TWI779071B - Material for thermal spray, thermal spray coating using the same and manufacture methods thereof - Google Patents

Abstract

The present invention relates to aluminum yttrium oxyfluoride thermal spraying materials, and more specifically, relates to aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet with the proportion of yttrium fluoride (YF ₃ ) being 30 to 70% by mass and the balance (YAG) thermal spray material and thermal spray film with excellent plasma resistance produced by mixing, granulating, and firing.

Description

Thermal spraying material, thermal spraying coating thereof, and manufacturing method thereof

The present invention relates to a method for producing a thermal spray material and a thermal spray film.

In the semiconductor manufacturing process, the importance of the plasma dry etching process is becoming more and more important for the microfabrication required for the high integration of substrate circuits such as silicon wafers.

In order to use it in such an environment, it has been proposed to use a material with excellent plasma resistance as a chamber member or to coat the surface of the member with a substance with excellent plasma resistance to increase the life of the member.

Among them, techniques for imparting new functionality by coating the surface of a substrate with various materials have been conventionally used in various fields. As one of such surface coating techniques, for example, there is known a thermal spraying method in which thermal spray particles made of materials such as ceramics are sprayed on the surface of a substrate in a softened or molten state by means of combustion or electric energy to form a thermal spray coating.

In general, thermal spray coating is performed by heating and melting fine powder, and spraying the molten powder toward the surface to be coated of the base material. The sprayed molten powder is rapidly cooled, the molten powder solidifies, and is laminated on the surface to be coated mainly by mechanical bonding force.

In the thermal spray coating, the plasma thermal spray coating that melts the powder using a high-temperature plasma flame must be used in the coating of high-melting-point metals such as tungsten or molybdenum and ceramics. The thermal spraying coating not only maintains the material properties of the base material, but is also conducive to the production of wear resistance, corrosion resistance, heat resistance and heat barrier, superhard, oxidation resistance, insulation, friction characteristics, heat dissipation, and radiation resistance of biological functions. In addition, it can coat a wide area of objects in a short time compared with other coating methods such as chemical vapor deposition or physical vapor deposition.

In addition, in the field of manufacturing semiconductor devices and the like, microfabrication is generally carried out on the surface of a semiconductor substrate by dry etching of plasma using a halogen-based gas such as fluorine, chlorine, or bromine. In addition, after dry etching, the inside of the chamber (vacuum container) where the semiconductor substrate is taken out is cleaned with oxygen plasma. At this time, in the chamber, members exposed to highly reactive oxygen plasma or halogen gas plasma may be corroded. Furthermore, if the corroded (eroded) portion falls off in the form of particles from the corresponding member, the particles adhere to the semiconductor substrate and become foreign substances that cause circuit defects (hereinafter, the corresponding foreign substances are referred to as particles).

Therefore, conventionally, in semiconductor device manufacturing equipment, for the purpose of reducing particle generation, a ceramic thermal spray coating having plasma corrosion resistance is provided on members exposed to plasma such as oxygen or halogen gas. .

Factors for such particle generation include detachment of reaction products adhered in the vacuum chamber, and chamber degradation due to the use of halogen gas plasma or oxygen plasma. In addition, according to studies by the present inventors, it has been confirmed that the number and size of particles generated from a thermal sprayed coating are greatly influenced by the composition of the thermal sprayed coating in a dry etching environment.

Specifically, the components of the etching device that are in contact with the halogen-based gas plasma are based on metal aluminum or aluminum oxide ceramics, and yttrium oxide or yttrium oxyfluoride with excellent corrosion resistance is used as the film. However, the uppermost surface of yttrium oxide reacts with fluorine-based gas at the initial stage of the process, which changes the plasma concentration in the device, and there is a problem that the conditions of the etching step become unstable (flow transition). In addition, although the yttrium fluoride thermal spray coating has low reactivity with fluorine-based gases, it has many surface cracks and lower hardness than yttrium oxide, so the etching rate is fast and the replacement cycle of components is shortened.

