TW201927724A - Material for thermal spray, thermal spray coating using the same and manufacture methods thereof - Google Patents

Abstract

The present invention relates to a yttrium aluminum oxyfluoride spray coating material and, more particularly, to a spray coating material with excellent plasma resistance that is produced by mixing, assembling, and baking 30-70% by mass of yttrium fluoride (YF3) and a balance of alumina (Al2O3) and yttrium aluminum garnet (YAG), and to a spray coating.

Description

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

The invention relates to a method for manufacturing a thermal spray material and a thermal spray coating.

In the semiconductor manufacturing process, in order to perform the microfabrication required for the high integration of substrate circuits such as silicon wafers, the importance of the plasma dry etching step becomes more and more important.

In order to use it in such an environment, it is proposed to use a material having excellent resistance to plasma as a chamber member or to form a film on the surface of the member with a substance having excellent resistance to plasma to increase the life of the member.

Among them, a technique for imparting new functionality by coating the surface of a substrate with various materials has been used in many fields in the past. As one of such surface coating technologies, for example, a thermal spray method is known in which thermal spray particles made of a material such as ceramics are sprayed on the surface of a substrate in a softened or molten state by means of combustion or electrical energy to form a thermal spray coating.

Generally, thermal spray coating is performed by heating and melting a fine powder, and spraying the molten powder toward a coated surface of a base material. The sprayed molten powder is rapidly cooled, the molten powder is solidified, and it is laminated on the coating target surface mainly using a mechanical bonding force.

In this thermal spray coating, plasma thermal spray coating using a high-temperature plasma flame to melt the powder must be used in coating of metals and ceramics such as tungsten or molybdenum with high melting points. The thermal spray coating not only shows that it maintains the material characteristics of the base material, but also is beneficial to the production of wear resistance, corrosion resistance, heat resistance and thermal barrier, super hard, oxidation resistance, insulation, friction characteristics, heat dissipation, and biological function radiation resistance characteristics. Compared with other coating methods such as chemical vapor deposition or physical vapor deposition, it can coat a wide area of objects in a short time.

Furthermore, in the manufacturing field of semiconductor devices and the like, micro-processing is generally performed on the surface of a semiconductor substrate by dry etching using a plasma of a halogen-based gas such as fluorine, chlorine, or bromine. In addition, after dry etching, the inside of the chamber (vacuum container) from which the semiconductor substrate was taken out was cleaned using an oxygen plasma. At this time, in the chamber, there is a possibility that the components exposed to the highly reactive oxygen plasma or halogen gas plasma may be corroded. In addition, if the corroded (eroded) portion comes off in a granular form from the corresponding member, such particles adhere to the semiconductor substrate and become foreign matter that causes circuit defects (hereinafter, the corresponding foreign matter is referred to as particles).

Therefore, in the past, in a semiconductor device manufacturing apparatus, in order to reduce the generation of particles, a ceramic thermal spray coating having a resistance to plasma erosion has been provided on a member exposed to a plasma such as oxygen or halogen gas. .

As a cause of such particles, in addition to the peeling of the reaction products adhering in the vacuum chamber, there may be a deterioration of the chamber due to the use of a halogen gas plasma or an oxygen plasma. In addition, according to the study by the present inventors, it was confirmed that the number or size of particles generated from the thermal spray coating under the dry etching environment is greatly affected by the components of the thermal spray coating.

Specifically, the components of the etching device that are in contact with the halogen-based gas plasma are based on metallic aluminum or vaporized aluminum ceramics, and use yttrium oxide or yttrium oxide having excellent corrosion resistance as a coating. However, yttrium oxide reacts with a fluorine-based gas at the uppermost surface at the beginning 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 speed is fast, and the replacement cycle of components is shortened.

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

First, Korean Published Patent No. 10-2017-0078842 (2017.07.07.) Relates to a film-forming powder containing a rare earth element oxyfluoride (Ln-OF), and the average particle diameter (D50) of the powder is 0.1 Thermal spraying materials having a pore volume of 10 μm or less and a diameter of 10 μm or less measured by a mercury intrusion method of 0.1 cm ³ / g or more and 0.5 cm ³ / g or less and having high corrosion resistance to chlorine-based plasmas Got the record. In addition, Korean Published Patent No. 10-2016-0131916 (2016.11.16.) Describes materials for thermal spraying. As constituent elements, it includes rare earth elements (RE), oxygen (O), halogen (X), and rare earths. Element-like 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, it is compared with the rare-earth element oxyhalogenation. The total intensity ratio [(IB + IC) / IA] of the peak intensity IA of the main peak of the substance, 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 have particles due to amorphous properties and rare-earth element fluorides that can be transformed into rare-earth element oxides by thermal spraying, and increase the plasma resistance. The amount of the rare earth element oxyhalide, which improves the physical properties of the thermal spray material.

