Plasma-resistant ceramic member and manufacturing method therefor

Abstract

Disclosed are a plasma-resistant ceramic member and a manufacturing method therefor. The plasma-resistant ceramic member according to the present invention comprises a first cation in a trivalent state (3+) including yttrium (Y), a second cation in a tetravalent state (4+), and an anion including oxygen (O), wherein the content of yttrium is 70 to 90 mol% on the basis of 100 mol% of the total of the first cation and the second cation, and the molar ratio of the total cation to the total anion is 1:1.55 to 1:1.65.

Description

Plasma-resistant ceramic component and method for manufacturing the same

[0001] The present invention relates to a plasma-resistant ceramic member and a method for manufacturing the same. More specifically, the present invention relates to a plasma-resistant ceramic member and a method for manufacturing the same, which can improve not only plasma resistance but also durability and etching process stability by controlling the components constituting the ceramic member.

[0002] Yttrium oxide (Y2O3) is also referred to as yttria. Yttrium oxide has excellent resistance to plasma and is widely used as a component in plasma-resistant ceramic materials. This yttrium oxide is used in a bulk sintered form or in the form of coatings, such as thermal spraying and physical vapor deposition.

[0003] Plasma processes generate highly active radicals, such as fluorine, and fluorine-containing ions to not only promote chemical reactions with the material but also induce physical etching as these ions are incident on the material's surface with high energy. When yttria, an oxide, is etched by a fluorine-containing plasma, the surface of the oxide material is altered to a composition containing fluorine during the etching process. The thickness of this altered layer is known to be tens of nanometers, and simultaneously, it has been analyzed that the fluorine content is significantly higher than the oxygen content.

[0004] Furthermore, previous studies have shown that the process of oxide etching in fluorine-based plasma is closely related to surface alteration. It is known that the etching of oxide ceramics consists of two stages: surface layer alteration caused by fluorine during the plasma etching process and physical etching resulting from the incidence of high-energy ions.

[0005] Korean Registered Patent Publication No. 10-2390123 (April 25, 2022, hereinafter, Patent Document 1) describes a bulk having an oxide composition; and an oxide composition component constituting the bulk being F - and Cl -A ceramic substrate comprising a surface layer modified to have a composition including one or more anions selected from the group consisting of F - and Cl - A raw material containing one or more anions selected from the group consisting of is vaporized by heating and adsorbed onto the surface of the ceramic substrate, and F - and Cl - A plasma-resistant ceramic substrate and a method for manufacturing the same are disclosed, characterized by being a layer modified to include one or more anions selected from the group consisting of

[0006] According to the above Patent Document 1, the surface of a ceramic substrate is fluoride anion (F - ) or chloride anion (Cl - It is modified into a composition containing ).

[0007] The problem that the present invention aims to solve is to provide an yttrium oxide-based ceramic component that can improve not only plasma resistance but also durability and etching process stability.

[0008] In addition, the problem that the present invention aims to solve is to provide a method for manufacturing a yttrium oxide-based ceramic component with excellent plasma resistance without a separate surface modification process by controlling the ratio of cations to anions of an oxide containing yttrium.

[0009] The problems that the present invention aims to solve are not limited to the above problems, and other unmentioned problems will be clearly understood by those skilled in the art from the following detailed description.

[0010] A plasma-resistant ceramic member according to an embodiment of the present invention for solving the above problem comprises a first cation of trivalent (3+) containing yttrium (Y), a second cation of tetravalent (4+), and an anion containing oxygen (O), wherein the content of yttrium is 70 to 90 mol% based on 100 mol% of the total first cation and second cation, and the molar ratio of the total cation to the total anion is 1:1.55 to 1:1.65.

[0011] The above second cation may include one or more of Ti, Zr, and Ce.

[0012] The above plasma-resistant ceramic member may have a ratio of oxygen to fluorine among the anions on the surface after etching with a fluorine-based plasma of 1 or more.

[0013] After etching the above plasma-resistant ceramic member in a fluorine-based plasma, the electron value of the second cation on the surface of the ceramic member changes from 4+ to 3+, so that the ratio of the second cation having a 3+ electron value to the second cation having a 4+ electron value can increase to 1.0 or more.

