contaminated particles will be generated on the surface of the chamber to its parts, so the chamber is internally contaminated. The possibility is greater. In particular, since the reaction gas containing fluorine and gas is injected into the plasma environment, the inner wall of the chamber and the internal components of the plasma_equipment are often in a severely rotted environment. Such a pure image of rot will first damage the genus of the species. The latter will generate pollutants and particles, which will increase the defect rate of products produced through internal processes and reduce product quality. 5 200815624 [^^明明发明发明概要 The present invention has been made in view of the above problems, and an object thereof is to provide a coating material for a chamber of a true two plasma process apparatus and its internal components, 5 for thermal spraying of ceramics During the process, internal defects of the protective coating are reduced, thereby improving corrosion resistance and extending component life. The present invention also provides a method of producing the above-described coating material for a semiconductor manufacturing facility. Further, the present invention provides a method of coating a member for a semiconductor manufacturing apparatus using the coating material. The thermal spray material of the present invention is a thermal spray material for a semiconductor manufacturing apparatus, and has a composition of (Α1χΥ1-χ)2〇3 (the range of χ is still 仍·仍_95·), and has an amorphous state ( Amorphous) structure. Wherein X can be from 0.5 to 0.95. Further, the thermal spray material may include a powder having a particle diameter of M00. The method for producing a thermal spray material for a semiconductor manufacturing apparatus of the present invention comprises the steps of: i) mixing eight 12 〇 3 particles and 1 〇 3 particles having a particle diameter of Oi-30 ^1 „1 to prepare a composition ( AlxYi Aha ranges from 0.05 to 0.95); ii) spray drying the material to prepare a synthetic powder; iii) calcining the synthetic powder at a temperature of 800-1500 ° C: wherein, the mixing chamber The step of describing the substance may further comprise the step of applying static electricity. The step of inducing and causing the Al2〇3 particles and the Υ2〇3 particles to carry charges of different polarities, respectively. And the step of applying static electricity comprises the following steps: Solvent 6 200815624 is added with poly-methyl metacrylic ammonium salt, which makes the octa 12 〇 3 particles carry a negative charge; 2) adding χκ & Ι醯 Ι醯 imine in the solvent (P〇ly- The ethylenium imide) causes the Y2〇3 particles to carry a positive charge. 5 The coating method of the thermal spray material for a semiconductor manufacturing apparatus of the present invention comprises the following steps: i) preparing a composition of (eight^_02〇3b is a range) ·〇5-0·95) thermal spray material (1) injecting a thermal spray material into the plasma flame, thereby heating the thermal spray material; and discharging a thermal spray material that is in a fully molten or semi-melted state by heating on the surface of the component for the semiconductor manufacturing apparatus 10. Forming an amorphous coating. The step of forming a coating layer may further comprise the step of forming a metal intermediate layer. Moreover, the step of forming a coating layer may further comprise gradually changing the composition of the thermal spray material. Ingredients to form a gradient coating. 15 Also, when coating, the composition of the thermal spray material can be gradually changed from (the same as or similar to the composition of the substrate to be coated) to (eight^)2〇3 The method of forming a gradient coating of the range 疋0.05-0.95) forms a gradient coating. In addition, in the step of opening the coating, the component may be a chamber of a vacuum plasma apparatus or a component inside the chamber. The coating material of the present invention is composed of a powder of eight 1203 and γ 2 () 3, and thus is widely used as a material of a semiconductor manufacturing equipment component, and is inexpensive. Moreover, the coating material is very As used in semiconductor technology, its stability has been verified, so it does not cause problems in other semiconductor processes. Using the coating material of the present invention, thermal spray coating is formed on the substrate. An amorphous coating is formed. Therefore, the volume produced when it becomes a solid does not change much, thereby reducing the internal defects of the coating. Moreover, the coating maintains high mechanical strength due to the reduction of internal defects of the coating. Therefore, the corrosion resistance in the environment of the rot can be improved. 5 In addition, by using the coating powder and the coating method of the present invention, mechanical strength and corrosion resistance can be formed in the chamber of the vacuum plasma processing apparatus and its internal components. Sexual coating. Therefore, the life of the component can be extended, the components of the manufacturing equipment can be frequently replaced, or the manufacturing equipment can be frequently repaired, thereby improving the productivity of the semiconductor. 10 In addition, in the semiconductor manufacturing process, the production rate of contaminated particles is reduced, thereby improving product quality. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view of a plasma stencil apparatus which is one of semiconductor manufacturing equipment. 15 帛 2 is a plasma grab profile of a plasma thermal spray apparatus. Fig. 3 is an electronic scanning transmission photograph of a YA (oxygen) coating profile formed by an external plasma gun. Figure 4 is an electron scanning micrograph of a γ2〇3 20 coating profile formed by internal plasma capture. Fig. 5 is a scanning electron micrograph showing the cracking of the liquid smelting pottery particles upon cooling. Figure 6 is a conditional diagram showing the crystallization phenomenon depending on temperature and temperature when the liquid substance is solidified by cooling. 8 200815624 Figure 7 is a schematic diagram showing the volume change process produced by the liquid material being cooled and solidified. Fig. 8 is a schematic diagram showing the principle of defect formation by the liquid substance becoming a crystalline solid. _ 5 Fig. 9 is a pattern diagram for explaining the conditions under which the crystal form is formed by cooling according to the type of material. w Fig. 10 is a schematic diagram for explaining the volume shrinkage process that occurs when the liquid material is cooled to form an amorphous material. • Fig. 11 is a process pattern diagram for explaining defects such as cracking and cracking when the liquid material is in an amorphous state. Fig. 12 is a schematic view for explaining a process of mixing different types of powders to prepare a composite powder for thermal spraying having a larger powder size. Figure 13 is an electron scanning micrograph of a ceramic powder for thermal spraying synthesized in accordance with the present invention. 15 Brother 14 is the result of X-ray analysis of pure Al2〇3 (x=zj). Figure 15 is the result of X-ray analysis of (Α1χγι-χ)2〇3(Χ = 〇·9) _ (χ=0·9). Figure 16 is the X-ray analysis result of (Α1χΥι-χ)2〇3 (χ = 0.6) (χ=0·6) 〇20 The 17th figure is (Α1χΥι-χ)2〇3 (χ = 0· 1) X-ray analysis results (χ=0·1) 〇 Figure 18 shows the results of high-purity γ2〇4Χ line analysis (χ=〇). Fig. 19 is a result of a line analysis of a coating formed by hot mouth coating under (aixy1x) 2q3 (x = g. 6) powder is not completely melted (χ = 〇 · 6). 9 200815624 Figure 20 is a low-magnification electron-scan micrograph (Χ200) of an amorphous coating of AU.56Υ0.44Ο3 material formed by thermal spraying. Figure 21 is a low-magnification electron scanning micrograph (Χ650) of an amorphous coating of AU.56Yo.4403 material formed by thermal spraying. 5 Figure 22 is a high-magnification electron-scan micrograph of an amorphous coating of eight 11.56¥〇.4403 material formed by thermal spraying. Figure 23 is a low-magnification electron scanning micrograph of an amorphous coating of Ah.25Υ〇.75 03 material formed by thermal spraying.