In addition, the material for thermal spraying disclosed in Korean Published Patent No. 10-2016-0131918 (2016.11.16.) Includes, as constituent elements, rare earths containing rare earth elements (RE), oxygen (O), and halogen (X). Elemental oxygen halide (RE-OX) has a molar ratio (X / RE) of halogen to rare earth elements of 1.1 or higher. Therefore, it has improved plasma resistance and excellent porosity and hardness.

In addition, Korean Published Patent No. 10-2017-0015236 (2017.02.08.) Relates to one or two or more yttrium-based thermal spray coatings having a thickness of 10 to 500 μm including yttrium oxide, yttrium fluoride, and yttria. describes the phenomenon of particles from the thermal spray coating of yttrium-based manufacturing techniques by using a particular solvent cleaning the respective surfaces of the film, so that the number of particles present in the surface of the particle size is reduced below 300nm to 1mm ³ 5 or less, it can be prevented.

As described above, in order to overcome the physical property limits of yttrium oxide or yttrium fluoride thermal spray materials, a mixed production of yttrium oxide and yttrium fluoride has been proposed in the past, so as to produce fluorooxidation that has improved physical properties such as plasma erosion, porosity, and hardness. Technology for yttrium thermal spray materials.

However, in the manufacture of yttrium oxyfluoride thermal spray coatings, the fluorine content of the thermal spray coatings is partially reduced due to high temperature reaction conditions and replaced by oxygen, resulting in differences in the composition of the thermal spray coatings. Problems such as spray coatings and the like, and improving the plasma-resistant properties of the yttrium oxyfluoride thermal spray coatings described in the prior literature are continuing industrial demands.

Know-how

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

Technical issues solved

The purpose of the present invention is to provide a method for improving the plasma-resistant properties of yttrium oxyfluoride thermal spray materials and thermal spray coatings.

Technical solutions

In order to achieve the above-mentioned object, an embodiment of the present invention provides a method for manufacturing a YOF-Al multi-component thermal spraying material. The ratio of yttrium fluoride (YF ₃ ) is 30 to 70% by mass and the balance is oxidized. Aluminum (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) are mixed, granulated, and fired to produce YOF-Al multi-component thermal spray 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 may be 0.01 μm or more and 7 μm or less. .

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 manufactured by the manufacturing method of the Y-O-F-Al multi-component thermal spraying material, and has an average particle diameter of 5 μm or more and 100 μm or less.

Another embodiment of the present invention provides a method for manufacturing a Y-O-F-Al multi-component thermal spray coating film, and thermally sprays the Y-O-F-Al multi-component thermal spray coating material to form a film on a substrate.

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

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

Another embodiment of the present invention provides a YOF-Al multi-component thermal spray coating film, which is characterized in that as constituent elements, it includes yttrium (Y), oxygen (O), fluorine (F), aluminum (Al), and aluminum elements. 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 (F / Y) of fluorine to the yttrium may be 0.7 to 1.3.

Invention effect

In the YOF-Al multi-component thermal spraying material of the present invention, during the thermal spraying manufacturing step, the composition of the oxygen and fluorine components contained in the thermal spraying film does not change, and the formation of cracks and pores in the conventional coating layer is suppressed. It is possible to form a denser thermal spray coating than conventional coating layers.

Therefore, the YOF-Al multi-component thermal spray coating of the present invention has higher hardness than the conventional yttrium fluoride and yttrium oxide, has a low porosity, and has improved resistance to plasma. It can extend the YOF-Al multi-component thermal spray coating film member. Replacement cycle.

As long as it is not defined otherwise, all technical and scientific terms used in this specification have the same meaning as those commonly understood by those having ordinary knowledge in the technical field to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.

Throughout this application, when referring to a certain part as "including" a certain constituent element, as long as there is no particularly contrary description, it means that other constituent elements are not excluded, and other constituent elements may be further included.

In the manufacturing steps of the semiconductor, 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 steps of the liquid crystal, an etching device or the like for forming a thin film transistor is used. Moreover, in these manufacturing apparatuses, the structure provided with the plasma generating means is employ | adopted for the purpose of high volume accumulation etc. by micromachining.