Therefore, recently, a technique has been disclosed in which yttrium oxyfluoride particles produced by mixing yttrium oxide and yttrium fluoride are used as a material for thermal spraying, thereby forming a thermal spraying film with high corrosion resistance to plasma (Patent Document 1~ 5).

First of all, Korean published patent No. 10-2017-0078842 (2017.07.07.) relates to a film-forming powder of oxyfluoride (Ln-OF) containing rare earth elements, and the average particle size (D50) of the powder is 0.1 From μm to 10μm, with a pore volume of 0.1cm ³ /g to 0.5cm ³ /g measured by mercury intrusion penetration method, and a thermal spraying material with high corrosion resistance of chlorine-based plasma recorded. In addition, Korean Published Patent No. 10-2016-0131916 (2016.11.16.) describes materials for thermal spraying. As constituent elements, rare earth elements (RE), oxygen (O) and halogen (X), rare earth elements The elemental oxyhalide (RE-OX) contains a ratio of 77% by mass or more.

In addition, Korean published patent No. 10-2016-0131917 (2016.11.16.) relates to a rare earth element oxyhalide thermal spraying material. In the X-ray diffraction pattern of the thermal spraying material, relative to the rare earth element oxyhalide The peak intensity IA of the main peak of the rare earth element oxide, the total intensity ratio [(IB+IC)/IA] of the peak intensity IB of the main peak of the rare earth element oxide and the peak intensity IC of the main peak of the rare earth element halide is less than 0.02.

The patent documents 2 and 3 reduce the amount of rare earth element oxides that generate particles due to amorphous characteristics and the amount of rare earth element fluorides that can be transformed into rare earth element oxides by thermal spraying, and increase the amount of rare earth element fluorides with further improved plasma resistance. The amount of the bulk rare earth element oxyhalide, thereby improving the physical properties of the thermal spraying material.

In addition, the thermal spraying material disclosed in Korean Publication Patent No. 10-2016-0131918 (2016.11.16.) includes rare earth elements (RE), oxygen (O) and halogen (X) as constituent elements. Elemental oxyhalides (RE-O-X) have a molar ratio of halogen to rare earth elements (X/RE) of 1.1 or more, so they have improved plasma resistance and excellent properties such as porosity and hardness.

In addition, Korean Published Patent No. 10-2017-0015236 (2017.02.08.) relates to yttrium-based thermal spray coatings with a thickness of 10 to 500 μm including one or more of yttrium oxide, yttrium fluoride, and yttrium oxyfluoride, It describes the production technology of yttrium-based thermal spray coating that can prevent the phenomenon of particle detachment by cleaning the surface of the corresponding coating with a specific solvent, so that the number of particles with a particle size of 300 nm or less existing on the surface is reduced to less than 5 in 1 mm ³ .

As mentioned above, in the past, in order to overcome the physical property limit of yttrium oxide or yttrium fluoride thermal spraying materials, it was proposed to mix and manufacture yttrium oxide and yttrium fluoride, so as to manufacture fluorine oxide with improved physical properties such as plasma erosion, porosity, and hardness. Technology for yttrium thermal spray materials.

However, in the production of yttrium oxyfluoride thermal spray coating, the fluorine component of the thermal spray coating is partially reduced due to high-temperature reaction conditions and replaced by oxygen, resulting in differences in the composition of the thermal spray coating, and it is still difficult to form a uniform composition. In view of the problems of the spray coating, etc., there is a continuous demand from the industry to improve the plasma resistance characteristics of the yttrium oxyfluoride thermal spray coating described in this prior art.

Known technical literature

Patent Document (Patent Document 0001) Korean Publication Patent No. 10-2017-0078842 (Patent Document 0002) Korean Publication Patent No. 10-2016-0131916 (Patent Document 0003) Korean Publication Patent No. 10-2016-0131917 (Patent Document 0004) Korean Publication Patent No. 10-2016-0131918 (Patent Document 0005) Korean Publication Patent No. 10-2017-0015236

Technical issues resolved

The object of the present invention is to provide a method for improving the plasma resistance characteristics of yttrium oxyfluoride thermal spraying material and thermal spraying film.

