KR20230173314A - Corrosion-resistant ceramic part and manufacturing method of the same - Google Patents

Abstract

Embodiments include a basic mixture consisting of yttria and a first metal compound, wherein the basic mixture includes 1 wt% to 35 wt% of the first metal compound, and the first metal includes zirconium, aluminum, and combinations thereof. Provided is an etch-resistant ceramic part selected from the group consisting of, and having an average grain size of 2 ㎛ or less, and a method for manufacturing the same.

Description

CORROSION-RESISTANT CERAMIC PART AND MANUFACTURING METHOD OF THE SAME}

Embodiments relate to etch-resistant ceramic parts and methods for manufacturing the same.

Recently, the circuit design of electronic devices has become increasingly finer, and higher dimensional precision is required for etching using plasma, so significantly higher power is being used. Inside this etching device using plasma, various parts exposed to plasma are built, for example, a focus ring, an edge ring, a shower head, etc.

These parts are etched by plasma and may require periodic replacement depending on the degree of etching. Frequent replacement, opening of the internal chamber of the plasma etching device, etc. can cause a decrease in the manufacturing yield and productivity of microelectronic devices, and to prevent this, parts with improved plasma etching resistance are required.

The above-described background technology is technical information that the inventor possessed to derive the implementation example or acquired during the derivation process, and cannot necessarily be said to be known technology disclosed to the general public before the application for the present invention.

With related prior art,

“Plasma processing device including electrically conductive parts and manufacturing method of the same” disclosed in Korean Patent No. 10-1811534;

There is a “process component with improved plasma etch resistance and a method for enhancing the plasma etch resistance of the process component” disclosed in Korean Patent Publication No. 10-2015-0068285.

The purpose of the embodiment is to provide a ceramic component with excellent strength and good plasma resistance and etching resistance, and a method for manufacturing the same.

Another purpose of the embodiment is to provide an etch-resistant ceramic component that has improved physical properties compared to existing etch-resistant components and can improve the manufacturing yield and productivity of microelectronic devices.

In order to achieve the above object, the etch-resistant ceramic part according to the embodiment,

Comprising a basic mixture consisting of yttria and a first metal compound,

The basic mixture includes 1 wt% to 35 wt% of the first metal compound,

The first metal is one selected from the group consisting of zirconium, aluminum, and combinations thereof,

The average grain size may be 2 ㎛ or less.

In one embodiment, the average grain size may be 1.6 ㎛ or less.

In one embodiment, the etch-resistant ceramic part may have a bending strength of 150 MPa to 280 MPa.

In one embodiment, the basic mixture includes 5 wt% to 35 wt% of the first metal compound,

The first metal is zirconium,

The first metal compound may include any one or more of zirconium oxide and zirconium carbide.

In one embodiment, the average grain size may be 1.1 ㎛ or less.

In one embodiment, the basic mixture includes 3 wt% to 15 wt% of the first metal compound,

The first metal is aluminum,

The first metal silver compound may include at least one of aluminum oxide and yttrium-aluminum composite oxide.

In one embodiment, the etch-resistant ceramic component may be applied as a component of a device exposed to plasma.

In order to achieve the above purpose, the method for manufacturing etching-resistant ceramic parts is,

A mixing step of preparing raw materials including yttria, first metal oxide, and additives;

A screening step of granulating and selecting the raw materials;

It includes a sintering step of molding and sintering the sorted product obtained in the sorting step,

The raw materials are,

A basic raw material mixture consisting of yttria and first metal oxide; and carbon-based materials;

The basic raw material mixture contains 1 wt% to 32 wt% of the first metal oxide,

The first metal may be one selected from the group consisting of zirconium, aluminum, and combinations thereof.

In one embodiment, the raw material further includes a dispersant and a solvent,

Granulation of the raw material may be carried out through spray drying.

In one embodiment, the sintering may be performed at a temperature of 1580°C to 1780°C.

The etch-resistant ceramic part according to the embodiment may have excellent strength, good plasma resistance, and etch resistance. It has improved physical properties compared to existing etch-resistant parts and can improve the manufacturing yield and productivity of microelectronic devices.