In these manufacturing steps, halogen-based corrosive gases such as fluorine-based and chlorine-based processes are used in the device because of their high reactivity. Examples of the fluorine-based gas include SF ₆ , CF ₄ , CHF ₃ , ClF ₃ , HF, and NF _{3. The} chlorine-based gas may include Cl ₂ , BCl ₃ , HCl, CCl ₄ , and SiCl ₄ . When microwaves or high frequencies are connected in the atmosphere, these gases are plasmatized. Device components exposed to these halogen-based gases or their plasmas have few metals other than material components on their surfaces and require high corrosion resistance. Therefore, the present invention aims to provide a plasma etching device. A method for manufacturing a YOF-Al multi-component thermal spraying material and a thermal spraying film having excellent plasma-resistant properties for coating a component.

The method for manufacturing the Y-O-F-Al multi-component thermal spray material is described in detail below.

According to an aspect of the present invention, there is provided a method for mixing and granulating alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) in a proportion of 30 to 70 mass% of yttrium fluoride (YF ₃ ). 2. A method for firing and manufacturing a YO-F-Al multi-component thermal spraying material.

Although the yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) materials have been studied as primary materials, they are used as ungranulated powders, or as ungranulated powders. The slurry can be used, but the fluidity of the material cannot reach the level required for thermal spraying. Preferably, the granulated particles are formed after the mixing, granulation and firing steps that are made into a spherical shape.

Preferably, the thermal spray material as a granulated powder is filled into the inside, which does not break but is stable in handling the powder. If there is a void portion, the void portion is likely to contain a poorer gas component. It is necessary to avoid this situation.

In the mixing and granulating step, a sintering aid and a dispersion medium are added to the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG), and after pulverization and mixing, After dehydration and drying process. If necessary, it can be mixed with a binding agent to produce slurry droplets, and then granulated and calcined to produce granulated particles. The binding agent is preferably an organic compound, and may be an organic compound composed of carbon, hydrogen, and oxygen, or carbon, hydrogen, oxygen, and nitrogen. For example, it may be carboxymethyl cellulose (CMC) or polyvinyl alcohol (PVA). , Polyvinylpyrrolidone (PVP) and so on.

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

In terms of the granulation step, the average particle diameter of the yttrium fluoride (YF ₃ ), aluminum oxide (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) particles is preferably 0.01 μm or more and 7 μm or less. In the case where 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 is reduced, the control of the particles is difficult, and it is difficult to form spherical granulated particles. When the diameter of the particles exceeds about 7 μm, the average diameter of the granulated particles formed by the agglomeration of the particles is too large, and it may be difficult to form a uniform thermal spray coating.

Then, the granulated particles are subjected to a firing step, and the preferred firing temperature is 500 to 1100 ° C. By firing in this temperature range, yttrium oxyfluoride and the aluminum compound are sufficiently reacted. When the firing temperature is less than 500 ° C, the mixing reaction is insufficient, and there is a possibility that a 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 film. Specifically, when the firing temperature is less than 800 ° C., the hardness of the thermal spray coating is insufficient, and therefore, the plasma resistance of the thermal spray material is low.

Under the condition that the firing temperature is within this range, the firing time is preferably 2 hours or more and 8 hours or less. Within this range, Y-O-F-Al multi-component compounds are sufficiently formed, and energy consumption is minimized.

The firing atmosphere may be an oxygen-containing atmosphere such as an atmospheric atmosphere, but an inert gas atmosphere such as argon or a vacuum atmosphere is preferred.

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

The aspect ratio of the powder of the thermal spray material of the present invention is expressed by the ratio of the long diameter to the short diameter of the particles. 1.0 or more and 5.0 or less are advantageous in forming a dense and uniform film. From this viewpoint, the aspect ratio The ratio is more preferably 1.0 or more and 4.0 or less, and particularly preferably 1.0 or more and 1.5 or less.

As far as thermal spray material powder is concerned, fluidity is an important element of the quality of thermal spray film. It is preferably made into a sphere. Otherwise, when manufacturing a thermal spray film, the given amount of powder cannot be transferred to the frame and cannot form the level we require. Of the film.

In addition, a method for manufacturing a Y-O-F-Al multi-component thermal spray coating film by subjecting the Y-O-F-Al multi-component thermal spray coating material to plasma thermal spraying to form an aluminum yttrium oxide film on a substrate will be described.