Technical solutions

In order to achieve the above-mentioned purpose, one embodiment of the present invention provides a method of manufacturing YOF-Al multi-component thermal spraying material, the proportion of yttrium fluoride (YF ₃ ) is 30 to 70 mass % and the rest is oxidized Aluminum (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) are mixed, granulated and fired to produce YOF-Al multi-component thermal spraying materials.

In a preferred embodiment of the present invention, the average particle diameter of the yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) particles can be more than 0.01 μm and less than 7 μm .

In a preferred embodiment of the present invention, the firing temperature may be 500 to 1100°C.

Another embodiment of the present invention provides a Y-O-F-Al multi-component thermal spraying material, which is produced by the method of manufacturing the Y-O-F-Al multi-component thermal spraying material, and has an average particle diameter of more than 5 μm and less than 100 μm.

Yet another embodiment of the present invention provides a method for manufacturing a Y-O-F-Al multi-component thermal spray film. The Y-O-F-Al multi-component thermal spray material is thermally sprayed to form a film on a substrate.

In a preferred embodiment of the present invention, the thermal spraying can be plasma thermal spraying.

Another embodiment of the present invention provides a Y-O-F-Al multi-component thermal spray film, which is formed by the manufacturing method of the Y-O-F-Al multi-component thermal spray film, and has a thickness of 50 to 400 μm.

Another embodiment of the present invention provides a Y-O-F-Al multi-component thermal spray coating, which is characterized in that, as constituent elements, it includes yttrium (Y), oxygen (O), fluorine (F) and aluminum (Al), the aluminum element The weight ratio (Al/Y+F) to the yttrium and fluorine is 0.025 to 0.25.

In a preferred embodiment of the present invention, the weight ratio of fluorine to the yttrium (F/Y) may be 0.7 to 1.3.

Invention effect

The Y-O-F-Al multi-component thermal spraying material of the present invention does not change the composition of the oxygen component and the fluorine component contained in the thermal spraying film during the thermal spraying manufacturing process, and suppresses the formation of cracks and pores that have occurred in the conventional coating layer. A thermal spray coating that is denser than conventional coatings can be formed.

Therefore, the Y-O-F-Al multi-component thermal spray coating film of the present invention has increased hardness compared with yttrium fluoride and yttrium oxide in the past, has low porosity, and the plasma resistance property improves, and can prolong the life of the Y-O-F-Al multi-component thermal spray coating film member. Replacement cycle.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those having ordinary skill in the technical field to which this invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the technical field.

Throughout the specification of the present application, when it is mentioned that a certain part "includes" a certain component, unless there is a specific statement to the contrary, it means that other components are not excluded, and other components may be further included.

In semiconductor manufacturing steps, a gate etching device, an insulating film etching device, a resist film etching device, a sputtering device, a CVD device, and the like are used. On the other hand, in the manufacturing process of liquid crystals, an etching device or the like for forming thin film transistors is used. In addition, in these manufacturing apparatuses, for the purpose of high integration by microfabrication, etc., a configuration including a plasma generating mechanism is employed.

In these manufacturing steps, halogen-based etching gases such as fluorine-based, chlorine-based, etc., as process gases are used for the device due to their high reactivity. As the fluorine gas, it can be SF ₆ , CF ₄ , CHF ₃ , ClF ₃ , HF, NF ₃ , etc., and the chlorine gas can be, for example, Cl ₂ , BCl ₃ , HCl, CCl ₄ , SiCl ₄ , etc. If microwave or high frequency etc. are connected in the atmosphere, these gases will be plasmaized. Device components exposed to these halogen-based gases or their plasma have very little metal on the surface except for material components, and are required to have high corrosion resistance. Therefore, the object of the present invention is to provide a device for plasma etching. Manufacturing method of YOF-Al multi-component thermal spray material and thermal spray film with excellent plasma resistance for coating components.

The method for manufacturing Y-O-F-Al multi-component thermal spraying material will be described in detail below.