Fig. 24 is a low-magnification electron scanning microscope photograph of an amorphous coating of 10 AI1.25Y0.75O3 substance formed by using an electrostatic mixing method. Fig. 25 is a graph showing the results of comparing the hardness of the coating of the coating of the embodiment of the present invention with the coating of the coating of the present invention. Figure 26 is a graph showing the results of comparison of the scratch resistance of the coatings of the examples of the present invention with respect to the coatings of the coatings of the present invention. Figure 27 is a graph showing the results of comparison of the anti-corrosion properties of the 丫203 thermal spray coating with the coating of the present invention on hydrochloric acid. Fig. 28 is a 20-line diagram showing the results of comparing the durability of the thermal spray coating of the present invention with the corrosion environment (plasma) of the coating of the embodiment of the present invention. Fig. 29 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 4 of the present invention. Fig. 30 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 5 of the present invention. 10 200815624 Manufacture of ===:__ The figure 32 is used to display a photo of the microscope of the present invention. Layer of the buns to understand the condition Ϊ, :! Γ to display at 300nm / min speed home h仵下# the invention

10 electron scanning micrographs. Stomach-hours_results [Goods] Detailed Description of Preferred Embodiments The following description of the embodiments of the present invention will be readily described by those skilled in the art. The invention may be embodied in a variety of different embodiments, and is not limited to the embodiments shown herein. Taking the plasma dry_read as shown in Fig. 1 as an example, the problem of the rot of the vacuum plasma chamber and its components will be specifically described. 15 material age type (four) equipment secret _ semi-conductive private film and other substrates or

The particular location of the film on the substrate to form the desired circuitry or structure on the substrate. The components of the device and its working principle are as follows. The gas of the last name enters the interior of the chamber through a hole 14 provided in the gas dispersion disk 13. After the residual gas enters 20, an RF current is applied to the upper electrode 2 and the lower electrode 9, causing plasma enthalpy to increase the reactivity of the etching gas. Thereafter, the enhanced reactive gas is impinged on the substrate 15 placed on the substrate holder 8, thereby etching the substrate or covering a portion of the film layer thereon. The etching gas may be selected from the group consisting of c4F8, C5H8, CH2F2, CF, CF, 11 200815624 CF3, CF4, SF6, NF3, f2 'ch2f2, CHF3, c2F6 and the like containing fluorine element F; C12, BC13, SiC14, HC1, etc. a gas containing a chlorine element 〇1; a gas containing a bromine element Br such as HBr, Bn, or CFsBr; and another mixed gas of one or more of gases such as a group, 〇2, Ar, and Η2. 5 However, the residual gas not only affects the substrate to be engraved, ie, the substrate 15, but also affects other parts. That is, the chamber of the surname device and its internal components are also subject to chemical and physical damage due to the extreme environment inside the chamber during the manufacturing process. The etching process is a process of removing the damaged portion by applying a physical-chemical impact to the entire surface of the substrate or a portion thereof by using a corrosive gas and an accelerating ion or plasma 10, so that the inner wall and the interior of the chamber are removed. Parts also suffer damage during this process. Specifically, the chamber and internal components are subject to chemical attack by highly chemically etched etching gases. At the same time, due to the bombardment of the 15th-speed ionized gas particles under the action of the RF electromagnetic field, the surface is subjected to: physical attack. As described above, if the chamber and internal components are damaged in the above process, it is necessary to replace or clean/repair the damaged partial etching equipment, and additional expenses are required therefrom. Moreover, in order to replace or clean/repair equipment, it is necessary to stop the production line, which will extend the product's construction period. Moreover, the contamination generated by the damaged chamber and the surface of the internal components may contaminate the etched object _ wafer * LCD glass substrate, thus increasing the defect rate of the semiconductor and LCD. Therefore, in order to improve the durability of the chamber and internal components of the vacuum plasma apparatus 12 200815624, various methods have appeared. A detailed description of the typical branches of the hollow space plasma chamber (4) and its (4) components. Generally, the loose-blade material of the vacuum plasma chamber is a metal loose material such as a stainless steel alloy, aluminum (or an alloy thereof) or titanium (or an alloy thereof), and a ceramic material such as Si〇2, Si or αι2ο3. v

The technique of forming a (four) 2 〇 3 shouting coating on the surface of the substrate by an anodizing process is widely used in the section of the D. However, there are many defects in the interior of the ceramic coating formed by this method, so that it is difficult to achieve high hardness and corrosion resistance, and there is also a disadvantage that the generation rate of contaminated particles is relatively high. Further, in the case of various metal materials and ceramic materials which are difficult to be anodized, a protective film is formed by using an external material having a high corrosion resistance and a low generation rate of contaminating particles. Moreover, it is also known to use the coating material alone or in combination for thermal spraying. However, if the shell is coated in this way, the properties of the coating are extremely deteriorated due to internal defects generated. It is close to the method of forming a protective film using a special-shaped ceramic material for the alloy material that can be applied to the anodizing technology. The most representative method of forming a protective film using a shaped ceramic material is thermal spraying. 20 Thermal spraying method is a technique of injecting metal or ceramic powder into a high-temperature plasma flame, thereby heating the powder and then layering it on the surface of the substrate to form a coating in a completely molten or semi-molten state. . Figure 2 is a schematic diagram of the structure of a plasma grab in an important part of the thermal spray equipment. The operation of the plasma gun 20 will be described in detail below. 13 200815624 First, the plasma gas (eight-1, N2, H2, He, etc.) injected through the gas injection port 21 passes through the negative electrode 22 and the positive electrode 24 to which high electric power (usually 30_100 v, 400-1000 A) is applied. During the interstitial process, a portion of the gas is cleaved to form a high temperature plasma-5 body flame 25 of 5000 to 15000 °C. In order to prevent corrosion of the plasma generating portion and the negative electrode terminal, the negative electrode 22 v is usually made of tungsten or tungsten reinforced metal material, and the positive electrode 24 is made of copper or copper alloy and has a cooling passage 23 inside thereof for preventing Due to the high temperature plasma, the positive electrode life is shortened. 10 Through plasma thermal spraying, the same or different materials can be coated on the surface of various materials such as metal and ceramic. The coating material uses powder or linear metal or Tauman. Next, the coating material is made into a powder, and then injected into the enthalpy plasma flame 25 through the powder injection port 27. The powder injection port 27 can be fixed to the plasma blast by a support frame 26 (hereinafter referred to as "external form, (External TYPE)), or can be disposed on the positive electrode 24 (hereinafter referred to as "internal form, (INTERNAL TYPE)" )on. The powder injected through the powder injection port 27 is flown to the 20-coated member 30 at a high speed (200 to 1 〇〇〇 m/s) in a state of being completely fused or partially melted by the high-temperature plasma flame, thereby forming a coating layer 29. When plasma thermal spraying of an oxide ceramic material, it can be operated in the atmosphere. However, materials such as metal materials or carbides and nitrides which cause an oxidation reaction or are easily decomposed under high temperature conditions are subjected to plasma thermal spraying in a vacuum or low pressure chamber. 14 200815624 However, the coating formed by thermal spraying; various types appearing in semiconductor manufacturing 4. ‘ still can’t completely solve