Figure 1 is a photograph taken through a scanning electron microscope of the fractured surface of the molded body (green body) obtained in Examples.
Figure 2 is a photograph of the fractured surface of the sintered body obtained in Examples taken at 3000 magnification through a scanning electron microscope.
Figure 3 is a photograph of the fractured surface of the sintered body obtained in Examples taken at 10000 magnification through a scanning electron microscope.
Figure 4 is a photograph taken at 10000 magnification through a scanning electron microscope of the fractured surface of the sintered body obtained in other examples.
Figure 5 is a graph showing the results of X-ray diffraction analysis of the sintered body obtained in Example 5.
Figure 6 is a graph showing the results of X-ray diffraction analysis of the sintered body obtained in Example 1.
Figure 7 is a graph showing the relative density of the sintered body obtained in Examples.
Figure 8 is a graph showing the bending strength of the sintered body obtained in Examples.
Figure 9 is a graph showing the plasma corrosion resistance of the sintered body, alumina, and yttria obtained in Examples.
Figure 10 is a photograph taken through a scanning electron microscope of the surface of the sintered body, alumina, and yttria obtained in Examples after plasma etching.
Figure 11 is a graph showing the thermal conductivity of the sintered body obtained in Examples.
Figure 12 is a graph showing the hardness of the sintered body obtained in Examples.
Figure 13 is a photograph taken through a scanning electron microscope of the surface of the sintered body obtained in Examples.
Figure 14 is a graph showing grain size according to temperature during sintering of the sintered bodies obtained in Examples.
Figure 15 is a graph showing the relative density according to temperature during sintering of the sintered bodies obtained in Examples.
Figure 16 is a graph showing the bending strength according to temperature during sintering of the sintered bodies obtained in Examples.
Figure 17 is a graph showing hardness according to temperature during sintering of the sintered bodies obtained in Examples.
Figure 18 is a graph showing the bending strength according to temperature in the sintered body obtained in Example 1 and the Yttria sintered body from NYC.
Figure 19 is a graph showing the bending strength according to the number of times of heating and quenching in the sintered body obtained in Example 1 and the Yttria sintered body from NYC.
Figure 20 is a photograph taken through a scanning electron microscope of the microstructure according to the zirconia content of the sintered body obtained in Examples and Comparative Examples.
Figure 21 is a graph showing the bending strength according to temperature of the sintered body obtained in Examples and Comparative Examples.

Hereinafter, one or more embodiments will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the invention. However, implementations may be implemented in various different forms and are not limited to the embodiments described herein. Throughout the specification, similar parts are given the same reference numerals.

In this specification, when a configuration “includes” another configuration, this means that other configurations may be further included rather than excluding other configurations, unless specifically stated to the contrary.

In this specification, when a configuration is said to be “connected” to another configuration, this includes not only cases where it is “directly connected,” but also cases where it is “connected with another configuration in between.”

In this specification, B being positioned on A means that B is positioned in direct contact with A or that B is positioned on A with another layer positioned in between, and B is positioned in contact with the surface of A. It is not interpreted as limited to doing so.

In this specification, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression, It means including one or more selected from the group consisting of.

In this specification, the description of “A and/or B” means “A, B, or A and B.”

In this specification, terms such as “first”, “second” or “A” and “B” are used to distinguish the same terms from each other unless otherwise specified.

In this specification, singular expressions are interpreted to include singular or plural as interpreted in context, unless otherwise specified.

Etch-resistant ceramic parts

In order to achieve the above object, the etch-resistant ceramic part according to the embodiment is

Comprising a basic mixture consisting of yttria (Y ₂ O ₃ ) and a first metal compound,

The basic mixture includes 1 wt% to 35 wt% of the first metal compound,

The first metal is one selected from the group consisting of zirconium, aluminum, and combinations thereof,

The etch-resistant ceramic part may have an average grain size of 2 ㎛ or less.

The basic mixture of the etch-resistant ceramic part may include 4 wt% to 30 wt%, 5 wt% to 20 wt%, and 5 wt% to 15 wt% of the first metal compound. By having this yttria and first metal compound content, the desired plasma etching resistance and mechanical properties can be satisfied.

The etching-resistant ceramic part may include a solid solution in which a first metal oxide is dissolved in yttria, or may include a yttrium-first metal composite oxide.

As shown in FIGS. 3 and 4, the etch-resistant ceramic part may include some precipitates on the yttria substrate. Additionally, the precipitates may be exposed at yttria grains or grain boundaries. The precipitate may exemplarily include first metal carbide, first metal oxide, yttrium-first metal composite oxide, etc., and zirconium carbide (ZrC _{, ZrO} (one integer), zirconium-yttrium composite oxide (Zr ₃ Y ₄ O ₁₂ ), yttrium-aluminum composite oxide (Y ₄ Al ₂ O ₉ ), aluminum carbide (Al ₄ C ₃ ), etc.