According to one aspect of the present invention, there is provided a method of mixing and granulating yttrium fluoride (YF ₃ ) with a ratio of 30 to 70% by mass and the balance of alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG). 1. A method of firing and manufacturing YO-F-Al multi-component thermal spraying materials.

Although the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) materials were studied as primary materials, they were used as ungranulated powders, or as powders containing ungranulated However, the fluidity of the material cannot reach the level required for thermal spraying. Preferably, granulated particles are formed through the steps of mixing, granulating and firing into a spherical shape.

Preferably, the thermal spraying material as a granulated powder is filled inside, which is not broken but stable in handling the powder, and if there is a void, it is easy to contain a relatively bad gas component in the void, thus from It is necessary from the perspective that this situation can be avoided.

In this mixing and granulating step, sintering aids and dispersion media are added to the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG), and after pulverization and mixing, Goes through dehydration and drying process. If necessary, it is added and mixed with a binder to produce slurry droplets, followed by granulation and firing to produce granulated particles. As a binder, organic compounds are preferred, and can be organic compounds composed of carbon, hydrogen, oxygen, or carbon, hydrogen, oxygen, and nitrogen, such as carboxymethylcellulose (CMC), polyvinyl alcohol (PVA) , polyvinylpyrrolidone (PVP), etc.

The yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), yttrium aluminum garnet (YAG) particles were subjected to a granulation process. As a granulation device, for example, a spray drying device can be used. In the spray drying apparatus, slurry liquid droplets containing a plurality of pulverized particles are dropped in hot air, whereby the liquid droplets are solidified to produce intermediate particles including a plurality of particles.

In terms of the granulation step, preferably, the average particle diameter of the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) particles is not less than 0.01 μm and not more than 7 μm. When the diameter of the particles is less than about 0.01 μm, the average diameter of the thermal spray coating powder having a granulated structure including the yttrium oxide particles decreases, making it difficult to control the particles and form spherical granulated particles. When the diameter of the particles exceeds about 7 μm, the average diameter of the granulated particles formed by agglomeration of the particles is too large, making it difficult to form a uniform thermal spray coating.

Then, the granulated particles are subjected to a firing step, preferably at a temperature of 500 to 1100°C. By firing in this temperature range, the yttrium oxyfluoride and the aluminum compound fully react. When the firing temperature is lower than 500° C., the mixing reaction is insufficient, and part of yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) may remain. More preferably, the firing temperature is 800 to 1000° C., which is effective in improving the plasma resistance of the multi-component thermal spray coating. Specifically, when the calcination temperature is lower than 800° C., the hardness of the thermal spray coating is insufficient, and therefore the plasma resistance of the thermal spray material decreases.

On the condition that the firing temperature is within this range, the firing time is preferably from 2 hours to 8 hours. If it is within this range, the Y-O-F-Al multi-component compound is sufficiently produced and energy consumption is minimized.

The firing atmosphere can use an oxygen-containing atmosphere such as an air atmosphere, but is preferably an inert gas atmosphere such as argon or a vacuum atmosphere.

The average particle diameter of the thermal spray material produced by mixing, granulating, and firing is 5 μm or more and 100 μm or less, which is advantageous in terms of improving the quality of the thermal spray coating. If the average particle diameter is less than 5 μm, the fluidity of the powder is low during thermal spray coating, and a uniform film cannot be exhibited, and the powder is oxidized before it is transferred to the frame, or it is not transferred to the center of the frame, and it is difficult to meet the requirements for forming a dense film. Droplet splash speed and heat result in the formation of a film with many pores or low hardness. If the average particle diameter exceeds 100 μm, then when the powder is injected into the plasma body, it cannot be completely melted, and unmelted parts will occur in the coating film, making it difficult to meet the quality of the thermal spray coating required by the present invention.

The aspect ratio (aspect ratio) of the thermal spraying material powder of the present invention is represented by the ratio of the major diameter and the minor diameter of the particles, and those of 1.0 or more and 5.0 or less are advantageous in forming a dense and uniform film. The ratio is more preferably from 1.0 to 4.0, and particularly preferably from 1.0 to 1.5.