[0014]

[0015] A method for manufacturing a plasma-resistant ceramic member according to an embodiment of the present invention for solving the above problem comprises: a step of providing a source comprising a first trivalent (3+) cation comprising yttrium (Y), a second tetravalent (4+) cation comprising yttrium (O), and an anion comprising oxygen (O), wherein the yttrium content is 70 to 90 mol% based on 100 mol% of the total first cation and second cation; and a step of coating a ceramic member on a substrate using the source, wherein the ceramic member comprises a first trivalent (3+) cation comprising yttrium (Y), a second tetravalent (4+) cation comprising yttrium (Y), and an anion comprising oxygen (O), wherein the yttrium content is 70 to 90 mol% based on 100 mol% of the total first cation and second cation, and the molar ratio of the total cation to the total anion of the ceramic member is 1:1.55 to 1:1.65.

[0016] The above second cation may include one or more of Ti, Zr, and Ce.

[0017] The above ceramic member may have a ratio of oxygen to fluorine among the anions on the surface after etching with a fluorine-based plasma of 1 or more.

[0018] The second cation is Ce or Ti, and some of the second cation may be converted into trivalent Ce or Ti during the step of coating the ceramic member.

[0019] The above coating can be performed by plasma spraying or physical vapor deposition.

[0020] The substrate on which the above coating is applied may be an aluminum oxide substrate, an aluminum nitride substrate, an anodized aluminum substrate, or a coating formed on such a substrate by thermal spraying or physical vapor deposition.

[0021] The above coating includes the step of sputtering in an atmosphere containing oxygen using a metal target other than an oxide as a source, and the metal target contains 70 to 90 mol% of yttrium and may contain one or more of Ti, Zr, and Ce.

[0022] The above coating includes a step of depositing by electron beam evaporation using an oxide ingot, wherein the oxide ingot contains 70 to 90 mol% of yttrium as a cation and may contain one or more of Ti, Zr, and Ce.

[0023] During deposition using the electron beam evaporation method, an ion beam can be used to assist the deposition.

[0024] The above method may further include a step of increasing the molar ratio of total cations to total anions of the ceramic member by heat treatment in an atmosphere containing oxygen.

[0025] The above heat treatment can be performed in the range of 200 to 800°C for 30 minutes to 4 hours.

[0026] According to the plasma-resistant ceramic member and the method for manufacturing the same according to the present invention, plasma resistance in fluorine-based plasma can be improved by lowering the physical etching rate by making the composition of the layer that is altered through the fluorination process by fluorine-based plasma close to an oxide during the plasma etching process.

[0027] Specifically, the plasma-resistant ceramic member according to the present invention can improve plasma resistance, durability, and etching process stability by controlling the ratio of cations to anions of an oxide containing yttrium.

[0028] In addition to the effects described above, the specific effects of the present invention are described together with the specific details for implementing the invention below.

[0029] FIG. 1 schematically shows a substrate coated with a ceramic member according to the present invention.

[0030] FIG. 2 schematically illustrates a method for manufacturing a ceramic member according to the present invention.

[0031] FIG. 3 schematically illustrates an example of an apparatus for manufacturing a ceramic member according to the present invention.

[0032] FIG. 4 schematically illustrates another example of an apparatus for manufacturing a ceramic member according to the present invention.

[0033] Figure 5 shows the relative etching rate relative to Y2O3 when the ratio of anions to cations of a component prepared with different CeO2 content of the evaporation source is 1.5 to 1.75.

[0034] FIGS. 6a to 6d show the results of analyzing the cross-section using electron energy loss spectroscopy (EELS) after performing plasma etching on a plasma-resistant ceramic member with added Ce according to Example 2.

[0035] Figure 7 shows the relative etching rates of a Y2O3 thin film and an 80Y-20Ce oxide thin film deposited by reactive sputtering technology and a Y2O3 sintered body compared to sapphire.

[0036] The advantages and features of the present invention and the methods for achieving them will become clear by referring to the embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below but may be implemented in various different forms. These embodiments are provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims.

[0037] When an element or layer is referred to as being "above" or "below" another element or layer, it includes not only being directly above or below another element or layer, but also cases where another layer or element is interposed in the middle.

[0038] The terms used herein are for describing the embodiments and are therefore not intended to limit the invention. In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. The term “comprising” as used in this specification does not exclude cases where the elements, components, steps, and / or actions mentioned are composed only of the elements, components, steps, and / or actions mentioned, nor cases where one or more other elements, components, steps, and / or actions are present or added, except where explicitly limited.

