WO2019124660A1 - Spray coating material and spray coating made of same spray coating material - 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

A sprayed coating made of a sprayed material and a sprayed material thereof

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

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

In order to be used in such an environment, methods have been proposed in which materials having excellent plasma resistance are used as chamber members or coatings are formed of materials having excellent plasma resistance on the surface of members.

Of these, techniques for imparting new functionality by coating the surface of a substrate with various materials have been used in various fields in the past. As one of such surface coating techniques, there is known a thermal spraying method in which a thermal sprayed coating is formed by spraying thermal sprayed particles made of a material such as ceramics, for example, on the surface of a substrate in a softened or melted state by combustion or electric energy.

Generally, a spray coating is performed by heating and melting fine powders and spraying molten powders toward the coated side of the base material. The injected molten powder is quenched and the molten powder solidifies and is laminated on the surface to be coated mainly by mechanical bonding force.

Plasma spray coating for melting the powders using the high-temperature plasma flame of the thermal spray coating is essentially used for the coating of metals and ceramics such as tungsten or molybdenum with a high melting point. The thermal spray coating is advantageous for producing a high-performance material that utilizes the material properties of the base material to exhibit characteristics of abrasion, corrosion, heat resistance and thermal barrier, hardness, oxidation resistance, insulation, friction characteristics, heat radiation, However, it is possible to coat objects with a large area in a short period of time in comparison with other coating methods such as chemical vapor deposition and physical vapor deposition.

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 using plasma of a halogen-based gas such as fluorine, chlorine or bromine. After the dry etcher, the interior of the chamber (vacuum container) from which the semiconductor substrate is taken out is cleaned using oxygen gas plasma. At this time, there is a possibility that the member exposed to the highly reactive oxygen gas plasma or the halogen gas plasma is corroded in the chamber. Then, when the corrosion (erosion) portion from the member falls into the particulate form, such a particle can be a foreign matter adhering to the semiconductor substrate and causing a defect in the circuit (hereinafter, the foreign matter is referred to as a particle).

Therefore, conventionally, in a semiconductor device manufacturing apparatus, a ceramic thermal spraying film having plasma corrosion resistance is provided on a member exposed to a plasma such as an oxygen gas or a halogen gas for the purpose of reducing the generation of particles.

The cause of the particle generation is deterioration of the chamber by using a halogen gas plasma or an oxygen gas plasma in addition to the exfoliation of reaction products adhered to the vacuum chamber. Further, according to a study by the present inventors, it has been confirmed that the number and size of particles generated from the thermal sprayed coating under a dry-etched environment are greatly affected by the composition of the thermal sprayed coating.

Particularly, the parts that come into contact with the halogen-based gas plasma of the etching apparatus employ yttrium oxide or yttrium fluoride which is excellent in corrosion resistance to metallic aluminum or aluminum oxide ceramics as a coating film. However, yttrium reacts with the fluorine-based gas at the uppermost surface of the initial stage of the process to change the concentration of the plasma in the apparatus, thereby causing an unstable etching process condition (process shift). In addition, the yttrium fluoride thermal spray coating has a low reactivity with the fluorine-based gas, but has a surface cracking and a low hardness compared with yttrium oxide, so that the etching rate is high and the replacement cycle of the member is shortened.

Therefore, recently, there have been disclosed techniques capable of forming a spray coating having high corrosion resistance to plasma by using yttrium oxyfluoride particles prepared by mixing yttrium oxide and yttrium fluoride as a solvent for use. (Patent Documents 1 to 5)

Korean Patent Laid-Open No. 10-2017-0078842 (Jul.07.07, 2017) discloses a film-forming powder containing oxyfluoride (Ln-OF) of a rare earth element, and has an average particle size (D50) is not more than 10 ㎛, and the volume of pores of less than diameter 10 ㎛ measured by mercury porosimetry 0.1 cm over ³ / g 0.5 cm ³ / g or less, the corrosion resistance against the chlorine-containing plasma is described for high-used material for . Korean Patent Laid-Open No. 10-2016-0131916 (Nov. 16, 2016) includes rare earth element RE, oxygen O and halogen element X as constituent elements and rare earth element oxyhalide RE- OX) is contained in a proportion of 77 mass% or more.

