JP2004190136A - Member inside plasma treatment vessel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a member inside a plasma treatment vessel in which the peeling of a sprayed coating formed as a top coat layer can be suppressed. <P>SOLUTION: A barrier coat layer 74 consisting of a material having excellent corrosion resistance to process gas comprising halogen elements is formed between a base material 71 and a sprayed coating 72, and the barrier coat layer 74 is subjected to sealing treatment with a resin or by a sol-gel method. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to an inner member of a plasma processing container, and more particularly to, for example, a deposition shield, an exhaust plate, a focus ring, an electrode plate, and an electrostatic chuck used in a plasma processing container in which a plasma atmosphere of a process gas containing a halogen element is formed. , A plasma processing vessel inner member such as a processing vessel inner wall material.

2. Description of the Related Art In a manufacturing process of semiconductors and liquid crystal devices, plasma processing using plasma is often used. In such plasma processing, fluoride such as C ₄ F ₈ or NF ₃ or BCl ₃ is used in a processing chamber. and SnCl ₄ chlorides such as, for using the gas containing a halogen element, including such bromide HBr, there is a problem that the processing container member is significantly corroded wear. Therefore, for example, the plasma processing container inner members such as the deposition shield, the exhaust plate, the focus ring, the electrode plate, the electrostatic chuck, and the processing container inner wall material are required to have high plasma resistance.

On the other hand, as a member inside such a plasma processing container, a sprayed coating having high corrosion resistance such as Al ₂ O ₃ or Y ₂ O ₃ is formed on the surface of a substrate made of Al, Al alloy, Al oxide, quartz, or the like. Has been proposed to improve the plasma resistance of the processing container inner member (for example, see Patent Document 1). Further, an anodic oxide coating may be further formed between the base material and the thermal spray coating. And, in order to improve the adhesion with the thermal spray coating, the surface of the base material or the anodic oxide coating is intentionally roughened by blasting or the like, and the peeling of the thermal spray coating is prevented in expectation of an anchor effect. .

  In the case of the above-described plasma etching apparatus, in addition to using a process gas containing a highly corrosive halogen element, pure water, a fluorine-based solvent, acetone, or the like is used to remove reaction products attached to the inside of the processing container. Since cleaning is periodically performed with a cleaning liquid such as an organic solvent, a process gas or a cleaning liquid for cleaning intrudes between the base material and the sprayed coating or between the base material and the anodic oxide coating. There is a problem that a corrosion product is generated on the surface of the base material by reacting with the gas or the cleaning liquid, and as a result, the sprayed coating is peeled off.

  That is, as shown in FIG. 21A, in the plasma processing container inner member 100, a reaction product 103 such as a CF polymer is formed on a surface of a thermal spray coating (top coat layer) 102 on a substrate 101 such as Al. The reaction product is periodically or irregularly removed by dipping in a predetermined cleaning liquid 104 as shown in FIG. 21B. Then, as shown in FIG. 21C, the process gas, the cleaning liquid, or the reaction product reacts with the through-holes of the thermal spray coating 102, the boundary portion with the thermal spray coating 102, or the portion damaged by plasma, gas, or the like. The liquid that has entered penetrates and reaches the surface of the substrate 101. As a result, a corrosion product is generated on the surface of the base material 101, or the unevenness formed on the base material surface for obtaining the anchor effect is smoothed, and the anchor effect is lost. As shown in d), it is considered that a portion 105 that separates from the base material 101 is formed in the thermal spray coating 102.

On the other hand, since Al ₂ O ₃ and Y ₂ O ₃ as described above have high reactivity with moisture in the air, when used as an inner wall material of a plasma processing container, a vacuum chamber which is a processing container is required. There is a possibility that a large amount of water is taken in when the chamber is opened to the atmosphere or when the vacuum chamber is wet-cleaned. When such a large amount of moisture is taken in, the inside of the vacuum chamber becomes hot or undergoes plasma discharge during the process, so that moisture is desorbed from the inner wall of the vacuum chamber and chemically reacts with the inner wall and the deposits of the chamber. However, there are serious disadvantages such as generation of particles, elongation of evacuation time, occurrence of abnormal discharge, and deterioration of film formation characteristics.

  On the other hand, in Patent Document 2, plasma is generated at the time of vacuum evacuation, the plasma is brought into contact with the inner wall surface of the chamber, the temperature is raised, and the attached water molecules are vaporized in a short time. A method of evacuating is disclosed. Further, Patent Literature 3 discloses that a heater is provided on a cover member of a vacuum chamber, the heater is controlled at the time of plasma processing, and the temperature of the inner wall of the vacuum chamber is constantly maintained at a predetermined temperature or higher, and the moisture adsorbed on the inner wall of the vacuum chamber is controlled. And a technique for reducing the amount of organic substances and quickly evaporating the adsorbed moisture and organic substances. Further, in Patent Documents 4 and 5, a detachable shield is provided on the inner wall of the vacuum chamber, and when the vacuum arrival time exceeds a predetermined value due to the influence of moisture or the like adsorbed by attached contaminants, the shield member is cleaned. A technique for instructing replacement is disclosed.