= Figure and Figure 4 are the coated surfaces formed by electron scanning microscopy. System, work U 5 l〇 15 2〇 Manufacturing (4), (4) (4) #, can be used as a semiconductor Θ and a wide range of applications. Figure 3 illustrates the use of the externally-formed u ^ ^ Temple ion gun to protect the 艨's "face, which has multiple irregularities. The coating formed under the conditions is different, but the characteristics are relatively excellent for plasma grazing, the sex (such as hardness), the amount of gas injected, the distance applied, and the sensitivity . Further, since the application of the coating = thermal spraying conditions is variable, there is a disadvantage that the energy efficiency is lowered. In addition, it is necessary to apply an excessively large electric power, and it is strong for you, and it is a high-melting molten ceramic, and at this time (10) a gas such as hydrogen which is advantageous for increasing the plasma temperature, a black dot is formed on the %Y2〇3 coating. Figure 4 is a port utilizing the inner shape. From the inside of the coated system (SPLAT) formed by the ionic body, the interface between the (4)^ droplet and the substrate conflict also produces a crack to the crack, and it is not in the booth, and I , I:: The coating is not only mechanical properties (such as hardness) U crack and its interface gap will become the formation of the reaction god. Moreover, the mechanical impact exerted by the rot-final jin will cause the coating material to be inside the manufacturing process or the cleaning process, and when the material is coated by the thermal spraying method, the internal crack of the slab of It is trapped, and Figure 5 is the gap. Fig. 5 is a view showing the actual engineering of the defect of the sheet (4) which is formed by the above-mentioned film (4) which is immersed in the surface of the substrate and which is formed by the plasma flame, and which is laminated with a scanning electron microscope. When it will cause a lot of problems, secondly, refer to Figure 5 to Xizhi, shouting in the Lilai method.

As shown in Figure 5, 2 = 41 ^ __ because of the melting of the powder, the powder is layered in the material to capture multiple cracks. In the case of thermal spraying, the surface of the dissolved H) surface is detailed and cooled to produce a sheet. The combination of the night I, the pottery of the pottery (such as Y and 〇 in him) is compared Λ ^ and the order of the elements is also kept irregular. Such a = if it cools below the melting point (Τ-), it becomes solid, and the bond between the groups of the elements becomes tight, and the element is arranged in a 15 regular crystal state. As described above, when performing thermal spraying, in the process of cooling and disintegrating the powder on the substrate table and cooling, the molten ceramic powder is transferred to a crystalline state by phase transformation, and the crystalline state causes the wafer to be spread. Form a crack. Figure 6 shows the conditions for crystallization based on time and 20 temperatures when the pottery material is cooled below the melting point. The ceramic has the fastest phase transition velocity near a certain temperature (e.g., Tm in Fig. 6), which rapidly changes to a crystalline state at this temperature. In the process from liquid to solid, if the cooling time is shorter than the time required for crystallization at this temperature (shown as t〇* in Fig. 6), the crystalline state cannot be formed. Therefore, the ceramic material 16 200815624 is converted into an irregular solid amorphous state between the constituent elements as in the liquid state. Fig. 7 shows the change in volume when the liquid substance is cooled to become a crystalline solid. 5 When the temperature drops, the ceramic material shrinks due to the shortening of the distance between adjacent atoms of its constituent elements, and when the crystalline state of the constituent elements is formed, the volume will suddenly become smaller (such as Λν in Fig. 7). ). The volume is so small that it is the cause of the internal cracks and interface gaps in the thermal spray process. Figure 8 shows the formation of such a defect. 10 In order for the liquid molten ceramic to be solidified by cooling, it is necessary to arrange the constituent elements to a predetermined position. Therefore, the more the types of constituent elements, the more complicated the atomic arrangement of the crystalline state, and the various types of elements need to be moved to their respective positions, so the arrangement takes a long time. Therefore, as shown in Fig. 9, if the type of constituent elements is increased, AmorM (representing amorphous materials) is composed of (ΑΐχΥι_χ) 2〇3 (X). The general term for the amorphous coating material in the range of 0·05_〇95), hereinafter referred to as "AmorM" as the amorphous material, takes a longer time to form a crystalline state at the same temperature. Therefore, AmorM is more likely to be formed into an amorphous state. The coating material of the embodiment of the present invention includes a multi-component ceramic, and as shown in Fig. 9, it takes a long time to form crystal sorrow. That is, it is easy to form an amorphous state during thermal spraying. Moreover, the coating of the embodiment of the present invention utilizes the multi-component ceramic of the embodiment of the present invention to make most of the coating amorphous. At this time, the coating layer at least 17 200815624 - 5 preferably comprises more than 50% of the amorphous state, and preferably forms an amorphous state of 1%. The amorphous state in the coating is less than 50%, which is equivalent to containing more than 50% of the crystalline state. Therefore, as described above, in the process of converting from a liquid state to a crystalline solid, the volume thereof is greatly changed, and defects are generated in the coating. Fig. 10 shows the change in volume when changing from a liquid phase to an amorphous state. As shown in Fig. 10, when it changes from a liquid state to an amorphous state, its volume does not change drastically. The reason for this is that the atomic arrangement of the amorphous solid is almost the same as the arrangement of atoms in the liquid state. Therefore, by forming the coating layer using the multi-component ceramic coating material of the present invention, an amorphous structure solid is formed, so that the volume does not drastically shrink at a specific temperature of 10. Therefore, internal defects such as longitudinal cracks and interface gaps in the sheet due to volume shrinkage when the liquid phase changes to a crystalline solid are not generated. The 11th Hall represents the process of changing from a liquid phase to an amorphous solid state. _ 15 • Next, the coating material forming the coating layer of the embodiment of the present invention will be described in detail. In order to easily form an amorphous coating layer, the coating material of the present embodiment includes a multi-component ceramic material, and this multi-component ceramic material contains three or more elements. 