Also, Korea Patent Publication No. 10-2016-0131917 No. (2016.11.16.), In the X-ray diffraction pattern of the material for use, to the peak intensity I _A of the main peak of the rare earth element oxy halide, a rare earth element oxide (I _B + I _C ) / I _A ) of the sum of the peak intensity I _B of the main peak of the rare earth element halide and the peak intensity I _C of the main peak of the rare earth element halide is less than 0.02 is used as the material for the rare earth element oxyhalide .

The above Patent Documents 2 and 3 disclose a method of reducing the amount of rare earth element fluoride which can be transformed into rare earth element oxide by spraying with a rare earth element oxide which generates particles due to the amorphous nature and to provide a rare earth element oxyhalogen The physical properties of the sprayed material were improved by increasing the amount of the cargo.

The use material disclosed in Korean Patent Laid-Open No. 10-2016-0131918 (Nov. 16, 2016) has a rare earth element oxyhalide including rare earth element (RE), oxygen (O) and halogen element (X) (RE-OX), and the molar ratio (X / RE) of the halogen element to the rare-earth element is 1.1 or more, thereby improving plasma resistance and excellent properties such as porosity and hardness.

In addition, Korean Patent Laid-Open No. 10-2017-0015236 (Feb. 27, 2017) discloses a yttrium-type thermal sprayed coating film having a thickness of 10 to 500 占 퐉 containing one or more of yttrium oxide, yttrium fluoride and yttrium oxyfluoride , And the surface of the coating film is washed with a specific solvent so that the number of particles having a particle diameter of 300 nm or less present on the surface is 1 mm ² A technique for manufacturing a yttrium-based thermal spray coating that can reduce the number of particles to less than 5 per particle to prevent the phenomenon of particle desorption.

As described above, in order to overcome the physical limitations of yttrium oxide or yttrium fluoride thermal spraying materials until now, yttrium oxyfluoride and yttrium fluoride have been mixed to produce yttrium oxyfluoride which improves physical properties such as plasma erosion resistance, porosity and hardness Techniques for manufacturing sprayed materials have been proposed.

However, in the preparation of the oxyfluoride thermal sprayed coating of yttrium, the fluorine component of the thermal sprayed coating is partially reduced and replaced with oxygen due to the high-temperature reaction conditions, resulting in a difference in the composition of the thermal sprayed coating and difficulty in forming a uniform thermal sprayed coating And there is a continuing demand for the improvement of the plasma plasma characteristics of the yttrium oxyfluoride coating film described in the above prior arts.

It is an object of the present invention to provide a method for improving the plasma plasma characteristics of a yttrium oxyfluoride thermal spraying material and a thermal spray coating.

In order to achieve the above object, one embodiment of the present invention is characterized in that the specific gravity of yttrium fluoride (YF ₃ ) is 30 to 70% by mass and the residue is mixed with alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) , Assembling, and firing to produce a YOF-Al multicomponent thermal spraying material.

In a preferred embodiment of the present invention, the average particle diameter of the yttrium fluoride (YF ₃ ), alumina (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 ° C to 1100 ° C.

Another embodiment of the present invention provides a Y-O-F-Al multicomponent thermal sprayed material prepared by the above-described method for producing a Y-O-F-Al multicomponent thermal spraying material and having an average particle diameter of 5 m or more and 100 m or less.

Another embodiment of the present invention provides a method for producing a Y-O-F-Al multi-component thermal spray coating that forms a coating on a substrate by spraying the Y-O-F-Al multicomponent thermal spraying material.

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

Another embodiment of the present invention provides a Y-O-F-Al multicomponent thermal sprayed coating formed by the method of producing the Y-O-F-Al multicomponent thermal sprayed coating and having a thickness of 50 탆 to 400 탆.