The plasma thermal spraying method generally includes a coating method in which a material for thermal spraying is put into a plasma sprayer, heated, accelerated, and deposited on a substrate to obtain a thermal sprayed film. In addition, the plasma thermal spraying method may be atmospheric plasma spraying (APS: atmospheric plasma spraying) performed in the atmosphere or reduced pressure plasma thermal spraying (LPS: low pressure plasma spraying), high pressure plasma spraying in the form of 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 sprayer of about 10000K to 15000K, so that the thermal spraying particles can be about 300m / s to 1000m / s. The speed hits the substrate and accumulates on the substrate.

The thermal spraying of the substrate of the present invention can be performed by means of thermal spraying of atmospheric piezoelectric slurry. In this case, the plasma gas is not particularly limited and may be appropriately selected. For example, nitrogen / hydrogen, argon / hydrogen, argon / helium, argon / nitrogen, and the like can be used. In the present invention, thermal spraying argon / hydrogen is preferred.

As a specific example of thermal spraying, in the case of argon / hydrogen plasma thermal spraying, atmospheric piezoelectric slurry thermal spraying using a mixed gas of argon and hydrogen in an atmospheric atmosphere may be used. Thermal spraying conditions such as thermal spraying distance or current value, voltage value, argon gas supply amount, hydrogen gas supply amount, etc. are set according to the application of the thermal spraying member and the like. The powder supply device is filled with a predetermined amount of thermal spraying material, and a dry powder hose is used to supply dry powder to the front end portion of the plasma thermal spraying gun by means of a 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 framing is achieved due to the force of the plasma sprayer. The liquid frame hits the substrate, so that the molten dry powder adheres, solidifies, and accumulates. By using this principle, the frame is moved left and right, up and down, and a Y-O-F-Al multi-component thermal spray coating is formed in a predetermined coating range on the substrate, so that a Y-O-F-Al multi-component film-forming component (thermal spray member) can be manufactured.

In the present invention, the substrate coated with the thermal spray coating is not particularly limited. For example, if it is a substrate that provides thermal spraying for such a thermal spraying material and includes a material that can have the required resistance, the material, shape, and the like are not particularly limited. 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, A combination of at least one or more of silicon carbide and quartz glass is selected.

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

Preferably, the surface of the substrate is treated according to the ceramic thermal spraying operation standard specified by JIS H 9302 before the plasma thermal spraying. For example, after removing rust, grease, and the like on the surface of the substrate, the surface is roughened by spraying abrasive particles such as Al ₂ O ₃ and SiC, and the surface is pretreated into a state where the thermal sprayed fluoride particles are easily attached.

In addition, the manufacturing method of the thermal spray coating film may be formed by supplying a thermal spray material disclosed herein to a thermal spray device based on a conventional thermal spray method in addition to plasma thermal spray. Suitable thermal spraying methods for thermal spraying such thermal spraying materials include, for example, thermal spraying methods such as high-speed frame thermal spraying, frame thermal spraying, and explosive thermal spraying.

The characteristics of the thermal spray coating may depend to some extent on the thermal spray method and the thermal spray conditions. However, no matter which thermal spraying method and thermal spraying conditions are used, by using the thermal spraying materials disclosed herein, a thermal spraying film having excellent resistance to plasma erosion can be formed compared to the case of using other thermal spraying materials. .

Preferably, the Y-O-F-Al multi-component thermal spray coating is formed in a thickness of 50 to 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 the cleaning operation. On the other hand, even if the structure is thick and exceeds 400 μm, the effect of improving the corrosion resistance cannot be expected, and it only causes high costs.

Conventional YF ₃ and YOF thermal sprayed films are crystalline films. When the powder melts and solidifies, it changes from amorphous to crystalline, forming cracks and pores in the coating layer. In the present invention, a part of the Al ₂ O ₃ component is added to the powder, and the corresponding substance has an amorphous characteristic when forming a thermal spray film. When a powder containing a substance having such characteristics is melted and solidified by means of a plasma, most of the powder changes from amorphous to crystalline, but a part of the Al ₂ O ₃ substance remains amorphous, which is expected to suppress the occurrence in the coating layer in the past. The formation of cracks and pores. As a result, the effect of cracks occurring in the grain boundary and the number of particles generated thereby was significantly reduced.

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

Preferably, in the constituents of the thermal spray coating, the weight ratio (F / Y) of fluorine to yttrium is 0.7 to 1.3. When the weight ratio (F / Y) of fluorine to this yttrium exceeds 1.3, the fluorine concentration is high, the hardness of the thermal spray coating is reduced, and the etching rate is increased.