20 The multi-component ceramic material may use a multi-component ceramic material comprising Al, Υ, and 〇, which are constituent elements of Al2〇3 and Y2〇3. The compositional element ratio of the multi-component ceramic material preferably satisfies the chemical formula (A1xY "x) 2 〇 3 (x is 〇·〇5-〇·95). If the X value is less than 0.05 or greater than 〇·95 ' In the process of forming a coating layer using the prepared powder, a 100% amorphous coating layer cannot be formed, thereby causing deterioration of physical and chemical properties such as deterioration in corrosion resistance, wherein the content of oxygen element can be based on thermal spray. 18 200815624 Change in temperature, spray distance, etc. of the flame during coating. Next, a method of preparing the multi-component ceramic material of the embodiment of the present invention is explained. The multi-component ceramic material of the present invention can be permeable to the following ceramics - 5 The method is made into a powder. One method of the ceramic synthesis method is to remove the unnecessary elements by heat treatment after mixing the chemicals containing A1 and Y, thereby finally preparing a powder composed of the elements A, Y, and yttrium. Among them, the chemical substance containing A1 is _Al(OH)3, ai(c3h5o3)3, A1(C18H3302)3, A1(C15H31C00)3, 10A12(S〇4)3, etc., and the chemical substance containing Y is Y2. (C03) 33H20, y2 (s〇4) 3 8H20, etc. The method for preparing the ceramic powder is described in detail in one step. The first method: firstly, the chemical substance containing A1 and Y is mixed to form (AlxYkhC^x is 0.05-0.95). Secondly, it is heated at a high temperature. The unstable substance other than Α1-Υ-0 is decomposed and removed by -15 to remove impurities such as c, -Η, 0, etc. W The second method: after dissolving the chemical substance in a solvent such as water or ethanol Heating to prepare a Α1-Υ-0 powder having a composition of (AlxYkMMx of 0.05-0.95). 2〇 The third method: first preparing a mixed powder of ruthenium metal and ruthenium metal having a particle diameter of Μ00 μηι, or Α1 and Υ After the alloy powder, the mixed powder is subjected to an oxidation treatment to synthesize the powder. Among them, when the ruthenium metal is in contact with oxygen at a normal temperature, the surface thereof is also oxidized to form ΑΙ2Ο3, which is for the purpose of facilitating oxidation reaction. It can increase the temperature and accelerate the oxidation reaction rate of 19 200815624 degrees. Moreover, it is also possible to make A1 metal powder to increase the reaction area. Not only A1 metal powder, Y metal powder and Ai and γ alloy powder can also pass through A1 The high-temperature oxidation method of the metal powder is oxidized in the same manner to prepare (A1203)x(Y2〇3)1-x ceramic. 5 Fourth method: After mixing the A1 metal and Y metal powder, the mixed powder is oxidized The treatment is carried out to prepare a bulk-like ceramic, which is then pulverized to obtain a powder having a particle diameter of 100 μm or less. This synthesis method is the same as the above-described high-temperature oxidation method, and is a method of oxidizing a metal element at a high temperature to form an oxide. The high-temperature oxidation method described above oxidizes the powder, and the one-step method oxidizes agglomerates having a particle diameter of several millimeters (mm) or several centimeters (cm). The problem of increased cost, but regardless of the size or shape of the metal alloy, if oxidation is performed in the bulk state, the ceramic material can be produced at a low price. The fifth method comprises mixing 粒径1_3〇 particles and ίο; particles to prepare a substance having a composition of (Α1χΥΐχ)2〇3 (4〇•(4)·95), and spray-drying to prepare Α1. A dry synthetic powder of γ, 〇 element and particle size Η00. The fifth method towel is prepared by preparing Αΐ2〇3, γ2()3 powder into a component f of ^^203 (χ 〇.〇5_G 95), and then combining with a solvent, a binder, a granule, etc. . Job, use 7 please. c is a gas jet such as air, or a fine groove is formed in a disk that rotates at a high speed, and is sprinkled through the groove to produce a powder having a particle diameter of 1 to 200 μm. The powder produced by this method is also required to be heated at a temperature of 900-1500 ° C due to its weak strength. After this heating process, the solvent, the binder, the dispersant and the like are vaporized, and finally the powder is simply taken up by j, and since the remaining ceramic powder is sintered, the powder strength is improved. The sixth method: preparing a multi-component mixed powder by the following steps: inducing a 5-lead and making a particle size of 0.1-3 〇μ_Α12〇#Υ2〇3 particles carrying different charges of different polarities; mixing particles with different static electricity to make The composition is a substance (the range of AlxY^C^x is 0.05_〇·95). When the Al2〇3 powder and the γ2〇3 powder were merely mechanically mixed, the Al2〇3 powder and the γ2〇 powder were not uniformly mixed. However, in the sixth method, as shown in Fig. 12, the two 1 〇 particles form a block due to static electricity in a solvent having a specific pH (for example, pH 6), so Α1ζ〇3 and ΙΟ3 can be mixed very much. Evenly. Therefore, a powder of excellent quality can be prepared. Wherein, the method of charging the powder is as follows: in order to make Αΐ2〇3 negatively charged, polymethylammonium salt (p〇ly_methyl 15 metacrylic ammonium salt) is added to the solvent, and in order to make Y203 positively charged Adding polypyridinium (P〇ly_ethylen imide) to the agent. The subsequent step of the production method is the same as the spray drying method, and only the preparation process for the powder for spray drying is changed. Therefore, the detailed description of the subsequent steps is omitted in the present invention. 20 The ceramic powder synthesized by the above various manufacturing methods is subjected to calcination treatment at a temperature of 9 Torr (M50 〇t) to prepare a thermal spray powder having an appropriate strength. Further, in the ceramic powder synthesis method of the embodiment of the present invention When the Al 2 〇 3 powder and the Υ 2 〇 3 powder are mixed, a solvent and a dispersing agent may be used in order to make the powder relatively easy to mix and uniformly disperse the particles mixed in 21 200815624. Moreover, in the post-treatment process such as a simmering process In order to maintain its shape, a surface agent can be used. The solvent used in the ceramic synthesis process is a mixture of one or more selected from the group consisting of water, acetone or isopropoxide (Isopmphylalchole), and the dispersant uses 5 咼 molecular polymer (high For the binder, a polymer compound (PVB76) or benzyi butyl phthalate or the like can be used. Fig. 13 shows the result of observing the appearance of the mixed powder by an electron scanning microscope, the mixing The powder is a multi-component mixed powder containing Al, Y, and 0 elements produced by the powder preparation method 10 of the embodiment of the present invention. The method for forming a coating by using the ceramic powder prepared by the powder preparation method of the embodiment of the