[0039] A plasma-resistant ceramic member and a method for manufacturing the same according to a preferred embodiment of the present invention will be described in detail below with reference to the attached drawings.

[0040]

[0041] FIG. 1 schematically shows a substrate coated with a ceramic member according to the present invention.

[0042] Referring to FIG. 1, the ceramic member (120) according to the present invention may be coated on a substrate (110). The substrate (110) may be, for example, a silicon substrate, a metal substrate such as aluminum, a ceramic substrate such as silicon oxide (SiO2), aluminum oxide (Al2O3), or aluminum nitride (AlN). Additionally, the substrate (110) may be anodized aluminum. Furthermore, the substrate (110) may be a coating formed on the aforementioned ceramic substrate, anodized aluminum substrate, etc., by various methods such as thermal spraying or physical vapor deposition.

[0043] In the present invention, the ceramic member (120) is based on yttrium oxide. Specifically, the plasma-resistant ceramic member according to an embodiment of the present invention comprises a first cation of trivalent (3+) containing yttrium (Y), a second cation of tetravalent (4+), and an anion containing oxygen (O), and the content of yttrium may be 70 mol% or more, specifically 70 to 90 mol%, based on 100 mol% of the total of the first cation and the second cation. If the yttrium content is less than 70 mol%, it may be susceptible to physical etching due to the addition of an excessive second cation, as described below. If the yttrium content exceeds 90 mol%, the improvement of plasma-resistant properties may be insufficient.

[0044] According to the results of measuring the physical etching rates of pure yttrium oxide and yttrium fluoride in a state where fluorine plasma is excluded and there is no degradation of the surface layer by fluorine from the plasma, the physical etching rate of yttrium fluoride (YF3) was found to be several times higher than that of yttrium oxide (Y2O3). Therefore, it can be seen that in order to increase the resistance of oxides to plasma etching, it is necessary to suppress the degradation of the surface layer caused by fluorine from the fluorine-based plasma during the etching process.

[0045] The inventors of the present invention focused on the structure of yttrium oxide. Yttrium oxide, or yttria, has a crystal structure derived from a fluorite structure. Zirconia (zirconium oxide, ZrO2), which has a typical fluorite structure, has oxygen ions that are anionic and is densely packed, and zirconium (Zr) that is a cation is located inside a hexahedral cube composed of eight oxygen ions.

[0046] In contrast, yttria has a molar ratio of yttrium cation to oxygen anion of 1:1.5, which is relatively insufficient compared to zirconia, which has a molar ratio of 1:2. Therefore, yttrium cations are located inside an octahedron composed of six anions, and the deficient oxygen ions have a crystal structure in which they have vacancies in the anion sites, rather than being densely packed in a fluorite structure like in zirconia.

[0047] The present invention was conceived based on the observation that in a fluorine-based plasma, high-energy fluoride ions easily penetrate the anion vacancies of yttrium oxide (yttria) and easily alter the surface layer of yttria, and that in order to increase plasma resistance, it is necessary to reduce or suppress the penetration of fluoride ions. Accordingly, the present invention aims to reduce the amount of anion vacancies into which fluoride can enter by providing a ceramic member in which at least a portion of the anion vacancies are pre-filled with oxygen ions, and thereby suppress the surface penetration of high-energy fluoride ions.

[0048] In order to realize this, 3-ga (3 + ) In the yttrium cation site, which is a 4-valent (4 +The aim was to substitute cations and supply additional oxygen ions to anion vacancies based on charge balance. Representative examples include Ti, Zr, and Ce, which are tetravalent cations, where the number of anions per two cations can be one greater than that of yttria (Y2O3). However, in the case of cations whose electron value can change, such as cerium (Ce) and titanium (Ti), both trivalent and tetravalent ions can coexist in the component during the manufacturing process; in this instance, the tetravalent cation (Ce 4+ , Ti 4+ Anion vacancies can be replaced with oxygen ions only by ). That is, by substituting the tetravalent cations Ti, Zr, or Ce at the yttrium cation site, the additional oxygen anions supplied can reduce anion vacancies and suppress the deterioration of the coating surface caused by fluoride ions during the plasma etching process.