When precipitates such as first metal compounds and sintering by-products containing the first metal are present in the etching-resistant ceramic parts, the volume ratio may be less than 12% of the total within any unit area of 10 ㎛ × 10 ㎛, , may have a volume ratio of 8% or less.

The size of the precipitate may be 3 ㎛ or less, and may be 1 ㎛ or less. The size of the precipitate may be 10 nm or more.

By having this volume ratio and size of the precipitates, an easy precipitation hardening effect can be expected.

The porosity of the etch-resistant ceramic part may be 5% or less, 2% or less, and 0.1% or less. The porosity may be 0.01% or more.

The first metal compound may be a zirconium compound, zirconium oxide and/or zirconium carbide, yttria-stabilized zirconia, etc. At this time, the basic mixture may contain 5 wt% to 35 wt%, 5 wt% to 25 wt%, and 5 wt% to 15 wt% of the zirconium compound. Etch-resistant ceramic parts containing such zirconium compounds can maintain the grain size at a certain level, and a precipitation hardening effect can be expected through certain precipitates. Additionally, plasma flow control can be facilitated. If the zirconium compound content exceeds the above range, there is a risk that the bending strength may be lowered due to grain coarsening during sintering, and the sintered density may also be lowered.

Additionally, the first metal compound may be an aluminum compound, and in this case, the basic mixture may include 3 wt% to 15 wt% and 3 wt% to 12 wt% of the aluminum compound. Etch-resistant ceramic parts containing such aluminum compounds can maintain the grain size at a certain level, and a precipitation hardening effect can be expected through certain precipitates.

The etch-resistant ceramic part may further include carbide containing a first metal. Carbide containing the first metal may be, for example, zirconium carbide, aluminum carbide, etc.

The etch-resistant ceramic component may also further include a carbon-based material. The carbon-based material may, for example, be carbon, graphite, or the like. The content of the carbon-based material may be 2 wt% to 30 wt%, 4 wt% to 20 wt%, and 5 wt% to 12 wt% based on the total weight.

The etch-resistant ceramic part may have an average grain size of 1.6 ㎛ or less, 1.1 ㎛ or less, and 0.8 ㎛ or less. The average grain size may be 0.1 ㎛ or more. The etching-resistant ceramic part has an appropriate grain size range, so that it can secure the desired etching resistance and at the same time exhibit good mechanical properties.

The bending strength of the etch-resistant ceramic component may be 150 MPa to 280 MPa, 165 MPa to 250 MPa, or 180 MPa to 250 MPa.

The relative density of the etching-resistant ceramic component may be 87.5% or more, 90% or more, 98% or more, or 99.9% or more. The relative density may be 99.99% or less.

If the etch rate of pure alumina (Al ₂ O ₃ ) is assumed to be 1 when exposed to 54 sccm of CF ₄ and 5 sccm of O ₂ for 800 minutes at a power of 800 W in a plasma treatment chamber at a pressure of 100 mTorr, the corrosion resistance The etch rate of the angular ceramic component may be 0.4 or less, 0.33 or less, and 0.27 or less. The etch rate may be 0.1 or more. By having this etch rate, the plasma etch lifespan can be secured and productivity reduction of microelectronic devices due to component replacement can be prevented.

The thermal conductivity of the etch-resistant ceramic component may be 3 W/mK to 15 W/mK, and 4 W/mK to 10.2 W/mK.

The hardness of the etch-resistant ceramic part may be 3 GPa to 15 GPa, or 4.6 GPa to 10 GPa.

The thermal expansion coefficient (10 ^-6 /℃) of the etch-resistant ceramic part may be 6 to 9, and 7 to 8.8 at 25 ℃ to 400 ℃.

The resistivity of the etch-resistant ceramic component may be 10 ^-2 Ωcm to 10 ⁰ Ωcm.

The etching-resistant ceramic component can be applied as a part of a device exposed to plasma, and for example, can be applied as a focus ring, edge ring, shower head, etc. inside a plasma etching device chamber.

Method for manufacturing etching-resistant ceramic parts

In order to achieve the above object, the method for manufacturing an etch-resistant ceramic part according to an embodiment is,

A mixing step of preparing raw materials including yttria, first metal oxide, and additives;

A screening step of granulating and selecting the raw materials;

It may include a sintering step of molding and sintering the sorted product obtained through the sorting step.