invention. The coating method of the embodiment of the invention comprises a thermal spraying method. The thermal spraying method comprises the steps of: injecting ceramic powder into a plasma flame for heating. A powder of 15 completely molten or semi-molten state is laminated on the surface of a plasma chamber member (hereinafter referred to as "substrate") to form a coating. First, a powder for coating is prepared. For thermal spraying The ceramic powder is a powder of the embodiment of the present invention, and a single powder having a particle diameter of 1-100 μm can be used. Further, it is also possible to use a primary fine 20 powder of several tens of nanometers and several micrometers (μιη) to be condensed into 1] 〇〇μηι. Next, the single powder or agglomerated powder is injected into the plasma flame. The injected powder is heated by the flame to be scattered and laminated on the surface of the substrate. Then, the laminated powder is rapidly cooled to form Coating. In order to carry out the coating work stably, and to improve the properties of the coating material, different working conditions can be set. Depending on the size and type of the equipment to be used and the coating powder to be used, the present invention will be described in detail below by way of an experimental example. In the fifth experimental example of the present invention, "ρτ_8" produced by the company Plazmatek of Switzerland was used. 〇” Power application system and “F4_HBS, type plasma grab” produced by Sulzer-Metco, USA. “The use of nitrogen and gas for the formation of plasma is controlled at 36L/min, rit/min. The applied power was set to 36 Kw (600 A, 60 V), and the injection speed of the coating powder was set to 1 〇g/min. 10 The distance between the plasma gun and the member to be coated was set to about 12 〇mm or so. In the experimental example of the present invention, the "PT-800" power application system produced by the Swiss piazmatek company and the "SG-100" type plasma gun manufactured by the US pmxair company were also used, and the argon gas usage amount was set to 4 〇L/ Minutes, -15 set the helium usage to 20 L/min, the applied power to 25 Kw, and the -spray distance to 120 mm. B First, the difference between the coating powder using the embodiment of the present invention and the use of a pure metal oxide (finger 1 & gamma oxide) will be described with reference to Figs. 13 to 17 . 20 In order to observe the degree of amorphous state formed in the coating under different powder conditions, the powder was prepared by adjusting the X value in (Α1χγι·χ)2〇3, and the generated powder was passed through the thermal spraying method. A coating is formed on the substrate for the chamber. Fig. 14 is a view showing X-ray diffraction values of a coating layer formed by coating a pure erbium 2 〇 3 powder by plasma thermal spraying. In order to compare with the ceramic powder 23 200815624 of the embodiment of the present invention, the pure ... 3 powder was applied by thermal spraying, and the enthalpy diffraction state was examined. As shown in Fig. 14, when a pure A "3 powder was used, a high intensity peak was observed at a specific diffraction angle (shown as ▽ in Fig. 14). This peak of 5 high intensities can occur in the presence of a repeating structure, whereby it can be seen that when a pure tantalum powder is used, there will be a crystalline state inside the coating. Fig. 15 is a view showing the result of the crepe analysis of the coating layer formed by thermal spraying using a coating powder having a composition of (Α1χΥ ι _χ) 2〇3, wherein 1 is 〇 9. As shown in Fig. 15, unlike the comparative object Fig. 13, at a certain diffraction angle, J1 does not have a peak i of the south intensity. Thus, it can be seen that the (Αΐ〇9γ〇ι) 2〇3 powder is suitable for forming the amorphous coating of the embodiment of the present invention. Next, the X value was adjusted to 〇·6, and the composition was (a1^YG4)2〇3, and after blistering, plasma spraying was performed to form a coating, and the coating was subjected to X-ray analysis. Figure 16 X-ray analysis of a coating composition of (Α1〇δΥ〇4)2〇3 It can be seen that when X is 0.6, the coating is still amorphous. Then, the X value was adjusted to (U, and a coating powder having a composition of (AkiY (> 9) 2 〇 3 was prepared, and then thermal spraying was performed. The composition of the figure 为 is (AU^ 9) 2. 3 The parallel analysis of the coating is carried out. As shown in Fig. 17, the peak of the micro-^ appears between the angle of the X-axis (2θ) 3〇 and 4〇. It can be seen that (A1( uY()9) The coating formed by the powder of 2〇3 powder is large and becomes amorphous, but a part thereof is formed into a crystalline state. "In addition, Fig. 18 shows that pure PET is applied by plasma thermal spraying. The X-ray diffraction value of the coating formed by the 3 r beam. For comparison with the ceramic 24 200815624 £ powder of the embodiment of the present invention, the pure y2〇3 powder was coated by the isotherm thermal spraying method, and the X-ray analysis apparatus was used. The diffraction state was measured. It can be seen from Fig. 18 that a strong peak appears at a specific angle. Thus, as described above, when it is coated by pure coating, part A is formed into a 5 crystal state. The comparison between the formed coating and the X-ray diffraction of the coating formed of pure tantalum shows that not only the position of the peak of the crystalline state is not Similarly, when the coating is formed from pure ruthenium 1203, the intensity of the diffraction peak as a whole is low. On the contrary, when the coating is formed from pure ruthenium 2〇3, it can be detected at a ratio of 3 〇. 〇4 〇. This indicates that the coating formed by pure ruthenium 1203 does not form a complete crystalline state, but forms a part of the amorphous state structure mixed with it. It can be seen that Α12〇3 is compared with Υ2〇3. It is easier to form an amorphous state. That is, in order to more easily form an amorphous state, it is preferable to set the range of 兀 to MW, and in this case, the Α1 component is more than γ. From the above experimental example, (Α1χΥι χ) 2 In 〇3, when the χ value is within the variable range of 〇Μ.9, a high-quality amorphous coating can be formed. Next, referring to Fig. 19, in the thermal spraying process, depending on the coating conditions, it is possible Defects that may occur. Figure 2 is a graph showing the results of X-ray analysis of a coating formed by plasma thermal spraying using the powder of the embodiment of the present invention. Here, (4) is (A10.6YG.4) 2Q3 a composition of powders, the set is simple with the secrets of the invention, but at low plasma temperatures Under the conditions, or in the state where the powder is not completely melted, it is thermally sprayed. 25 200815624 As shown in Fig. 19, as a whole, a peak is formed at a partial angle. Therefore, it can be seen that the mixture is mixed in the amorphous structure. Some crystalline states. This is because the thermal state of the plasma is directly transmitted to the coating due to low plasma temperature or incomplete melting of the powder. 