Therefore, the YOF-Al multi-component thermal spraying film produced by means of atmospheric plasma is superior in hardness and porosity compared with the original thermal spraying film of yttrium fluoride and oxyfluoride yttrium, and has better etching than the original The yttrium oxide thermal spray coating applied to the semiconductor chamber used in the step has a better level.

In addition, the YOF-Al composition confirmed in the mixed, granulated, and fired thermal spray material is also detected in the thermal spray coating film generated by the atmospheric plasma method. Using this, it is easy to use Control the physical properties of the thermal spray coating under different components.

Hereinafter, the present invention will be described in more detail through examples. However, the following embodiments are merely examples of the present invention, and the present invention is not limited by the embodiments.

<Example>

The yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) were appropriately mixed, granulated, and fired to obtain a powdered thermal spray material. The thermal spray material was produced by changing the composition ratio of the primary material composed of 30 to 70% by mass of YF ₃ and (Al ₂ O ₃ + YAG).

<Example 1>

(1) Manufacturing process of thermal spray materials

A granulated powder was obtained by mixing a binder with yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) powders by means of a spray dryer. This granulated powder was sintered after degreasing to obtain a sintered powder.

(2) Manufacturing process of thermal spray coating

Using the thermal spray material and the plasma gun prepared in step (1), argon and hydrogen flow into the heat source gas. While moving the thermal spray gun, the plasma is generated at a power of 40 to 50 kW. The raw material powder is melted to form 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 is shown in Table 1 below.

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

Raw materials are provided to produce a thermal spray coating having a composition ratio of the primary material as shown in Table 1 below, and the thermal spray material is granulated. The heat treatment temperature of the granulated thermal spray material is shown in Table 1 below. . Then, a thermal spray coating film was formed on the obtained thermal spray material under the same conditions as in Example 1.

The thermal spray coatings produced according to Examples 1 to 6 and Comparative Examples 1 to 6 were analyzed, and experimental data showing the component ratio of each element as shown in Table 1 were obtained. In order to measure the physical properties of the thermal spray coatings of the respective examples, the following experiments were performed, and the physical property values thus obtained are summarized in Table 1 below. In addition, for reference, Comparative Examples 7 to 9 also show the physical properties of the thermal spray coatings conventionally used. The YOF-Al multi-component thermal spray coating was analyzed by scanning electron microscope (SEM) for x-ray spectroscopy (EDS), and detected Y, O, F, and Al components. It has x-ray diffraction analysis (XRD) ) Crystal properties during analysis.

Table 1

＜ Experimental Example 1-Measurement of Concentration of Components in Thermal Spray Coatings ＞

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

The analysis of the component content is to cut the thermal spray coating into a surface orthogonal to the surface of the base material, and then grind the obtained cross section with embedded resin. Then use an electron microscope (JEOL, JS-6010) to measure the cross section of the cross section image by EDS. . In the EDS measurement, the composition was confirmed by using a CPS value to confirm a value of 100,000 counts or more in one minute.

＜ Experimental Example 2-Observation of Thermal Spray Coatings ＞

FIG. 1 is a scanning electron microscope (SEM) photograph of a side of a thermal spray film of Comparative Examples (Comparative Examples 7, 8, 9) and Examples (Example 1) of the present invention. Scanning electron microscope (SEM) photographs confirming that the pore area of the multi-component thermal spray coating produced in Example 1 is smaller than the thermal spray coating produced in Comparative Examples 7, 8, and 9.

In addition, Table 1 shows the porosity obtained from the pore area shown in the cross sections of the thermal spray coatings produced in Comparative Examples (Comparative Examples 7, 8, 9) and Examples (Example 1). . The porosity was measured as shown below. That is, the thermal spray coating was cut into a surface orthogonal to the surface of the substrate, and the obtained cross-section was embedded with resin, and then 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) to specify the area of the stomata in the cross-sectional image, and the area ratio of the area of the stomata to the cross-section was calculated to obtain the Porosity.

The porosity of the thermal spray coatings 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 show a porosity value of 1 to 2%, and show that the density of the multi-component thermal sprayed film of the present invention is higher than that of conventionally used components of the thermal sprayed film.