Another embodiment of the present invention is a method of manufacturing a semiconductor device, comprising the steps of: preparing a semiconductor substrate including yttrium (Y), oxygen (O), fluorine (F), and aluminum (Al) F) of 0.025 to 0.25 is provided.

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

The YOF-Al multicomponent thermal spraying material according to the present invention does not cause a change in the composition of the oxygen component and the fluorine component contained in the thermal sprayed coating during the spray manufacturing process, and suppresses the formation of cracks and pores which have occurred in the conventional coating layer It is possible to form a thermal spray coating more densely than a conventional coating layer.

The YOF-Al multicomponent thermal sprayed coating of the present invention has an increased hardness and lower porosity than yttrium fluoride and yttrium oxide of the prior art, and improved plasma plasma characteristics, The cycle can be extended.

1 is a scanning electron micrograph (SEM) photograph of a side surface of a thermal sprayed coating according to Comparative Examples (Comparative Examples 7, 8 and 9) and Example (Example 1) according to the present invention.

2 is a scanning electron micrograph (SEM) photograph of the surface of the thermal sprayed coating according to the comparative examples (Comparative Examples 7 and 8) and Example (Example 1) according to the present invention.

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

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In the semiconductor manufacturing process, a gate etcher, an insulating film etcher, a resist film etcher, a sputtering apparatus, a CVD apparatus, and the like are used. On the other hand, in the liquid crystal manufacturing process, an etcher device for forming a thin film transistor is used. In these manufacturing apparatuses, a plasma generating mechanism is provided for the purpose of high integration by micromachining.

As the process gas in these manufacturing processes, halogen-based corrosion gases such as fluorine-based and chlorine-based gases have been used in the above-mentioned apparatus due to their high reactivity. Examples of the fluorine-based gas include SF ₆ , CF ₄ , CHF ₃ , ClF ₃ , HF and NF _3. Examples of the chlorine-based gas include Cl ₂ , BCl ₃ , HCl, CCl ₄ and SiCl ₄ . When a microwave or a high frequency wave is introduced into the plasma, these gases are converted into plasma. Since the apparatus members exposed to these halogen-based gases or plasma thereof are required to have very few metals other than material components on their surfaces and to have high corrosion resistance, the present invention relates to a plasma- YOF-Al multi-component thermal spraying material and a method for producing a thermal spray coating.

Hereinafter, a method for producing a Y-O-F-Al multicomponent thermal sprayed material will be described in detail.

In one aspect of the present invention, yttrium fluoride (YF ₃ ) has a specific gravity of 30 to 70% by mass and the balance is mixed with alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) Thereby providing a method for manufacturing a sprayed material.

The use of yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) materials, which are primary materials, as unstructured powders or slurries containing ungrafted powders However, it is preferable to form the granulated particles through mixing, granulation, and firing processes in which the flowability of the material does not reach the level required for thermal spraying and is manufactured in a spherical shape.

It is preferable that the sprayed material as the assembled powder is filled up to the inside. This is because it is stable and does not break when handling the powder, and if there is a void portion, it is easy to contain an undesirable gas component in the void portion, It is necessary in that it can do.

In the mixing and granulating process, the sintering auxiliary agent and the dispersion medium are added to the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG), followed by pulverization and mixing, followed by dehydration and drying. If necessary, the granulated particles may be further mixed with a binder to prepare a slurry droplet, followed by granulation and firing. As the binder, organic compounds are preferable, and organic compounds composed of carbon, hydrogen and oxygen, or carbon, hydrogen, oxygen and nitrogen, such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and the like.

The yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) particles undergo the assembly process. As the assembling apparatus, for example, a spray drying apparatus can be used. In the spray drying apparatus, a droplet of a slurry containing a plurality of pulverized particles is dropped in a hot air stream, whereby the droplet is solidified and the intermediate particles including a plurality of particles are assembled.

In terms of the assembly process, it is preferable that the yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) particles have an average particle diameter of 0.01 μm or more and 7 μm or less. When the diameter of the particles is less than about 0.01 탆, the average diameter of the powder for spray coating having the granulation structure containing the yttrium oxide particles may be small, and it is difficult to control the particles, and spherical granules are difficult to form. When the diameter of the particles exceeds about 7 탆, the average diameter of the granulated particles formed by the granulation is too large, so that it is difficult to form a uniform thermal spray coating.