5 In addition, during the coating process, when the substrate or When the temperature of the coated surface is so high that the amorphous state undergoes a phase transition and is transferred to a crystalline state, a part of the amorphous state undergoes a phase transition and is transferred to a crystalline state, thereby forming a structure in which the amorphous state and the crystalline state are mixed. Most of the coating layer formed under the above conditions is amorphous, and in 10 is a part of the crystalline state, and the interstitial space of the pores and the tabs is not formed inside the coating. It can be seen that even if the conditions for forming the coating are insufficient, the coating formed under the above conditions has more excellent characteristics than the coating using pure Al or pure γ oxide. Next, the coating of the first experimental example 15 of the present invention will be described with reference to Figs. 20 to 22. In the first experimental example, after preparing a multi-component powder having a composition of (A1〇78Yq 2士〇3, an internal coating was used to form an amorphous coating. Hereinafter, the first experimental example of the present invention will be employed. The amorphous coating is called AmorMl. Fig. 20 and Fig. 21 are the results of observation by electron scanning microscopy after the cross section of the AmorMl coating is mirrored. Although it is found in Fig. 20 and Fig. 21 A little cracking phenomenon, but the longitudinal cracks and gaps between the sheets in the common thermal sprayed crystalline coatings were not observed. Figure 22 is a high-magnification projection electron microscope to observe AmorMl amorphous 26 200815624 Results of the sad coating. It can be confirmed from Fig. 22 that the AmorM1 coating has an amorphous structure. Next, the coating of the second experimental example of the present invention will be described through Fig. 23. In the second experimental example, the constituents were prepared. It is (8: 1) 625 ¥ () 375) 2 〇 3 - 5 multi-component powder, and an amorphous coating layer is formed using an internal plasma gun. Hereinafter, the second experimental example of the present invention The crystalline coating is called AmorM2. - Figure 23 is A photograph of the electron scanning micrograph taken after mirroring the cross section of the AmorM2 coating. As shown in Fig. 23, AmorM20 has a shape similar to the A reading M1 coating of Fig. 22. #, does not produce 10 pieces of internal longitudinal cracks and gaps between the sheets are spread. Further, the coating of the third experimental example of the present invention is the same as the composition of Am〇rM2, but is used to uniformly disperse Al2〇3 powder and Y203 powder. , a method of absorbing $ and carrying a negative charge and a positive charge, respectively. The 24th chart does not use an electron scanning microscope to observe the result of the coating of the third experimental example. It can be seen from the figure that due to electrostatic mixing Method, • The powder is kept in a uniform composition in all parts, so there is no shape interface, which forms a high-quality coating. Moreover, as shown in Fig. 24, partially crystalline particles are dispersed in the coated part. Surface (lower part of the photo). This is due to the low temperature of the plasma flame 20, the incompletely condensed crystalline state in the powder, or due to the temperature of the surface of the coated part and the substrate. The result of the phase transition of the amorphous material to the crystalline state. The following is a description of the mechanical and chemical properties of the AmorMmmor M2 coating, as shown in Figures 25 to 28. The figures to the figure show Ba Li (10) and 27 200815624

Comparison of mechanical and chemical properties of AmorM2 coatings with coatings made using conventional γ2〇3, a12〇3 powders. Fig. 25 is a view showing the measurement results of the mechanical strength of the coating layer formed by the embodiment of the present invention and the coating layer formed by using the yttrium oxide and the cerium oxide. Hereinafter, a coating layer made of a sulfoxide compound is referred to as Comparative Example 1, and a coating layer made of cerium oxide is referred to as Comparative Example 2. As shown in the figure of Fig. 25, the AmorMI and AmorM2 amorphous coatings were improved in hardness value by 75 % by % to 1% by comparison with Comparative Example 2, and had hardness values similar to those of Comparative Example 1 excellent in mechanical strength. Fig. 26 is a graph showing the results of the scratch resistance measurement of the coating of the examples of the present invention and the coating of the comparative example. As shown in Fig. 26, the AmorMl and AmorM2 amorphous coatings had a scratch resistance of up to 1 〇 or more as compared with Comparative Example 2. When the scratch resistance was measured, the depth of the scratch was measured after applying a 30 N force to the surface of the coated surface by a sharp diamond tip. Fig. 27 is a graph showing the results of measurement of corrosion resistance of the coating layers of the examples of the present invention and the coatings of Comparative Examples. As shown in Figure 27, AmorMl and AmorM2 amorphous coatings also have good corrosion resistance to acidic chemicals such as HC1. The Y-axis of the graph indicates the reduction in quality after 2 〇. The coating of the examples of the present invention was reduced in quality by 1/5 compared with Comparative Example 2. Therefore, it can be seen that the corrosion reaction rate is about 1/5 of Comparative Example 2. The corrosion resistance was measured by immersing the coated member in an HCl solution having a concentration of 2 N for 24 hours under normal temperature conditions, and measuring the amount of quality reduction after taking out. 28 200815624 Figure 28 shows the results of the long-term measurement of the plasma vacuum chamber of the embodiment of the present invention. Referring to Fig. 28, the durability of the coating layer of the embodiment of the present invention to the plasma environment was 5 times or more superior to that of Comparative Example 1. For the evaluation of durability, 5 is a method of measuring the depth of a surname after etching a coated member by using one of semiconductor manufacturing equipment, that is, a plasma engraving apparatus, and using CF4 + 〇2 gas. The durability measurement conditions are specifically described below. Based on the condition that Si〇2 is etched by 100 nm per minute, the (injection speed of 10) is 3〇sccni (standard cubic centimeters per minute), the gas injection rate of 02 is set to 6sccm, and the input power to the main electrode. Set to 900 W, the bias power was set to 90 W, the squeezing chamber pressure was set to 5 mtorr, and the chamber interior temperature was maintained at 25 ° C. The coatings of Comparative Example 1 and Comparative Example 2 and the present invention were compared in Table 1. The characteristics of the coating of 15 examples were carried out. The data in Table 1 are the results of the measurement under the above-described durability measurement conditions. Table 1 Sample Characteristics Comparative Example 1 (Α12〇3) Comparative Example 2 (Υ2〇3) Example ( AmorM) Hardness (Hv.200g) 800-850 300(1)-500(6) 700-750 Scratch Depth, μηι 1 10(E)-22(I) 1.2 Corrosion resistance#(g/g) — 0.55 0.09-0.11 ICP plasma corrosion resistance d (nm / min) 9.5 1.7-1.8 1.6-1.9 defects (wrap interface gap, pores) There are good as shown in Table 1, the hardness of the coating of the examples of the present invention Comparative Example 1 Phase 29 200815624, the corrosion resistance is similar to or superior to that of Comparative Example 2, and thus the coating of the present invention Not only does it have the advantages of a general coating, but it does not easily cause other defects. Therefore, the coating of the embodiment of the present invention has excellent physical and chemical characteristics as compared with the comparative example. Further, in order to explain the present invention in more detail Excellent characteristics, durability test of plasma vacuum chamber under corrosive conditions. Table 2 • Coating variable example 4 D (mm) —— Ar (Psi) --- 30 He (psi) 115 powder Supply speed (RPM) 3 Carrier gas supply speed _ (psi) 