[0049] In the case of oxides containing Ti, Zr, or Ce along with yttrium, the ratio of anions to cations is higher compared to yttrium oxide. That is, while the molar ratio of cations to anions in yttrium oxide is 1:1.5, in the case of oxides containing Ti, Zr, or Ce along with yttrium, the ratio of anions can be higher, such as 1:1.55 to 1:1.65. As a result, in the case of oxides containing Ti, Zr, or Ce as cations along with yttrium, the oxygen anion content is high, resulting in fewer oxygen vacancies and inhibiting fluorine penetration into the surface. Through this, the surface of the ceramic component is maintained in a form closer to an oxide during the etching process. Therefore, since a surface closer to an oxide can be maintained during the etching process using fluorine-based plasma rather than yttria, the physical etching rate can be slowed down, and plasma resistance and durability are achieved.

[0050] In addition, Ce on the surface of the plasma-resistant ceramic component during the fluorine-based plasma etching process 4+ , Ti 4+ Ions like Ce 3+ , Ti3+ It can be reduced to, and this can also contribute to increasing the oxygen content on the surface of the ceramic member during the etching process. For example, after etching a plasma-resistant ceramic member in a fluorine-based plasma, the electron value of the second cation on the surface of the ceramic member changes from 4+ to 3+, so that the ratio of the second cation having a 3+ electron value to the second cation having a 4+ electron value can increase to 1.0 or higher. Generally, etching causes physical sputtering accompanied by chemical changes on the surface. At this time, the oxygen ions (O) sputtered 2- If there is 1 ) , in order to balance the charge, fluoride ions (F - Fluoridation of the surface layer can proceed as two ions are substituted onto the surface. However, when the electron value changes—more specifically, when the electron value changes in a way that causes cations to be reduced—the number of fluoride ions required to balance the charge decreases. For example, when a component is etched by a fluorine-based plasma, the Ce contained in the component 4+ Ga Ce 3+ When the change occurs, only one fluorine atom needs to be replaced on the surface of the ceramic component when one oxygen atom is sputtered. As a result, when the surface of the plasma-resistant component is etched in a fluorine-based plasma, the fluorine content on the surface is reduced, contributing to the improvement of etching characteristics.

[0051] Meanwhile, the ratio of cations to anions in the plasma-resistant ceramic material is preferably 1.55 to 1.65, and more preferably 1.60 to 1.65. If the ratio of cations to anions in the plasma-resistant ceramic material does not reach 1.55, it is very close to yttrium oxide, so the effects of the present invention described above may not be sufficiently obtained. On the other hand, if the amount of tetravalent cations introduced to fill the anion vacancies is excessively increased, the cations themselves may be vulnerable to physical etching. That is, since the elements forming tetravalent cations (Ti, Zr, Ce) are more vulnerable to fluorine-based plasma than yttrium, if too much is added, the ratio of anions to cations becomes excessively high exceeding 1.65, and the effect of suppressing physical etching may be offset.

[0052] To achieve a total cation-to-anion ratio of 1.55 to 1.65 of the plasma-resistant ceramic material, the tetravalent element among the cations may be included in an amount of about 10 to 30 mol%. If necessary, the ratio of anions may be increased to the above range through heat treatment in an oxygen-containing heat treatment atmosphere.

[0053] The second cation may include one or more of Ti, Zr, and Ce.

[0054] The second cation in the raw material is tetravalent Ce 4+ ions or Ti 4+ It exists as ions, but during the manufacturing process of ceramic components, some of it becomes trivalent cations (Ce 3+ or Ti 4+ It can be converted into ). However, the amount converted to a trivalent cation may be sufficiently small. For example, from the Ce spectrum analyzed by photoelectron spectroscopy (XPS) or electron energy loss spectroscopy (EELS), Ce 3+ / Ce 4+ The ratio of is 0.5 or less, or from the Ti spectrum, Ti 3+ / Ti 4+ The ratio of can be 0.5 or less.

[0055] The plasma-resistant ceramic member according to the present invention may have a ratio of oxygen to fluorine among the anions on the surface after etching with a fluorine-based plasma of 1 or more.

[0056]

[0057] FIG. 2 schematically illustrates a method for manufacturing a ceramic member according to the present invention. Referring to FIG. 2, the method for manufacturing a ceramic member according to the present invention includes a ceramic coating step (S210) and a heat treatment step (S220). The heat treatment step (S220) is not essential and may be additionally performed when the anion ratio of the ceramic member obtained in the coating step (S210) does not reach a target value.

[0058] In the ceramic coating step (S210), a ceramic member is coated on a substrate containing a first cation of trivalent (3+) containing yttrium (Y), a second cation of tetravalent (4+), and an anion containing oxygen (O), wherein the yttrium content is 70 to 90 mol% based on 100 mol% of the total first cation and second cation.