As far as thermal spraying material powder is concerned, fluidity is an important factor for the quality of thermal spraying film. It is better to make it into a spherical shape. Otherwise, when manufacturing thermal spraying film, the given amount of powder cannot be transferred to the frame and cannot form the required level. membrane.

In addition, a method for producing a Y-O-F-Al multicomponent thermal spray coating in which an aluminum yttrium oxyfluoride film is formed on a substrate by plasma thermal spraying the Y-O-F-Al multicomponent thermal spray material will be described.

The plasma thermal spraying method generally includes a coating method in which a thermal spraying material is injected into a plasma injector, heated, accelerated, and deposited on a substrate to obtain a thermal spraying film. In addition, the plasma thermal spraying method can be atmospheric plasma thermal spraying (APS:atmospheric plasma spraying) in the atmosphere or decompression plasma thermal spraying (LPS: low pressure plasma spraying), high pressure plasma thermal spraying (high pressure plasma spraying) in a pressure vessel above atmospheric pressure. According to this plasma thermal spraying, for example, as an example, the thermal spraying material is melted and accelerated by means of a plasma injector at about 10000K to 15000K, so that the thermal spraying particles can be heated at a speed of about 300m/s to 1000m/s The speed hits the substrate and accumulates on the substrate.

Thermal spraying of substrates according to the invention can be carried out by means of atmospheric piezoelectric plasma thermal spraying. At this time, the plasma gas is not particularly limited and can be appropriately selected. For example, nitrogen/hydrogen, argon/hydrogen, argon/helium, argon/nitrogen, etc. can be used. In the present invention, thermal spraying argon/hydrogen is preferable.

As a specific example of thermal spraying, in the case of argon/hydrogen plasma thermal spraying, atmospheric pressure plasma thermal spraying using a mixed gas of argon and hydrogen in an air atmosphere may be used. Thermal spraying conditions such as thermal spraying distance, current value, voltage value, argon gas supply, and hydrogen gas supply are set according to the application of the thermal spraying member. Fill the powder supply device with a predetermined amount of thermal spray material, and use the dry powder hose to supply the dry powder to the front end of the plasma thermal spray gun with the help of carrier gas (argon). The dry powder is continuously supplied to the plasma spark, so that the thermal spray material is melted and liquefied, and the liquid frame is realized by the force of the plasma injector. The liquid frame hits the substrate so that the molten dry powder adheres, solidifies and builds up. Using this principle, the frame is moved left and right, up and down, and a Y-O-F-Al multi-component thermal spray film is formed on the substrate within the predetermined coating range, so that Y-O-F-Al multi-component film-forming parts (thermal spray components) can be manufactured.

In the present invention, the base material coated with the thermal spray coating is not particularly limited. For example, the material, shape, and the like are not particularly limited as long as the base material used for thermal spraying of such a material for thermal spraying includes a material that can have required resistance. As a material constituting such a base material for thermal spraying, for example, aluminum, nickel, chromium, zinc and alloys thereof, aluminum oxide, aluminum nitride, silicon nitride, aluminum oxide, aluminum nitride, silicon nitride, etc. Choose from a combination of at least one of silicon carbide and quartz glass.

Such a substrate is, for example, a member constituting a semiconductor device manufacturing apparatus, and may be a member exposed to highly reactive oxygen plasma or halogen gas plasma.

Preferably, the surface of the substrate is treated according to the ceramic thermal spraying operation standard stipulated in JIS H 9302 before plasma thermal spraying. For example, after removing rust, grease, etc. on the surface of the substrate, abrasive particles such as Al ₂ O ₃ , SiC, etc. are sprayed to roughen the surface, and the fluoride thermal spray particles are pretreated to be easily attached.

In addition, in addition to plasma thermal spraying, the manufacturing method of this thermal spray coating can be formed by supplying the thermal spray material disclosed here to the thermal spray apparatus based on the conventional thermal spray method. A suitable thermal spraying method for thermally spraying such a material for thermal spraying is, for example, a thermal spraying method such as a high-speed frame thermal spraying method, a frame thermal spraying method, or an explosive thermal spraying method.