In the mixing step, the raw materials are,

A basic raw material mixture consisting of yttria and first metal oxide; and carbon-based materials;

The basic raw material mixture contains 1 wt% to 32 wt% of the first metal oxide,

The first metal may be one selected from the group consisting of zirconium, aluminum, and combinations thereof.

The basic mixture of the raw materials may contain 4 wt% to 30 wt%, 4 wt% to 20 wt%, and 5 wt% to 15 wt% of the first metal oxide. By having this yttria and first metal oxide content, it is possible to manufacture ceramic parts that satisfy the desired plasma etching resistance and mechanical properties.

The first metal oxide of the raw material may be zirconium oxide or yttria-stabilized zirconia. At this time, the basic mixture of the raw materials may contain 5 wt% to 30 wt%, 5 wt% to 20 wt%, and 5 wt% to 15 wt% of the zirconium oxide. By including this zirconium oxide, the grain size can be maintained at a certain level in the subsequent sintering process, and a precipitation hardening effect can be expected through certain precipitates. If the zirconium oxide content exceeds the above range, there is a risk that the bending strength may be lowered due to grain coarsening during sintering, and the sintered density may also be lowered.

Additionally, the first metal oxide of the raw material may be aluminum oxide. At this time, the basic raw material mixture may contain 3 wt% to 12 wt% and 3 wt% to 10 wt% of the aluminum oxide. By including such aluminum oxide, the grain size can be maintained at a certain level in the subsequent sintering process, and a precipitation hardening effect can be expected through certain precipitates.

In the mixing step, carbon-based materials may include, for example, carbon, phenol resin, graphite, etc. At this time, the raw material may include 0.1 to 30 parts by weight, and 3 to 15 parts by weight of the carbon-based material, based on 100 parts by weight of the basic raw material mixture.

In the mixing step, the raw materials may further include additives, and the additives may further include dispersants, binders, solvents, etc. The dispersant and binder may each contain 0.1 to 10 parts by weight based on 100 parts by weight of the basic raw material mixture, and the solvent is used so that the solid-liquid ratio (solid/liquid) is 0.1 to 0.3 based on the volume of solid components of the raw material. It can be included. The dispersant may be a dispersant that has a surfactant effect and may include ammonium polyacrylate, polar methacrylic acid, polycarboxylic acid, etc. The binder may include polyvinyl butyral, polyvinyl alcohol, polymethyl methacrylate, polyacrylic ester, etc., and the solvent may include deionized water, ethanol, etc.

The mixing step may be evenly mixed through a ball-mill process, etc., and may be carried out for 1 to 10 hours.

Granulation of the raw material may be performed through spray drying, for example, in a Disc Atomizer type spray drying device. At this time, the rotation speed of the disk may be 5,000 rpm to 20,000 rpm, the temperature of the inlet may be 100 ℃ to 140 ℃, and the temperature of the outlet may be 40 ℃ to 60 ℃. And the feeding rate may be 40 ml/min to 80 ml/min.

The selection step may be performed by selecting the granulated material to a particle size of 5 ㎛ to 80 ㎛.

Molding of the sorted product obtained through the above sorting step can be carried out through cold isostatic pressing, and thus a molded body and a green body can be obtained.

Sintering in the sintering step may be performed in a gas furnace, electric furnace, etc. At this time, the sintering temperature may be 1580°C to 1780°C, 1580°C to 1700°C, and 1600°C to 1700°C. By having this sintering temperature range, it can stably contribute to grain refinement and minimize the possibility of pores occurring.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Example 1 - Preparation of etch-resistant ceramic parts

In a basic mixture of yttria powder having a particle size of D ₅₀ 0.46 ㎛ from Treibacher and zirconia powder from Toray, the zirconia powder content was set to 10 wt%. A slurry was prepared by mixing 0.1 parts by weight of Aron A-6114 ammonium polyacrylate, 7.8 parts by weight of phenol carbon-based binder, and ethanol solvent so that the solid/liquid volume ratio was 20%, based on 100 parts by weight of the basic mixture.

The prepared slurry was ball-milled for 3 hours. Afterwards, granules were prepared by spray drying in a Disc Atomizer type spray drying device at a disk rotation speed of 10,000 rpm, an inlet temperature of 120°C, an outlet temperature of 50°C, and a feeding rate of 60 ml/mim.