[0059] The second cation may include one or more of Ti, Zr, and Ce.

[0060] The second cation is Ce or Ti, and a portion of the second cation may be converted into trivalent Ce or Ti during the ceramic coating step (S210). That is, during the ceramic coating process, Ce 4+ Part of Ce 3+ It can be converted to, and Ti 4+ Part of Ti 3+ It may also be converted to. However, the amount converted to trivalent cations may be sufficiently small. For example, from the Ce spectrum analyzed by photoelectron spectroscopy (XPS) or electron energy loss spectroscopy (EELS), Ce 3+ / Ce 4+ The ratio of is 0.5 or less, or from the Ti spectrum, Ti 3+ / Ti 4+The ratio of can be 0.5 or less.

[0061] Various substrates may be used, and preferably, the substrate may be an aluminum oxide substrate, an aluminum nitride substrate, or an anodized aluminum substrate. Additionally, the substrate may be a coating formed on various ceramic substrates, anodized aluminum substrates, etc., by various methods such as thermal spraying or physical vapor deposition.

[0062]

[0063] Ceramic coating can be performed by plasma spraying or physical vapor deposition.

[0064] For example, the ceramic coating step (S110) may include a step of depositing using an oxide ingot by electron beam evaporation. The oxide ingot used may contain 70 to 90 mol% of yttrium as a cation and may contain one or more of Ti, Zr, and Ce. FIG. 3 shows an example of an electron beam evaporation deposition apparatus for manufacturing a ceramic member according to the present invention. During deposition by electron beam evaporation, an ion beam may be used to assist the electron beam deposition.

[0065] As another example, the ceramic coating step (S110) may include a step of sputtering in an oxygen-containing atmosphere using a metal target other than an oxide as a source. The metal target used may contain 70 to 90 mol% of yttrium and may contain one or more of Ti, Zr, and Ce. FIG. 4 shows an example of a sputtering apparatus for manufacturing a ceramic member according to the present invention.

[0066]

[0067] Ceramic members coated by the methods described above may have a molar ratio of total cations to total anions of 1:1.55 to 1:1.65.

[0068]

[0069] In the heat treatment step (S220), heat treatment is performed in an atmosphere containing oxygen to increase the ratio of anions. As mentioned above, the heat treatment step (S220) is not essential and may be performed additionally when the ratio of anions of the ceramic member obtained in the coating step (S210) does not reach the target value.

[0070]

[0071] The heat treatment step (S220) can be performed for about 30 minutes to 4 hours in the range of 200 to 800°C. If the heat treatment temperature is too low, below 200°C, the degree to which oxygen ions fill the anion vacancies may be insufficient. On the other hand, even if the heat treatment temperature exceeds 800°C, it is difficult to expect further improvement in effect.

[0072]

[0073] As described above, the plasma-resistant ceramic member according to the present invention can improve plasma resistance, durability, and etching process stability by controlling the ratio of cations to anions of an oxide containing yttrium.

[0074]

[0075] Examples

[0076] Hereinafter, the structure and operation of the present invention will be explained in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and should not be interpreted in any way as limiting the present invention.

[0077] Details not listed here can be sufficiently technically inferred by a person skilled in this field, so their explanation will be omitted.

[0078]

[0079] Example 1) Experiment on increasing the ratio of anions using electron beam deposition

[0080] A 50 mm diameter silicon substrate, mirror-polished to have an average surface roughness of 10 nm or less, was mounted on the fixed part of an electron beam deposition apparatus as shown in Fig. 3 (distance between the evaporation source (ingot) and the silicon substrate: 480 mm). The ratio of Y:Ce, the cations of the evaporation source, was adjusted, and an electron beam was incident on the evaporation source. When the evaporation source melted and vaporization began, the shutter above the evaporation source was opened to form a coating layer 2 μm thick on the substrate. At this time, the temperature of the substrate where the plasma-resistant coating was deposited was 600°C, the rotation speed was 20 rpm, the vacuum level of the deposition chamber was 0.1 mTorr, and the deposition rate was 2 nm / sec.