  However, since the techniques of Patent Documents 2 to 5 all deal with the adsorption of moisture, their effects are limited and have not yet reached a fundamental solution.

JP-A-8-339895 (page 3, FIG. 2) JP-A-8-181117 JP-A-11-54484 JP-A-11-54487 JP-A-2002-124503

  The present invention has been made in view of the above-mentioned problems of the related art, and an object of the present invention is to provide a new and improved plasma treatment capable of suppressing peeling of a thermal spray coating formed as a top coat layer. It is to provide a member in a container.

  Another object of the present invention is to provide a plasma processing container inner member in which moisture is less likely to be released during plasma processing.

  In order to solve the above problems, according to a first aspect of the present invention, there is provided a plasma processing container internal member having a base material and a coating formed by spraying ceramics on the surface thereof, wherein the ceramics constituting the coating is: , B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd, at least one of which is sealed with a resin. And a member inside the plasma processing vessel.

  According to a second aspect of the present invention, there is provided an inner member of a plasma processing vessel having a base material and a coating formed on the surface thereof by spraying ceramics, wherein the coating is B, Mg, Al, Si, Ca, A first ceramic layer made of a ceramic containing at least one element selected from the group consisting of Cr, Y, Zr, Ta, Ce, and Nd; and B, Mg, Al, Si, Ca, Cr, Y, Zr, A second ceramics layer made of ceramics containing at least one element selected from the group consisting of Ta, Ce and Nd, and at least a part of at least one of the first and second ceramics layers is sealed with a resin. Provided is an inner member of a plasma processing container, which is subjected to hole processing.

  In the first and second aspects of the present invention, the resin is preferably selected from the group consisting of SI, PTFE, PI, PAI, PEI, PBI, and PFA.

  According to a third aspect of the present invention, there is provided an inner member of a plasma processing container having a base material and a coating formed on the surface thereof by spraying ceramics, wherein the ceramics constituting the coating are B, Mg, Al, A plasma comprising at least one element selected from the group consisting of Si, Ca, Cr, Y, Zr, Ta, Ce, and Nd, at least a portion of which is sealed by a sol-gel method. A member inside a processing container is provided.

  According to a fourth aspect of the present invention, there is provided a plasma processing container inner member having a base material and a coating formed on the surface thereof by spraying ceramics, wherein the coating is formed of B, Mg, Al, Si, Ca, A first ceramic layer made of a ceramic containing at least one element selected from the group consisting of Cr, Y, Zr, Ta, Ce, and Nd; and B, Mg, Al, Si, Ca, Cr, Y, Zr, A second ceramic layer made of a ceramic containing at least one element selected from the group consisting of Ta, Ce and Nd, wherein at least a part of at least one of the first and second ceramic layers is formed by a sol-gel method. An inner member of a plasma processing container, which is subjected to a sealing process.

  In the third and fourth aspects of the present invention, it is preferable that the sealing treatment is performed using an element selected from elements belonging to Group 3a of the periodic table.

In a fourth aspect the first of the present invention, examples _of the _{ceramic, B 4 C, MgO, Al} 2 O 3, SiC, Si 3 N 4, SiO 2, CaF 2, Cr 2 O 3, Y 2 O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , at least one selected from the group consisting of CeF ₃ and Nd ₂ O ₃ can be suitably used.

  According to a fifth aspect of the present invention, there is provided an inner member of a plasma processing vessel having a base material and a coating formed on the surface thereof, wherein the coating comprises: a main layer formed by spraying ceramics; And a barrier coat layer made of a ceramic containing an element selected from the group consisting of Al, Si, Ca, Cr, Y, Zr, Ta, Ce, and Nd. I do.

In the fifth aspect of the present invention, as the barrier coat layer, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , At least one ceramic selected from the group consisting of YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ can be suitably used. Further, as the barrier coat layer, a thermal sprayed coating at least part of which is sealed with a resin can be used, and the resin includes SI, PTFE, PI, PAI, PEI, PBI, and PFA. Those selected from the group are preferred. Alternatively, as the barrier coat layer, a thermal spray coating, at least a part of which is subjected to a sealing treatment by a sol-gel method, may be used, wherein the sealing treatment is selected from elements belonging to Group 3a of the periodic table. It is preferable to carry out using.

  According to a sixth aspect of the present invention, there is provided an inner member of a plasma processing container having a base material and a coating formed on the surface thereof, wherein the coating is formed of a main layer formed by spraying ceramics; And a barrier coat layer made of engineering plastic formed between the main layer and the main layer.

  In the sixth aspect of the present invention, a plastic selected from the group consisting of PTFE, PI, PAI, PEI, PBI, PFA, PPS, and POM can be suitably used as the engineering plastic.

In the fifth and sixth aspect of the present invention, the main _{layer, B 4 C, MgO, Al} 2 O 3, SiC, Si 3 N 4, SiO 2, CaF 2, Cr 2 O 3, Y 2 O _At least one ceramic selected from the group consisting of ₃ , YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ can be suitably used.