The characteristics of the thermal spray coating may depend to some extent on the thermal spray method and its thermal spray conditions. However, regardless of the thermal spraying method and thermal spraying conditions, by using the thermal spraying material disclosed here, compared with the case of using other thermal spraying materials, it is possible to form a thermal spraying film with excellent plasma erosion resistance. .

Preferably, the Y-O-F-Al multi-component thermal spray coating is formed with a thickness of 50-400 μm. At this time, if the thickness is less than 50 μm, sufficient corrosion resistance may not be obtained, and the surface of the substrate may be partially exposed due to cleaning operations. On the other hand, even if the structure is thicker than 400 μm, the effect of improving the corrosion resistance cannot be expected, and only high cost is incurred.

Conventional YF ₃ and YOF thermal spray coatings are crystalline films, which change from amorphous to crystalline when the powder melts and solidifies, forming cracks and pores in the coating layer. In the present invention, a part of Al ₂ O ₃ is added to the powder, and the corresponding substance has an amorphous property when forming a thermal sprayed film. When powders containing substances with such characteristics are melted and solidified by means of plasma, most of them change from amorphous to crystalline, but a part _of the _Al2O3 substance remains amorphous, which is expected to suppress the occurrence of the previous coating layer. formation of cracks and pores. As a result, the effect of remarkably reducing the number of cracks (cracks) generated in grain boundaries (grain boundaries) and thus the number of particles (particles) generated therefrom was exhibited.

The multi-component thermal spray coating is composed of yttrium (Y), oxygen (O), fluorine (F) and aluminum (Al). Preferably, the weight ratio of aluminum to the yttrium and fluorine is [Al/(Y+ F)] from 0.025 to 0.25. In the thermal spray coating, when the weight ratio [Al/(Y+F)] of the aluminum element to yttrium and fluorine is less than 0.025, the Al ₂ O ₃ amorphous part is insufficient, and the hardness of the thermal spray coating is low, and improvement cannot be achieved. The effect of plasma resistance.

Preferably, the weight ratio (F/Y) of fluorine to yttrium in the composition of the thermal spray coating is 0.7 to 1.3. When the weight ratio (F/Y) of fluorine to yttrium exceeds 1.3, since the fluorine concentration is high, the hardness of the thermally sprayed film decreases, resulting in an increase in etching rate.

Therefore, compared with the original yttrium fluoride and yttrium oxyfluoride thermal spraying coatings, the Y-O-F-Al multi-component thermal spraying coating produced by means of atmospheric plasma has excellent hardness and porosity, and has a higher level than the original etching The semiconductor chamber used in the step uses a more excellent level of yttria thermal spray coating.

In addition, the Y-O-F-Al component confirmed in the mixed, granulated, and fired thermal spray material is also detected in the same way in the thermal spray coating produced by the atmospheric plasma method. Using this point, it is easy to Control the physical properties of thermal spray coating under different components accurately.

The present invention will be described in more detail below by way of examples. However, the following examples are merely examples of the present invention, and the present invention is not limited by the examples.

<Example>

Properly mixing, granulating and firing yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) to obtain a powder state thermal spraying material. The thermal spraying material was produced by changing the component ratio of the primary material composed of 30 to 70% by mass of YF ₃ and the remainder of (Al ₂ O ₃ +YAG).

＜Example 1＞

(1) Manufacturing process of thermal spraying materials

Granulated powders were obtained by means of a spray dryer after mixing binders in yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) powders. This granulated powder was degreased and then sintered to obtain a sintered powder.

(2) Manufacturing process of thermal spray coating

Using the thermal spray material and plasma gun prepared in step (1), flow argon and hydrogen gas as the heat source gas, and generate plasma at a power of 40 to 50 kW while moving the thermal spray gun. The plasma body melts the raw material powder and forms a coating film on the base material. The thickness of the coating film was formed to have a thickness of 150 to 200 μm, and the component ratio of the obtained thermal spray coating film was as described in Table 1 below.