Thereafter, the granulated particles are subjected to a sintering step, and the sintering temperature is preferably 500 ° C to 1100 ° C. By firing in this temperature range, yttrium oxyfluoride and aluminum compound react sufficiently. If the sintering temperature is less than 500 ° C, the mixing reaction is insufficient and 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 Deg.] C to 1000 [deg.] C is effective in improving the plasma resistance of the multi-component thermal sprayed coating. Concretely, when the firing temperature is less than 800 ° C, the hardness of the thermal sprayed coating is not sufficient, and the plasma resistance of the thermal sprayed material is lowered.

The firing time was set to be 2 Hour to 8 hours or less is preferable . Within this range, sufficient YOF-Al multicomponent compounds are produced and energy consumption is minimized.

An oxygen-containing atmosphere such as an atmospheric atmosphere can be used as the firing atmosphere, but an inert gas atmosphere such as argon gas or a vacuum atmosphere is preferable.

The average particle diameter of the sprayed material produced by mixing, assembling and firing is preferably 5 탆 or more and 100 탆 or less in terms of improving the quality of the sprayed coating. If the average particle diameter is less than 5 탆, the flowability of the powder during the spray coating is low, so that a uniform film can not be realized. The powder is not oxidized or transferred to the frame center before the powder is delivered to the frame, It is difficult to satisfy such a requirement that a film having a high porosity or a low hardness is formed. If the average particle diameter is more than 100 占 퐉, the powder is not completely melted when injected into the plasma, resulting in an unmelted portion in the coating film, which makes it difficult to satisfy the quality of the thermal spraying film required in the present invention.

The aspect ratio of the spraying material powder of the present invention is expressed by the ratio of the long diameter to the short diameter of the particles, and 1.0 or more and 5.0 or less is preferable from the viewpoint of forming a dense and uniform film, and the aspect ratio is 1.0 More preferably 4.0 or less, and particularly preferably 1.0 or more and 1.5 or less.

It is most preferable that the spraying material powder is formed into a spherical shape, which is an important factor of the quality of the sprayed film. Otherwise, when the sprayed coating is formed, a certain amount of powder is not transferred to the frame, I can not.

Further, a method for producing a Y-O-F-Al multi-component thermal spray coating film in which the Y-O-F-Al multi-component thermal spraying material is plasma-sprayed to form an aluminum oxyfluoride film on the substrate will be described below.

The plasma spraying method generally includes a coating method in which a spraying material is obtained by charging a material to be used for the plasma jet, and heating and accelerating the material to deposit on the substrate. The plasma spraying method can be applied to atmospheric plasma spraying (APS) in air, low pressure plasma spraying (LPS) spraying at a pressure lower than atmospheric pressure, plasma spraying in a pressure vessel higher than atmospheric pressure, Such as high pressure plasma spraying or the like. According to this plasma spraying, for example, by spraying and accelerating the sprayed material by a plasma jet of about 10000 K to 15000 K, the sprayed particles are collided with the substrate at a speed of about 300 m / s to 1000 m / s So that it can be deposited.

The spraying of the substrate of the present invention can be performed by atmospheric pressure plasma spraying. 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. .

As a specific example of the spraying, in the case of argon / hydrogen plasma spraying, atmospheric plasma spraying using a mixed gas of argon and hydrogen in an air atmosphere can be mentioned. Conditions for spraying such as spraying distance, current value, voltage value, argon gas supply amount, hydrogen gas supply amount, etc. are set according to the use of the sprayed member. A predetermined amount of the spray material is charged into the powder feeder, and the powder is supplied to the tip of the plasma event by the carrier gas (argon) using the powder hose. By continuously supplying the powder during the plasma flame, the sprayed material is melted and liquefied, and is liquid-phase framed by the force of the plasma jet. The molten powder adheres, solidifies, and deposits by touching the liquid phase frame on the substrate. By this principle, a Y-O-F-Al multi-component film forming component (sprayed member) can be manufactured by forming a Y-O-F-Al multi-component thermal spray coating within a predetermined coating range on a substrate while moving the frame left and right and up and down.