The granules were selected to have a particle size of 5 ㎛ to 80 ㎛, and the selected material was subjected to cold isostatic pressing (CIP) molding to produce a green body.

The sintered body was manufactured by sintering the molded body for 7 hours in a graphite electric furnace at a temperature of 1630° C. and an argon gas atmosphere at normal pressure.

Example 2 - Preparation of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 5 wt%, and other conditions were the same as Example 1 to prepare a sintered body.

Example 3 - Preparation of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 3 wt%, and other conditions were the same as Example 1 to prepare a sintered body.

Example 4 - Preparation of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 1 wt%, and other conditions were the same as Example 1 to prepare a sintered body.

Example 5 - Preparation of etch-resistant ceramic parts

In Example 1, zirconia was replaced with alumina, the alumina content of the basic mixture was changed to 10 wt%, and other conditions were the same as in Example 1 to prepare a sintered body.

Example 6 - Preparation of etch-resistant ceramic parts

In Example 1, zirconia was replaced with alumina, the alumina content of the basic mixture was changed to 5 wt%, and other conditions were the same as in Example 1 to prepare a sintered body.

Example 7 - Preparation of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 20 wt%, a gas furnace was used instead of an electric furnace, and other conditions were the same as Example 1 to prepare a sintered body.

Example 8 - Preparation of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 30 wt%, a gas furnace was used instead of an electric furnace, and other conditions were the same as Example 1 to prepare a sintered body.

Example 9 - Preparation of etch-resistant ceramic parts

In Example 1, the sintering temperature was changed to 1638°C, and other conditions were the same as Example 1 to produce a sintered body.

Example 10 - Preparation of etch-resistant ceramic parts

In Example 1, the sintering temperature was changed to 1686°C, and other conditions were the same as Example 1 to produce a sintered body.

Example 11 - Preparation of etch-resistant ceramic parts

In Example 1, the sintering temperature was changed to 1684°C, a gas furnace was used instead of an electric furnace, and other conditions were the same as in Example 1 to produce a sintered body.

Comparative Example 1 - Manufacturing of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 40 wt%, a gas furnace was used instead of an electric furnace, and other conditions were the same as in Example 1 to prepare a sintered body.

Comparative Example 2 - Manufacturing of etch-resistant ceramic parts

In Example 1, the zirconia content of the basic mixture was changed to 50 wt%, a gas furnace was used instead of an electric furnace, and other conditions were the same as in Example 1 to prepare a sintered body.

The conditions of the examples and comparative examples are shown in Table 1.

division first metal
oxide first metal
Oxide (wt%) Sintering conditions (℃) Example 1 _ZrO2 10 1659 Example 2 _ZrO2 5 1659 Example 3 _ZrO2 3 1659 Example 4 _ZrO2 One 1659 Example 5 Al ₂ O ₃ 10 1659 Example 6 Al ₂ O ₃ 5 1659 Example 7 _ZrO2 20 1659 (gas furnace) Example 8 _ZrO2 30 1659 (gas furnace) Example 9 _ZrO2 10 1638 Example 10 _ZrO2 10 1686 Example 11 _ZrO2 10 1684 (gas furnace) Comparative Example 1 _ZrO2 40 1659 (gas furnace) Comparative Example 2 _ZrO2 50 1659 (gas furnace)

Experimental example - Molded body (green body) fracture surface and molding density analysis

Fracture surfaces of molded bodies (green bodies) obtained in Examples 1 to 4 (ZrO ₂ content 10 wt%, 5 wt%, 3 wt%, 1 wt%) and Example 6 (Al ₂ O ₃ content 5 wt%) was photographed through a scanning electron microscope, and the results are shown in Figure 1.

Referring to Figure 1, there was no significant difference in the shape of the fracture surface depending on the amount of zirconia added. The green density of the molded body showed a tendency to slightly increase depending on the zirconia content.

Experimental example - Fracture surface of sintered body, microstructure analysis

The fracture surfaces of the sintered bodies obtained in Examples 1 to 5 (ZrO ₂ content 10, 5, 3, 1, 20 wt%) and Examples 5 and 6 (Al ₂ O ₃ content 10, 5 wt%) were examined using a scanning electron microscope. was filmed, and the results are shown in Figures 2 to 4. Figure 2 was taken at 3000 magnification, and Figures 3 and 4 were taken at 10000 magnification.