20 Current (eight) 电压 Voltage (V) 39.5 ^Ion body grab > tracing speed (mm/sec) Experiment yuu Example 5 150 40 65 3 20 37.3 1000 40 85 3.5 50 40.8 The composition of the components used in this experiment was the same as that of AmorM2, and /, the powder was prepared to have a particle size of 1 〇 6 〇 μηι. Moreover, according to the comparative example and the experimental example of Table 2 10 Conditions were used to produce a coating. ^ Figure 29 shows the results of X-ray analysis of the coating of Experimental Example 3 of the present invention. From Fig. 29, a plurality of peaks can be observed, the coating as a whole is amorphous, but also partially crystalline. Figure 30 and Figure 31 Denote results by X-ray analysis of a coating made according to the present invention in Experimental Example 4 and Experimental Example 5 for 15. It can be observed from Fig. 30 and Fig. 31 that Experimental Example 4 and Experimental Example 5 differ from Experimental Example 3 in that almost 100% of an amorphous state is formed under the conditions. Prior to testing for corrosion resistance, the coatings of the respective experimental examples were first tested for hardness. The hardness of the coating was measured by a Vickers hardness tester with a load of 200 g. The test results are shown in Table 3. 30 200815624 Table 3 Conditions_Experimental Example 4 Experimental Example 5 Experimental Example 6 Hardness Value (Hv) 645 593 750 The results of Table 3 show that the hardness of Experimental Example 4 which produces partial crystal sorrow is similar to that of Experimental Example 5 and Experimental Example 6, When the layer is formed into an amorphous state as a whole, that is, it contains a partially crystalline state, and does not have a too large influence on the hardness. „ 5 In addition, when the coating consists of 100% amorphous state, that is, when the inside of the coating is not formed with pores, the hardness value increases. Therefore, as shown in Experimental Example 5 and • Experimental Example 6, 100% The hardness of the amorphous coating is also changed according to the coating conditions. Secondly, as described above, the corrosion resistance of each of the 10 coatings was measured under conditions prone to rot #. Si〇2 was carried out under the conditions of being etched at a rate of 300 nm/min. Specifically, the injection rate of CF4 gas was set to 40 sccm, the injection speed of 〇2 was set to 10 sccm, and the input power of the main electrode was set to 1000 W. The set power was set to 150 W, the pressure in the chamber was set to _ 15 5 mton·, and the temperature inside the chamber was maintained at 25 ° C. Moreover, the time to be exposed to the plasma environment was set to 1 hour. Comparative Example 2 Experimental Example 4 Experimental Example 5 Experimental Example 6 Average etching rate (nm/min) 77.2 20.22 15.83 10.5 3.58 Figures 32 and 33 show the results of observing the surface of the coating before and after the etching by an electron scanning microscope. 32 figure representation The surface of the coating before engraving, the surface of the coating after etching is shown in Fig. 3. The observation results are shown in Table 4. 20 Table 4 ____ 31 200815624 The etching rate of the experimental example of the present invention is shown from the average etch rate of Table 4. It is much slower than the comparative example. It can be seen that the coating of the embodiment of the present invention also has strong durability under strong oxidizing conditions. Experimental Example 4 is an experimental example of forming a partially crystalline state, which is associated with 100% non- The experimental example of the crystalline state shows a faster etching (corrosion) speed compared to the experimental example 5 of 6. It can be seen that the corrosion can be most effectively prevented only when the coating constitutes 100% amorphous. Moreover, comparing the results of Table 1 and Table 4, it can be concluded that in a weaker rot environment (the rotatory button speed is 1 〇〇nm/min based on Si 〇 2), the embodiment of the present invention When the coating was compared with Comparative Example 2, the corrosion rate was not different, but in a strong corrosive environment (corrosion rate of 300 nm/min based on Si〇2), the coating of the embodiment of the present invention The layer exhibited a much slower rate of corrosion than Comparative Example 2. It can be seen that the embodiment of the present invention The layer still has a very excellent resistance to corrosion in a highly corrosive environment. In addition, the invention may further comprise the step of forming a metallic intermediate layer, 15 which is intended to increase the bond strength of the thermal spray. The invention may further comprise a step of forming a plurality of coating layers by successively changing the composition of the substrate and the member to be coated (formation method of gradient coating). A metal intermediate layer is formed on the substrate to be different in physical and chemical properties of the coating from the substrate. In the case of a material, the problem that the coating layer is easily peeled off due to the fragility of the interface can also be solved. Between the coating layer and the coated member of the embodiment of the present invention, the intermediate layer can be formed by the following method, and the non-inventive of the present invention is applied. Crystalline material.丨) When Zr〇2 is coated on an aluminum substrate, an intermediate layer may be formed using a material such as NiCrAiγ having a small thermal expansion coefficient. 2) On the aluminum metal, the FeCr-based amorphous metal with high strength and excellent corrosion resistance can be used to form the intermediate layer. On the metal substrate, an intermediate layer may be formed using Cr, Ni, Fe, or an alloy including the metal. 4) On the substrate of Al2〇3, Si, Si〇2 or the like, the amorphous material of the present invention may be applied after the intermediate layer is formed using the same substance. 5 Thus, by the method of forming the metal intermediate layer of the present invention, peeling of the coating layer can be prevented, and corrosion resistance can be further improved. In addition, the coating and the component of the embodiment of the present invention may not have an intermittent second coating layer (intermediate layer), but a gradient coating layer, specifically, after preparing a powder of the same or similar substance as the substrate. The content of the amorphous coating material of the present invention is gradually increased by 10 during the coating process. This method can improve the durability of the coating. Moreover, preferred embodiments of the invention may be employed in conjunction with other coating forming techniques, or in the use of the amorphous coating of the present invention on a portion of the thermally sprayed coating. The present invention is not limited thereto, and various modifications and changes made within the scope of the invention, the scope of the invention, and the scope of the invention are all within the scope of the invention. L. Fig. Cui Cuiming; 3 20 Fig. 1 is a longitudinal sectional view of a plasma etching apparatus which is one of semiconductor manufacturing equipment. Figure 2 is a plasma grabbing profile of a plasma thermal spraying device. Not intended. Figure 3 is a plasma gun formed by an external form. 33 200815624 YA (People) Transfer (4) Photographs of poems. Painted _ (10) into the peach 曰 曰 的 surface of the electron scanning micrograph. The picture of the 5th is used to show the detachment of the sputum. Brother 6 is a liquid material 纟 time crystallization phenomenon ^t 条件 见 的 的 condition pattern diagram.