In the present invention, the substrate coated with the thermal sprayed coating is not particularly limited. For example, the material, the shape, and the like are not particularly limited as long as it is a substrate including a material capable of providing desired resistance to the spraying of such a material for use. Examples of the material constituting such a sprayed substrate include at least one of aluminum, nickel, chromium, zinc and their alloys, alumina, aluminum nitride, silicon nitride, silicon carbide and quartz glass constituting members for semiconductor manufacturing apparatuses It is preferable to select one or more combinations.

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

It is preferable that the surface of the substrate is treated in accordance with the ceramics spraying working standard prescribed in JIS H 9302 before plasma spraying. For example, after removing rust, grease, and the like on the surface of the substrate, grinding particles such as Al ₂ O ₃ and SiC are sprayed to roughen the surface, and the pre-treatment is performed so that the fluoride sprayed particles are easily adhered.

In addition to the plasma spraying, the method for producing the thermal spray coating can be formed by providing the thermal spraying material disclosed herein to a thermal spraying apparatus based on a known thermal spraying method. Examples of the spraying method for appropriately spraying the material for use include a spraying method such as a high-speed frame spraying method, a frame spraying method, and an explosive spraying method.

The characteristics of the sprayed coating may depend to some extent on the spraying method and the spraying conditions. However, even when any spraying method and spraying condition are employed, it is possible to form a sprayed coating excellent in plasma erosion resistance as compared with the case of using other spraying materials by using the spraying materials disclosed herein.

The Y-O-F-Al multicomponent thermal sprayed coating is preferably formed to a thickness of 50 mu m to 400 mu m. In this case, if the thickness is less than 50 占 퐉, sufficient corrosion resistance may not be obtained, and there is also a possibility that the surface of the substrate is partially exposed by the cleaning operation. On the other hand, even if it is thicker than 400 탆, the effect of improving the corrosion resistance can not be expected in particular, but the cost is high.

Conventional YF ₃ and YOF sprayed films are crystalline films, and when the powder is melted and solidified, it transforms from amorphous to crystalline and forms 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 material has an amorphous property when forming a sprayed film. Powder containing such a substance is transformed from amorphous to crystalline by melt-solidification by plasma, but some Al ₂ O ₃ materials remain as amorphous to inhibit the formation of cracks and pores in the conventional coating layer Is predicted. As a result, cracks occurring in grain boundaries and the number of particles caused thereby are remarkably reduced.

Wherein the multi-component thermal spray coating is composed of yttrium (Y), oxygen (O), fluorine (F) and aluminum (Al), and the weight ratio [Al / (Y + F)] of the aluminum element to yttrium and fluorine is 0.025 To 0.25. When the weight ratio of aluminum element to yttrium and fluorine [Al / (Y + F)] is less than 0.025 in the thermal sprayed coating, the Al ₂ O ₃ amorphous portion is insufficient and the hardness of the thermal sprayed coating is low, The effect of improvement can not be achieved.

It is preferable that a weight ratio (F / Y) of fluorine to yttrium among the constituents of the thermal sprayed coating is 0.7 to 1.3. When the weight ratio (F / Y) of fluorine to yttrium is more than 1.3, the hardness of the thermal sprayed coating is lowered due to the high fluorine concentration, and the etching rate is increased.

Therefore, the YOF-Al multi-component thermal sprayed film produced by atmospheric plasma has superior hardness and porosity level compared with the yttrium fluoride yttrium and yttrium fluoride yttrium coating and is superior to the yttrium oxide thermal spray coating used in semiconductor chambers used in the conventional etching process .

Also, it is easy to control the physical properties of the thermal sprayed film according to the composition, by utilizing the fact that the Y-O-F-Al component confirmed in the mixed, assembled, and sintered thermal spraying materials is also detected in the thermal sprayed coating produced by the atmospheric plasma method.