Referring to Figure 2, pores were observed on the fractured surfaces of the sintered bodies with zirconia content of 1 wt% and 3 wt%, and as the zirconia content increased, the pores tended to decrease. In Example 6 where alumina was added, the pores were Almost didn't show up.

Referring to Figures 3 and 4, it was confirmed that precipitates were generated at the grains and/or grain boundaries of the sintered body.

Experimental example - XRD analysis of sintered body

The _{results obtained} through _an

Referring to Figure 5, in Example 5 in which alumina was added, yttria and yttrium-aluminum composite oxide (Y ₄ Al ₂ O ₉ ) peaks appeared.

Referring to Figure 6, in Example 1 in which zirconia was added, it was confirmed that the peak of zirconia hardly appeared in the sintered body, and the peak of yttria appeared.

Experimental Example - Sintered body density and strength analysis

The density and bending strength of the sintered body obtained in Examples 1 to 5 (ZrO ₂ content 10, 5, 3, 1, 20 wt%) and Examples 5 and 6 (Al ₂ O ₃ content 10, 5 wt%) were calculated using Universal It was measured using a Testing Machine (H&P), and the results are shown in Figures 7 and 8.

Referring to Figure 7, the sintered density tended to increase as the amount of zirconia added increased.

Referring to FIG. 8, the bending strength value of the sintered body was measured to be the highest in Example 1 in which zirconia was added at 10 wt%, and Example 6 in which 5 wt% of alumina was added also showed similar results.

Experimental example - analysis of plasma properties

When exposed to 54 sccm of CF ₄ and 5 sccm of O ₂ for 800 minutes at a power of 800 W in a plasma treatment chamber at a pressure of 100 mTorr, the etch rate of pure alumina (Al 2 O 3 ) was set to 1, and the etch rate of pure alumina (Al ₂ O ₃ ) was set to 1. Tria, the etching rate of the sintered body obtained in Examples 1 to 4 and Example 6 (ZrO ₂ content 10, 5, 3, 1, Al ₂ O ₃ content 5 wt%) was measured, and the surface state after etching was examined using a scanning electron microscope. The images were taken through, and the results are shown in Figures 9 and 10.

Referring to FIG. 9, it can be seen that the examples have an etch rate similar to or better than that of yttria, and with reference to FIG. 10, it can be seen that the examples show a relatively even etch surface.

Experimental Example - Analysis of sintered body thermal conductivity and hardness

The thermal conductivity and hardness of the sintered body and yttria obtained in Examples 1 to 4 and Example 6 (ZrO ₂ content 10, 5, 3, 1, Al ₂ O ₃ content 5 wt%) were measured using a Dilatometer and Vickers hardness meter. and the results are shown in Figures 11 and 12.

Referring to FIG. 11, the lowest thermal conductivity was measured in Example 1 in which 10 wt% of zirconia was added to the basic mixture.

Referring to Figure 12, it was confirmed that the hardness value tended to increase as the amount of zirconia added increased.

Experimental Example - Microstructure, density, strength and hardness analysis according to sintering conditions

The microstructures of the sintered bodies obtained in Examples 1, 9, 10, and 11 (sintering conditions 1659°C, 1638°C, 1686°C, 1684°C (gas furnace)) were photographed using a scanning electron microscope, and the results are shown in Figure 13. indicated. In addition, the average grain size and relative density of the sintered body were measured, and the results are shown in Figures 14 and 15. In addition, the bending strength and hardness of the sintered body were measured using a Universal Testing Machine (H&P), and the results are shown in Figures 16 and 17.

Referring to Figures 13 and 14, the grain size tended to become smaller as the temperature decreased during electric furnace sintering.

Referring to Figure 15, it was confirmed that the relative densities were all 99.3% or more.

Referring to Figures 16 and 17, the bending strength and hardness of the sintered body in Example 1 under 1659°C electric furnace conditions showed the highest results.

Experimental example - Sintered body bending strength, thermal shock analysis

The bending strength according to temperature of the yttria sintered body of Nippon Yttrium Co., Ltd. (NYC) and the sintered body obtained in Example 1 (ZrO ₂ content of 10 wt%) was measured according to the Universal Testing Machine (H&P), 120 After water cooling of the sintered body heat-treated for 30 minutes at ℃ was performed 3, 6, and 9 times, the three-point bending strength was measured at 25 ℃, and the results are shown in Figures 18 and 19.