<Examples 2 to 6 and Comparative Examples 1 to 6>

Raw materials were prepared to produce a thermal spray film with the composition ratio of the primary material having the composition ratios listed in Table 1 below, and the thermal spray material was granulated. The heat treatment temperature of the granulated thermal spray material was shown in Table 1 below. . Then, using the obtained thermal spray material, the thermal spray coating was formed under the same conditions as in Example 1.

The thermal spray coatings produced in Examples 1 to 6 and Comparative Examples 1 to 6 were analyzed to obtain experimental data showing the component ratio of each element as shown in Table 1. In order to measure the physical properties of the thermal sprayed coatings of the respective examples, the following experiments were conducted, and the physical property values thus obtained are summarized in Table 1 below. In addition, for reference, the physical properties of conventionally used thermal spray coatings are shown together with Comparative Examples 7 to 9. When the Y-O-F-Al multi-component thermal spraying film is analyzed by X-ray spectroscopy (EDS) using a scanning electron microscope (SEM), Y, O, F, and Al components are detected, and X-ray diffraction analysis (XRD) ) Crystalline properties during analysis.

Table 1

<Experimental Example 1 - Measurement of Component Concentration of Thermal Spray Coating>

In order to analyze the changes in the Y, O, F, and Al components in the thermal spray coatings produced in Examples 1 to 6 and Comparative Examples 1 to 9, EDS analysis was performed, and the results are shown in Table 1.

Component content analysis is to cut the thermal spray coating into a plane perpendicular to the surface of the substrate, and perform EDS measurement on the cross-sectional image using an electron microscope (JEOL, JS-6010) after performing resin in-line grinding on the obtained cross-section . During the EDS measurement, the components were confirmed by using the CPS value to confirm the numerical value of 100,000 or more samples within 1 minute.

＜Experimental example 2-Observation of thermal spray coating＞

The first figure is a scanning electron microscope (SEM) photo of the thermal sprayed film side of the comparative example (comparative example 7, 8, 9) and embodiment (embodiment 1) of the present invention, by the thermal sprayed film side of the first figure Scanning electron microscope (SEM) photographs of the above, it was confirmed that the pore area of the multi-component thermal spray coating produced according to Example 1 was smaller than that of the thermal spray coating produced according to Comparative Examples 7, 8, and 9.

In addition, Table 1 shows the porosity (porosity) obtained from the pore area shown in the cross-section of the thermal spray coating produced in Comparative Examples (Comparative Examples 7, 8, and 9) and Examples (Example 1). . The measurement of the porosity was performed as follows. That is, the thermal spray coating was cut into a plane perpendicular to the surface of the base material, and resin insert grinding was performed on the obtained cross section, and the cross-sectional image was taken using an electron microscope (JEOL, JS-6010) (Fig. 1). This image was analyzed using image analysis software (MEDIA CYBERNETICS, Image Pro), thereby specifying the area of the stomata in the cross-sectional image, and calculating the ratio of the area of the stomata to the cross section, thereby obtaining Porosity.

The porosity of the thermal spray coating produced in Comparative Example 8 and Comparative Example 9 showed a value of 3 to 4%, and the porosity of the yttrium fluoride (YF3) thermal spray coating formed according to Comparative Example 7 showed a value of 2 ~3%. However, Examples 1 and 2 showed a value of 1 to 2% porosity, showing that the multi-component thermal spray coating of the present invention has an increased density than conventionally used component thermal spray coatings.

Fig. 2 is a scanning electron microscope (SEM) photograph of the surface of a thermal sprayed film of a comparative example (comparative examples 7 and 8) and an example (example 1) of the present invention. According to the scanning electron microscope (SEM) photo of the surface of the thermal sprayed coating in Fig. 2, it was observed that the number of cracks on the surface of the thermal sprayed coating produced according to Comparative Examples 7 and 8 was higher than that of the multi-component thermal sprayed coating produced according to Example 1. Significant reduction of spray film surface.

＜Experimental Example 3-Hardness Measurement＞

The "Hardness" column in Table 1 shows the Vickers hardness measurement results of each thermal spray coating. The measurement of Vickers hardness is to use a microwave hardness tester, with the help of a diamond indenter with an angle of 136° between opposite surfaces, and apply a test force of 294.2 mN to obtain the Vickers hardness (Hv0.2).