The 10th figure is a pattern diagram showing the volume change process produced when the liquid substance is solidified by cooling. Figure 8 is a schematic diagram showing the principle of formation of defects generated when a liquid substance becomes a crystalline solid. Fig. 9 is a schematic view for explaining the conditions for forming a crystalline solid phase upon cooling depending on the type of material. The figure H) is a schematic diagram for explaining the volume contraction process which occurs when the liquid substance is cooled to form the amorphous state 15.

The figure 11 is a process pattern for explaining the occurrence of defects such as cracks when the liquid substance is in an amorphous state. Figure 12 is a schematic diagram for explaining the process of mixing different types of powders to prepare a composite powder for thermal spraying having a larger powder size. 20 is a photomicrograph of an electron scanning micrograph of a ceramic powder for thermal spraying synthesized in accordance with the present invention. Figure 14 is the X-ray analysis result of pure Al2〇3 (x=1). Figure 15 shows the results of X-ray analysis (χ=0·9) of (AIxYkhOXx = 〇·9). 34 200815624 Figure 16 is the X-ray analysis result of (ΑΙχΥ, -ΑίΜχ = 0.6) (χ=0·6) 〇 Figure 17 is the X-ray analysis result of (AIxYhMMx = 0.1) (χ=0·1) 〇5 Figure 18 is the X-ray analysis result of high purity Υ203 (χ=0). Fig. 19 is a X-ray analysis result (x = 0.6) of a coating layer formed by thermal spraying in a state where (AlxY^hG^xiA) powder is not completely melted. Figure 20 is a low-magnification electron scanning micrograph (X200) of an amorphous coating of A1!.56YG.4403 material formed by thermal spraying. 10 Figure 2 is a low-magnification electron-scan micrograph (X650) of an amorphous coating of All.56Y〇.44〇3 material formed by thermal spraying. Figure 22 is a high-magnification electron scanning micrograph of an amorphous coating of Ah.56Yo.4403 material formed by thermal spraying. Figure 23 is a low-magnification electron scanning micrograph of a non-15 crystalline coating of Ah.25Y0.75O3 material formed by thermal spraying. Fig. 24 is a low-magnification electron scanning microscope photograph of an amorphous coating of an AI1.25Y0.75O3 substance formed by using an electrostatic mixing method. Fig. 25 is a graph showing the results of comparing the hardness of the thermal spray coating of Al2〇3, Y203 with the coating of the embodiment of the present invention. Fig. 26 is a graph showing the results of comparison of the scratch resistance of the thermal spray coatings of the examples of the present invention for exhibiting the coatings of the examples of the present invention. Figure 27 is a graph showing the results of comparison of the corrosion resistance of the Υ203 thermal spray coating with the coating of the embodiment of the present invention on hydrochloric acid. 35 200815624 Figure 28 is a graph showing the results of comparing the durability of the AI2O3, Y2O3 thermal spray coating with the corrosion environment (plasma) of the coating of the embodiment of the present invention. Fig. 29 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 4 of the present invention. Fig. 30 is a graph showing the results of X-ray analysis of the coating produced by the conditions of Experimental Example 5 according to the present invention. Fig. 31 is a graph showing the results of X-ray analysis of the coating layer produced by the conditions of Experimental Example 6 according to the present invention. 10 Fig. 32 is an electron scanning micrograph showing a coating of an embodiment of the present invention. Fig. 33 is an electron scanning micrograph showing the results of etching for one hour of the coating of the embodiment of the present invention under the condition that SiO 2 was etched at a rate of 300 nm / min. 15 [Description of main component symbols] 2···Upper electrode 22...Negative electrode 8···Substrate holder 23...Cooling channel 9···Lower electrode 24···Positive electrode 13...Gas dispersion disk 25...Particle body flame 14... Hole 26...bracket 15...substrate 27...powder injection port 20...plasma gun 29...coating 21...gas injection port 30...coated member 36

Claims (1)

200815624 X. Patent application scope: 1. A thermal spray material for semiconductor manufacturing equipment, wherein the teaching material is an amorphous structure having a composition of (Α1χΥι_χ) 2〇3, 1 medium, It is 0.05-0.95. </ br> Χ 2 · The thermal spray material as described in the scope of the patent application, wherein X ranges from 0.5 to 0.95. 3. The thermal spray material of claim 1, wherein the thermal coating material comprises a powder having a particle size of 1-100 4 melon. 4. A method of injuring a thermal spray material for use in a semiconductor manufacturing apparatus, wherein the method comprises the steps of: mixing a particle size of 〇·1-30 μπ^ΜΟ3 particles and an Ah godson, and preparing the product (eight 乂1乂) _ 〇 〇 3 composed of substances, wherein | χ槐 is 0.05-0.95; spray drying the substance to prepare a synthetic powder; at 800-1500. (: temperature simmering the powder. 5 · as claimed The method for producing a thermal spray material according to Item 4, wherein the step of -mixing the substance further comprises an electrostatic application step of inducing and carrying the erbium 2 〇 3 particles and the AO 3 particles with different polarities 6. The method of preparing a thermal spray material according to claim 5, wherein the electrostatic application step comprises: adding a poly-methyl metacrylic ammonium salt to the solvent. a salt that causes the Α12〇3 37 200815624 particle to be negatively charged; and a poly-birth imine (pQiy_e_n imide) added to the solvent to cause the Y2〇3 particle to be positively charged. guide Manufacturing apparatus (4) a coating method of the glare material, comprising the following steps: preparing a substance having a composition of (1:1 士士〇3, wherein X is 0.05-0.95; injecting the thermal spray material into a plasma flame and performing twisting; The thermal spray material in a fully molten or semi-molten state through the heating process is laminated on the surface of the component for the semiconductor manufacturing apparatus to form a coating of an amorphous structure. The method for coating a thermal spray material according to Item 7, wherein: the step of forming a coating further comprises the step of forming a metal intermediate layer. 9. The thermal spray material according to claim 7 a coating method, wherein: the step of forming a coating further comprises the step of gradually changing the composition of the thermal spray material to form a gradient coating. 10. The thermal spray material according to claim 9 a coating method, wherein: during the coating process, the composition of the thermal spray material is gradually changed from the same or similar composition to the substrate to be coated ( 1 χΥ χ χ 〇 , , , , 2008 2008 2008 2008 2008 2008 2008 2008 2008 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热The component is a chamber of a vacuum plasma device or a component inside the chamber. 39