[0081] Table 1 shows the ratio of anions before and after etching for cases where the ratio of anions to cations is 1.5, 1.55, and 1.6. These three test specimens correspond to cases where the mol% of Ce cations among the total cations is 0, 10, and 20 mol%. However, when increasing the anion content using CeO2, the electron valence after deposition is 3 depending on the high vacuum deposition conditions. + It may contain some Ce ions, but this is to a sufficiently small extent. The ratio of cations to anions indicated in Table 1 is due to the electron valence of Ce being 4 + This applies to the case.

[0082] Fluorine-based plasma etching was performed by flowing CF4:Ar:O2 at flow rates of 30, 5, and 10 sccm, respectively. The pressure of the etching chamber was 10 mTorr, the top power was 600 W, and the bottom power was 150 W. A coated test specimen was mounted on a 4-inch silicon substrate and etching was performed.

[0083] Even though the anion / cation ratio before etching increased slightly to 1.6, compared to when yttrium oxide (anion / cation = 1.5) was etched, the degree of fluorine degradation of the surface after etching was significantly reduced, making it closer to an oxide. Additionally, referring to Table 1, when the anion / cation ratio is 1.6, it can be seen that the ratio of oxygen to fluorine among the anions on the surface after etching with a fluorine-based plasma is greater than 1.

[0084] [Table 1]

[0085]

[0086] Figure 5 shows the relative etching rate compared to Y2O3 when the ratio of anions to cations is 1.5 to 1.75 with varying Ce content in the evaporation source. Referring to Figure 5, the lowest etching rate was observed when the ratio of Ce cations in the evaporation source was 20 mol%, i.e., when the ratio of anions to cations was 1.6, indicating the best plasma resistance. It can be seen that for Ce, a ratio of anions to cations of 1.6 to 1.65 is desirable.

[0087] Meanwhile, referring to Figure 5, it shows that when the ratio of Ce cations exceeds 30 mol%, that is, when the ratio of anions to cations exceeds 1.65, the plasma resistance may deteriorate as the amount of Ce, which is susceptible to plasma and added to increase anions, also increases.

[0088]

[0089] Example 2) Surface characteristics of a plasma-resistant ceramic component after etching using Ce

[0090] After performing plasma etching on a plasma-resistant ceramic member (80Y-20Ce(Y0.2Ce)) with added Ce according to Example 1, the results of analyzing the cross-section using electron energy loss spectroscopy (EELS) are shown in FIGS. 6a to 6d.

[0091] Referring to FIGS. 6a to 6d, at a surface thickness of less than 20 nm, Ce 3+ / Ce 4+ α is 1.0 or higher and internally Ce 3+ / Ce 4+ It shows that is 0.5 or less. Ce in the surface layer during etching with fluorine-based plasma 4+ Ga Ce 3+ It can be seen that changing to contributes to further increasing the oxygen content of the surface layer.

[0092]

[0093] Example 3) Sputtering using a Y-Ce metal target

[0094] A 50 mm diameter silicon substrate, mirror-polished to have an average surface roughness of 10 nm or less, was mounted on the fixed part of a reactive sputtering apparatus as shown in Fig. 4 (distance between the substrate and the metal target: 140 mm). It was selected based on the fact that an excellent etching rate was observed when Ce cations accounted for 20 mol% of the total cations, as confirmed in the previous electron beam deposition experiment. The sputtering target was yttrium-cerium metal, and the cerium content was adjusted to 20 mol% during alloy fabrication. A 1 μm thick coating layer was formed on the substrate using a deposition technique capable of forming an oxide thin film through a chemical reaction between valence oxygen gas sputtered out by an argon gas plasma and the substrate surface. At this time, the substrate on which the plasma-resistant coating was deposited was not intentionally heated, and the chamber temperature was maintained at 60°C or lower. The vacuum level of the deposition chamber was maintained at 10 mTorr, the deposition time at 30 minutes, and the applied current at 3.3 A.

[0095] Plasma-resistant materials to which reactive sputtering was applied were etched in a fluorine-based plasma. Etching was performed by flowing CF4:Ar:O2 at flow rates of 30, 10, and 5 sccm, respectively. The pressure of the etching chamber was 10 mTorr, the top power was 600 W, and the bottom power was 150 W. A coated test specimen was mounted on a 4-inch silicon substrate, and etching was performed. After etching, the etching depth was measured on the surface using a surface step height measuring instrument (AlphaStep).

[0096] Figure 7 shows the relative etching rates of a Y2O3 thin film and an 80Y-20Ce (Y0.2Ce) oxide thin film deposited by reactive sputtering technology, compared to a Y2O3 sintered body and sapphire.