As shown in Table 1, the yttrium-based thermal spray coating film of Comparative Examples 7 to 9 shows 300 to 400Hv hardness, but the Y-O-F-Al multi-component thermal spray coating film in Examples 1 and 2 shows 450 to 500Hv hardness, so the present invention It has improved mechanical properties compared to conventional yttrium thermal spray coatings.

<Experimental example 4 - Etching rate measurement>

The "Plasma Etch Rate" column in Table 1 shows the results of evaluating the etching rate when each thermal spray coating was exposed to plasma under the following conditions. That is, first, the members to which the thermal spray coatings of Comparative Examples 7 to 9 and Examples 1 and 2 were adhered were attached to the members in contact with the upper electrodes in the chamber of the parallel plate type semiconductor device manufacturing apparatus. Furthermore, a 2-hour trial run of plasma dry etching was carried out on a stage where a silicon wafer was mounted in a chamber. The pressure in the chamber was kept at 0.1torr, and the etching gas containing carbon tetrafluoride was supplied. During 2 hours, 700W of high-frequency power was connected to the upper part, and 250W of high-frequency power was connected to the lower part, so that the etching process occurred. Plasma.

After this plasma etching step, three-dimensional analysis (KEYENCE, VK-X150K 3D analysis) of components installed in the chamber of semiconductor device manufacturing equipment was performed to obtain the etching rate of the thermal spray coating.

As shown in Table 1, Comparative Examples 7 to 9 exhibited etch rates in the range of 3.12 to 3.99 μm/h, on the contrary, Examples 1 and 2 exhibited etch rates in the range of 2.88 to 3.01 μm/h, showing The plasma etch rate of the present invention is reduced.

The specific part of the content of the present invention has been described in detail above, and this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereto, which is self-evident for those skilled in the art. Accordingly, the substantial scope of the present invention is defined by the appended claims and their equivalents.

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Fig. 1 is a scanning electron microscope (SEM) photograph of a side surface of a thermal sprayed film of a comparative example (comparative examples 7, 8, 9) and an example (example 1) of the present invention.

Fig. 2 is a scanning electron microscope (SEM) photograph of the surface of a thermal sprayed film of a comparative example (comparative examples 7 and 8) and an example (example 1) of the present invention.

Claims (9)

A method for manufacturing YOF-Al multi-component thermal spraying materials, which includes: the proportion of yttrium fluoride (YF ₃ ) is 30 to 70 mass % and aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) is mixed, granulated, and fired to produce YOF-Al multi-component thermal spraying materials. The method described in claim 1 of the patent application, wherein the average particle diameter of the yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) particles is 0.01 μm or more, 7 μm the following. The method described in claim 1 of the patent application, wherein the firing temperature is 500 to 1100°C. A Y-O-F-Al multi-component thermal spraying material, which is prepared by the method of any one of items 1 to 3 in the scope of the patent application, with an average particle diameter of more than 5 μm and less than 100 μm. A method for manufacturing a Y-O-F-Al multi-component thermal spray film, which includes: performing thermal spraying on the Y-O-F-Al multi-component thermal spray material as described in item 4 of the scope of the patent application to form a film on a substrate. The method described in item 5 of the scope of the patent application, wherein the thermal spraying is plasma thermal spraying. A Y-O-F-Al multi-component thermal spray film is formed by the method for manufacturing a Y-O-F-Al multi-component thermal spray film as described in item 5 of the scope of the patent application, with a thickness of 50 to 400 μm. A Y-O-F-Al multi-component thermal spray film, wherein, as constituent elements, including yttrium (Y), oxygen (O), fluorine (F) and aluminum (Al), the aluminum element relative to The weight ratio (Al/Y+F) of yttrium to fluorine is 0.025 to 0.25. In the Y-O-F-Al multi-component thermal spraying film described in item 8 of the scope of the patent application, the weight ratio of fluorine to yttrium (F/Y) is 0.7 to 1.3.

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