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

<Examples>

Yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ), and yttrium aluminum garnet (YAG) were appropriately mixed, assembled, and fired to obtain a powdery thermal sprayed material. The composition ratio of the primary material consisting of 30 to 70 mass% of YF ₃ and (Al ₂ O ₃ + YAG) remnant was changed to prepare a sprayed material.

&Lt; Example 1 >

(1) Manufacturing process of spraying material

A binder powder was mixed with yttrium fluoride (YF ₃ ), alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG) powders, followed by spray drying to obtain granulated powders. The granulated powder was degreased and then sintered to obtain a sintered powder.

(2) Manufacturing process of spray coating

The plasma is generated at a power of 40 to 50 kW while flowing the argon and hydrogen gas using a heat source gas by using the thermal spray material and the plasma gun prepared in the step (1), and the material powder is melted using the generated plasma A coating film was formed on the base material. The thickness of the coating film was set to be 150 to 200 탆, and the proportions of components of the obtained thermal spray coating were as shown in Table 1 below.

&Lt; Examples 2 to 6 and Comparative Examples 1 to 6 >

The raw materials were blended so as to produce a thermal spray coating having the composition ratios of the primary materials shown in Table 1 below, and the thermal spraying temperatures of the sprayed materials were as shown in Table 1 below. Thereafter, the sprayed coating was formed under the same conditions as in Example 1 using the obtained sprayed material.

The thermal sprayed coatings prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were analyzed to obtain experimental data showing composition ratios of the respective elements as shown in Table 1. In order to measure the physical properties of the thermal sprayed coatings of the examples, the following tests were conducted and the physical properties obtained therefrom are summarized in Table 1 below. For reference, physical properties of the thermal sprayed coatings used in the past are also shown in Comparative Examples 7 to 9. Y-O, F, and Al components are detected during X-ray spectroscopy (EDS) analysis of YOF-Al multi-component spray coatings by electron microscopy (SEM). X-ray diffraction (XRD) .

[Table 1]

Experimental Example 1 - Measurement of component concentration of sprayed coating [

In order to analyze the changes in Y, O, F and Al component contents in the thermal sprayed coatings prepared in Examples 1 to 6 and Comparative Examples 1 to 9, an EDS analysis was carried out and the results are shown in Table 1 .

The component content was determined by cutting the sprayed coating to a plane orthogonal to the surface of the substrate, polishing the obtained cross-section by resin embedding and polishing, and then measuring the EDS of the cross-sectional image using an electron microscope (JEOL, JS-6010) The CPS value was confirmed as a sample with a value of more than 100,000 counts for 1 min.

Experimental Example 2 - Observation of sprayed coating &gt;

1 is an electron micrograph (SEM) photograph of a side surface of a thermal sprayed coating according to Comparative Examples 7, 8 and 9 and Example 1 of the present invention, SEM photographs showed that the area of the pores of the multi-component thermal sprayed coating prepared in Example 1 was smaller than that of the thermal sprayed coatings prepared in Comparative Examples 7, 8, and 9.

The porosity obtained through the area of the pores shown in cross sections of the thermal sprayed coatings prepared in the comparative examples (Comparative Examples 7, 8, 9) and Example (Example 1) is shown in Table 1. The porosity was measured in the following manner. That is, the thermal sprayed coating was cut into a surface orthogonal to the surface of the substrate, and the obtained cross-section was resin buried and polished, and then the cross-sectional image was taken using an electron microscope (JEOL, JS-6010) (FIG. The image was analyzed by using image analysis software (MEDIA CYBERNETICS, Image Pro) to determine the area of the pore portion in the cross-sectional image and calculating the ratio of the area of the pore portion to the cross-section.

The porosity of the thermal sprayed coating prepared in Comparative Example 8 and Comparative Example 9 was 3% to 4%, and the porosity of the thermal sprayed YF ₃ coating formed in Comparative Example 7 was 2% to 3% %. However, Examples 1 and 2 show values of porosity of 1% to 2%, indicating that the density of the multi-component thermal spray coating according to the present invention is higher than that of conventionally used thermal spray coatings.