[0097] Referring to Figure 7, compared to sapphire (sap), the etching rate of the sintered Y2O3 film was 17.8% and that of the reactive sputtered Y2O3 film was 17.3%, which are similar, but the plasma resistance of the Ce cation-substituted Y2O3 film was 14.1%, which is about 20% improved.

[0098]

[0099] Although embodiments of the present invention have been described above with reference to the attached drawings, the present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical concept or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

[0100] <Explanation of Symbols>

[0101] 110 : Entry

[0102] 120 : Coating layer (ceramic component)

Claims

1. A first trivalent (3+) cation including yttrium (Y), a second tetravalent (4+) cation including one or more of Ti, Zr, and Ce, and an anion including oxygen (O), Based on 100 mol% of the total of the first and second cations above, the yttrium content is 70 to 90 mol%, and A plasma-resistant ceramic member having a molar ratio of total cations to total anions of 1:1.55 to 1:1.

65.

2. In Paragraph 1, A plasma-resistant ceramic member having a ratio of oxygen to fluorine among anions on the surface of the ceramic member after etching in a fluorine-based plasma, which is 1 or greater.

3. In Paragraph 1, A plasma-resistant ceramic member in which, after etching in a fluorine-based plasma, the electron value of the second cation on the surface of the ceramic member changes from 4+ to 3+, and the ratio of the second cation having a 3+ electron value to the second cation having a 4+ electron value increases to 1.0 or more.

4. A step of preparing a source comprising a first trivalent (3+) cation including yttrium (Y) and a second tetravalent (4+) cation including one or more of Ti, Zr, and Ce, wherein the yttrium content is 70 to 90 mol% based on 100 mol% of the total of the first and second cations; and The method comprises the step of coating a ceramic member on a substrate using the above source, wherein the ceramic member comprises a first cation of trivalent (3+) containing yttrium (Y), a second cation of tetravalent (4+), and an anion containing oxygen (O), and the yttrium content is 70 to 90 mol% based on 100 mol% of the total first cation and second cation. A method for manufacturing a plasma-resistant ceramic member in which the molar ratio of total cations to total anions of the ceramic member is 1:1.55 to 1:1.

65.

5. In Paragraph 4, A method for manufacturing a plasma-resistant ceramic member, wherein, after etching in a fluorine-based plasma, the ratio of oxygen to fluorine among the anions on the surface of the ceramic member is 1 or greater.

6. In Paragraph 4, A method for manufacturing a plasma-resistant ceramic member, characterized in that the second cation is Ce or Ti, a portion of the second cation is converted into trivalent Ce or Ti during the step of coating the ceramic member, and the ratio of the amount of 4+ ions to the amount of 3+ ions among cations other than yttrium is 2 or more.

7. In Paragraph 4, A method for manufacturing a plasma-resistant ceramic member, wherein the above coating is performed by plasma spraying or physical vapor deposition.

8. In Paragraph 4, A method for manufacturing a plasma-resistant ceramic member, wherein the above-mentioned substrate is an aluminum oxide substrate, an aluminum nitride substrate, an anodized aluminum substrate, or a coating formed on such substrate by thermal spraying or physical vapor deposition.

9. In Paragraph 4, The above coating includes the step of sputtering in an oxygen-containing atmosphere using a metal target other than an oxide as a source, and A method for manufacturing a plasma-resistant ceramic member, wherein the metal target comprises 70 to 90 mol% of yttrium and one or more of Ti, Zr, and Ce.

10. In Paragraph 4, The above coating includes the step of depositing by electron beam evaporation using an oxide source, and A method for manufacturing a plasma-resistant ceramic member, wherein the oxide source is a cation containing 70 to 90 mol% of yttrium and containing one or more of Ti, Zr, and Ce.

11. In Paragraph 10, A method for manufacturing a plasma-resistant ceramic component by using an ion beam to assist deposition during deposition by electron beam evaporation.

12. In Paragraph 4, A method for manufacturing a plasma-resistant ceramic member, further comprising: a step of, after the step of coating the ceramic member, heat-treating the substrate coated with the ceramic member in an atmosphere containing oxygen to increase the molar ratio of total cations to total anions of the ceramic member.

13. In Paragraph 12, A method for manufacturing a plasma-resistant ceramic member, wherein the above heat treatment is performed in the range of 200 to 800°C for 30 minutes to 4 hours.

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