FIG. 2 is a scanning electron microscope (SEM) photograph of the surfaces of the thermal spray coatings of Comparative Examples (Comparative Examples 7, 8) and Examples (Example 1) of the present invention. From the scanning electron microscope (SEM) photograph of the surface of the thermally sprayed film in FIG. 2, it was observed that the number of cracks appearing on the surface of the thermally sprayed film produced according to Comparative Examples 7 and 8 was higher than that of the multi-component heat produced according to Example 1. Significant reduction in 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 Vickers hardness is measured using a microwave hardness tester and a Vickers hardness (Hv0.2) obtained when a test force of 294.2 mN is applied by means of a diamond indenter with an angle of 136 ° between opposite surfaces.

As shown in Table 1, the yttrium-based thermal spray coatings of Comparative Examples 7 to 9 exhibited a hardness of 300 to 400 Hv, but the YOF-Al multi-component thermal spray coatings of Examples 1 and 2 exhibited a hardness of 450 to 500 Hv. Therefore, the present invention It has higher mechanical properties than conventional yttrium thermal spray coatings.

<Experimental Example 4-Measurement of Etching Speed>

The "Plasma Etch Rate" column in Table 1 shows the results of evaluating the etching rate when each thermal spray coating was exposed to the 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 attached were mounted on a member that was in contact with an upper electrode in a chamber of a parallel flat-type semiconductor device manufacturing apparatus. In addition, a silicon wafer was mounted on a platform in a chamber, and a trial operation of plasma dry etching was performed for two hours. The pressure in the chamber was kept at 0.1torr, and an etching gas containing carbon tetrafluoride was supplied. During a period of 2 hours, 700W high-frequency power was connected to the upper part, and 250W high-frequency power was connected to the lower part. Plasma.

After the plasma etching step, three-dimensional analysis (KEYENCE, VK-X150K 3D analysis) was performed on the components that were installed in the chamber of the semiconductor device manufacturing device, thereby obtaining the etching rate of the thermal spray coating.

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

The specific part of the content of the present invention has been described in detail above. This specific description is only a preferred embodiment, and the scope of the present invention is not limited thereto. It is self-evident that those skilled in the art can belong to this field. Therefore, the substantial scope of the present invention is defined by the appended claims for patent scope and their equivalents.

no

FIG. 1 is a scanning electron microscope (SEM) photograph of the side of a thermal spray coating of Comparative Examples (Comparative Examples 7, 8, 9) and Examples (Example 1) of the present invention.

FIG. 2 is a scanning electron microscope (SEM) photograph of the surfaces of the thermal spray coatings of Comparative Examples (Comparative Examples 7, 8) and Examples (Example 1) of the present invention.

Claims (10)

A method for manufacturing a YOF-Al multi-component thermal spraying material, comprising: changing the ratio of yttrium fluoride (YF ₃ ) to 30 to 70% by mass and the remainder of alumina (Al ₂ O ₃ ), yttrium aluminum garnet (YAG) Mix, granulate, and fire to produce YOF-Al multi-component thermal spray materials. The method according to item 1 of the scope of patent application, wherein the average particle diameter of the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) particles is 0.01 μm or more and 7 μm the following. The method of claim 1, wherein the firing temperature is 500 to 1100 ° C. A Y-O-F-Al multi-component thermal spraying material is prepared by a method according to any one of items 1 to 3 of the scope of patent application, and has an average particle diameter of 5 μm or more and 100 μm or less. A method for manufacturing a Y-O-F-Al multi-component thermal spray coating film, comprising: thermally spraying the Y-O-F-Al multi-component thermal spray coating material described in item 4 of the patent application scope, to form a film on a substrate. The method according to item 5 of the patent application scope, wherein the thermal spraying is plasma thermal spraying. A Y-O-F-Al multi-component thermal spray coating is formed by the method of manufacturing a Y-O-F-Al multi-component thermal spray coating as described in item 5 of the patent application scope, and has a thickness of 50 to 400 μm. A Y-O-F-Al multi-component thermal spray coating is formed by the method of the Y-O-F-Al multi-component thermal spray coating described in item 5 of the scope of patent application, and has a thickness of 50 to 400 μm. A YOF-Al multi-component thermal spray coating film, which includes yttrium (Y), oxygen (O), fluorine (F), and aluminum (Al) as constituent elements. The weight ratio of the aluminum element to the yttrium and fluorine ( Al / Y + F) is 0.025 to 0.25. The Y-O-F-Al multi-component thermal spray coating according to item 9 of the scope of the patent application, wherein the weight ratio (F / Y) of fluorine to yttrium is 0.7 to 1.3.