Referring to Figure 18, compared to the Yttria sintered body from NYC, the sintered body of Example 1 (E.1) showed excellent bending strength in all temperature ranges.

Referring to Figure 19, compared to the Yttria sintered body from NYC, the sintered body of Example 1 (E.1) showed excellent bending strength at all times of quenching.

Experimental example - Physical properties and microstructure analysis according to the amount of first metal oxide added

Yttria sintered body from Nippon Yttrium Co., Ltd. (NYC), Examples 1, 7, 8, and Comparative Examples 1 and 2 (ZrO ₂ content 10, 20, 30, 40, 50 wt%) The microstructure was photographed using a scanning electron microscope, and the results are shown in Figure 20. In addition, the bending strength of each sintered body and the bending strength according to temperature were measured using the Universal Testing Machine (H&P), thermal conductivity and thermal expansion coefficient were measured using LFA (Laser Flash Analysis, Netzsch) equipment, and average grain size. was measured, and the results are shown in Figure 21 and Table 2.

division NYC Y ₂ O ₃ Example 1
(E. 1)
_ZrO2 10wt% Example 7
(E. 7)
ZrO ₂ 20wt% Example 8
(E. 8)
_ZrO2 30wt% Comparative Example 1
(CE 1)
_ZrO2 40wt% Comparative Example 2
(CE 2)
_ZrO2 50wt% density(%) 98.4 99.5 99.8 99.6 97.4 95.6 Bending strength (MPa) 150 243 259 252 184 204 Thermal conductivity (W/mK) 13.6 6.1 4.1 3.3 2.3 2.1 25~400℃ thermal expansion coefficient
(10 ^-6 /℃) 7.4 7.6 8.1 8.6 8.8 9.0 Average grain size (㎛) 1.42 0.7 1.53 1.14 3.92 2.69

Referring to Figure 20 and Table 1, the examples in which the zirconia addition amount was 30 wt% or less showed an average grain size of 2 ㎛ or less, and in the comparative examples in which the zirconia addition amount was 40 wt% or more, the crystal grains became coarse and some pores were also confirmed. did.

Referring to Figure 21, it was confirmed that the bending strength at 200°C was 230 MPa or more in the Examples, and was 170 to 210 MPa in the Comparative Example, which was lower than the Examples.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims are also possible. falls within the scope of rights.

Claims (10)

Comprising a basic mixture consisting of yttria and a first metal compound,
The basic mixture includes 1 wt% to 35 wt% of the first metal compound,
The first metal is one selected from the group consisting of zirconium, aluminum, and combinations thereof,
Etch-resistant ceramic parts with an average grain size of 2 ㎛ or less.
According to paragraph 1,
An etch-resistant ceramic part wherein the average grain size is 1.6 ㎛ or less.
According to paragraph 1,
An etch-resistant ceramic component having a bending strength of 150 MPa to 280 MPa.
According to paragraph 1,
The basic mixture includes 5 wt% to 35 wt% of the first metal compound,
The first metal is zirconium,
The first metal compound includes at least one of zirconium oxide and zirconium carbide.
According to paragraph 4,
An etch-resistant ceramic part wherein the average grain size is 1.1 ㎛ or less.
According to paragraph 1,
The basic mixture includes 3 wt% to 15 wt% of the first metal compound,
The first metal is aluminum,
The first metal silver compound includes at least one of aluminum oxide and yttrium-aluminum composite oxide.
According to paragraph 1,
Etch-resistant ceramic parts applied as parts of devices exposed to plasma.
A mixing step of preparing raw materials including yttria, first metal oxide, and additives;
A screening step of granulating and selecting the raw materials;
It includes a sintering step of molding and sintering the sorted product obtained in the sorting step,
The raw materials are,
A basic raw material mixture consisting of yttria and first metal oxide; and carbon-based materials;
The basic raw material mixture contains 1 wt% to 32 wt% of the first metal oxide,
A method of manufacturing an etch-resistant ceramic part, wherein the first metal is selected from the group consisting of zirconium, aluminum, and combinations thereof.
According to clause 8,
The raw materials further include a dispersant and a solvent,
A method of manufacturing an etching-resistant ceramic part, in which granulation of the raw material is carried out through spray drying.
According to clause 8,
A method of manufacturing an etch-resistant ceramic part, wherein the sintering is carried out at a temperature of 1580 ℃ to 1780 ℃.