2 is a scanning electron micrograph (SEM) photograph of the surface of the thermal sprayed coating according to the comparative examples (Comparative Examples 7 and 8) and Example (Example 1) according to the present invention. 2, the number of cracks appearing on the surface of the thermal sprayed coating prepared by Comparative Examples 7 and 8 was remarkably reduced on the surface of the multi-component thermal sprayed coating produced by Example 1 through the scanning electron microscope (SEM) photograph of the surface of the thermal sprayed coating Respectively.

<Experimental Example 3 - Hardness Measurement>

The column of &quot; Hardness &quot; in Table 1 shows the measurement results of the Vickers hardness of the respective thermal sprayed coatings. The Vickers hardness was measured using a microhardness tester (company name, model name), and the Vickers hardness (Hv 0.2) obtained when a test force of 294.2 mN was applied by a diamond indenter having a face angle of 136 degrees.

As shown in Table 1, the yttrium-based thermal sprayed coatings of Comparative Examples 7 to 9 exhibited a hardness of 300 to 400 Hv, whereas the YOF-Al multicomponent thermal sprayed coatings of Examples 1 and 2 exhibited 450 to 500 Hv hardness The present invention has improved mechanical properties over conventional yttrium spray coatings.

Experimental Example 4 - Measurement of etching rate [

The column of "Plasma Etch Rate" in Table 1 shows the result of evaluating the etching rate when each thermal sprayed film is exposed to plasma under the following conditions. That is, first, the members having the thermal sprayed coatings of Comparative Examples 7 to 9 and Examples 1 and 2 were provided on the member in contact with the upper electrode in the chamber of the parallel plate type semiconductor device manufacturing apparatus. Then, a silicon wafer was placed on the stage in the chamber, and a dummy run was performed for 2 hours to perform the plasma dry etching. The plasma in the etching treatment was generated by applying a high frequency power of 700 W at the top and 250 W at the bottom for 2 hours while maintaining the pressure in the chamber at 0.1 torr and supplying an argon gas containing carbon tetrafluoride.

The etch rate of the sprayed coating was obtained by three-dimensional analysis (KEYENCE, VK-X150K 3D analysis) of the members that were installed in the chamber of the semiconductor device manufacturing apparatus after the plasma etching process.

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

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

1. A method for producing a YOF-Al multicomponent thermal sprayed material by mixing 30 to 70% by mass of yttrium fluoride (YF ₃ ) and the balance of alumina (Al ₂ O ₃ ) and yttrium aluminum garnet (YAG).
2. The method according to claim 1,

   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 or less.
3. The method according to claim 1,

   Wherein the calcining temperature is in the range of 500 ° C to 1100 ° C.
4. A Y-O-F-Al multicomponent thermal sprayed material produced by the method of any one of claims 1 to 3, wherein the Y-O-F-Al multicomponent thermal spraying material has an average particle diameter of 5 mu m or more and 100 mu m or less.
5. A method for producing a Y-O-F-Al multicomponent thermal sprayed coating, wherein the Y-O-F-Al multicomponent thermal spraying material of claim 4 is sprayed to form a coating on a substrate.
6. 6. The method of claim 5,

   Wherein the spray is a plasma spray. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
7. A Y-O-F-Al multicomponent thermal sprayed coating formed by the method for producing a Y-O-F-Al multicomponent thermal spray coating according to claim 5 and having a thickness of 50 탆 to 400 탆.
8. A Y-O-F-Al multicomponent thermal sprayed coating formed by a method for producing a Y-O-F-Al multicomponent thermal spray coating of claim 6 and having a thickness of 50 탆 to 400 탆.
9. In the multi-component thermal spray coating,

   (Al / Y + F) of 0.025 to 0.25 in terms of yttrium (Y), oxygen (O), fluorine (F) and aluminum YOF-Al multi-component thermal spray coating.
10. 10. The method of claim 9,

    Wherein the weight ratio (F / Y) of fluorine to yttrium is 0.7 to 1.3.

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