  According to a seventh aspect of the present invention, there is provided a plasma processing container internal member having a substrate and a coating formed on the surface thereof, wherein the coating comprises at least one element belonging to Group 3a of the periodic table. The inner member of the plasma processing container is provided, wherein at least a part of the coating is hydrated with steam or high-temperature water.

  According to an eighth aspect of the present invention, there is provided a member inside a plasma processing vessel having a substrate and a film formed on the surface thereof, wherein the film contains at least one element belonging to Group 3a of the periodic table. A first ceramics layer comprising a ceramic containing at least one element belonging to Group 3a of the periodic table; and a second ceramics layer comprising a ceramic containing at least one element belonging to Group 3a of the periodic table, wherein at least one of the first and second ceramics layers is provided. Provided is an inner member of a plasma processing vessel, characterized in that at least a part thereof is hydrated by steam or high-temperature water.

In the seventh and eighth aspects of the present invention, a thermal sprayed coating formed by thermal spraying or a thin film formed by a thin film forming technique can be used as the coating. As the ceramics constituting the _coating, it is preferable that one selected from _{Y 2 O 3, CeO 2,} Ce 2 O 3, Nd 2 O 3.

  According to a ninth aspect of the present invention, there is provided a member inside a plasma processing vessel having a substrate and a coating formed on the surface thereof, wherein the coating comprises at least one element belonging to Group 3a of the periodic table. A first ceramics layer made of ceramics containing the first ceramics layer, and a second ceramics layer formed by spraying the ceramics, wherein at least a part of the first ceramics layer is hydrated with steam or high-temperature water. To provide a member inside the plasma processing vessel.

In the ninth aspect of the present invention, as the first ceramics layer, a thermal sprayed coating formed by thermal spraying or a thin film formed by a thin film forming technique can be used. Further, it is preferable that the ceramic constituting the first ceramic layer is selected from Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ . Further, as the ceramics constituting the second ceramics layer, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF _{3 , ZrO 2, TaO 2, CeO} 2, Ce 2 O 3, CeF 3 and at least one selected from the group consisting of _Nd 2 _{O 3} is preferred.

  According to a tenth aspect of the present invention, there is provided a plasma processing container internal member having a substrate and a coating formed on the surface thereof, wherein the coating comprises at least one element belonging to Group 3a of the periodic table. Provided is a member inside a plasma processing container, which has a hydroxide layer made of a hydroxide containing the same.

In the tenth aspect of the present invention, as the hydroxide layer, a thermal spray coating formed by thermal spraying or a thin film formed by a thin film forming technique can be used. The hydroxide constituting the hydroxide layer is preferably selected from Y (OH) ₃ , Ce (OH) ₃ , and Nd (OH) ₃ . Further, at least a part of the hydroxide layer may be subjected to a sealing treatment.

  In the first to tenth aspects of the present invention, an anodic oxide coating may be provided between the base material and the coating. In this case, the anodic oxide coating is sealed with a metal salt aqueous solution. It is preferable that holes have been treated. Further, the anodic oxide film may be one subjected to a sealing treatment with a resin selected from the group consisting of SI, PTFE, PI, PAI, PEI, PBI, and PFA.

An eleventh aspect of the present invention is characterized in that the ceramic sintered body includes at least one element belonging to Group 3a of the periodic table, and at least a part of the ceramic sintered body has been hydrated with steam or high-temperature water. Provided in the plasma processing container. In this case, it is preferable that the ceramic sintered body is obtained by subjecting a ceramic selected from Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ to a hydration treatment.

According to a twelfth aspect of the present invention, there is provided a member inside a plasma processing container, comprising a ceramic sintered body containing a hydroxide containing at least one element belonging to Group 3a of the periodic table. In this case, the hydroxide contained in the ceramic sintered body is preferably selected from Y (OH) ₃ , Ce (OH) ₃ , and Nd (OH) ₃ .

  According to the present invention, since various layers functioning as barriers are provided in the plasma processing vessel inner member having the structure having the base material and the coating formed by thermal spraying, the base material surface is provided with a process gas or a cleaning liquid. Exposure can be prevented, and peeling of the coating formed by thermal spraying can be suppressed.

  Further, according to the present invention, a ceramic containing at least one element belonging to Group 3a of the periodic table is subjected to hydration treatment or a hydroxide containing at least one element belonging to Group 3a of the periodic table is provided. By forming a layer or a sintered body containing a substance, it is possible to obtain a structure in which water is hardly adsorbed and hardly desorbed. it can.

Hereinafter, embodiments of the present invention will be described in detail.
FIG. 1 is a longitudinal sectional view showing an example of a plasma etching processing apparatus which is a plasma processing apparatus having a member inside a plasma processing container to which the present invention is applied. In the figure, reference numeral 2 denotes a vacuum chamber forming a processing vessel, which is formed of a conductive material such as aluminum so as to form an airtight structure, and the vacuum chamber 2 is grounded for safety. In addition, a cylindrical deposition shield 2a is disposed on the inner surface of the vacuum chamber 2 to prevent the inner surface from being damaged by plasma. In the vacuum chamber 2, a gas shower head 3 also serving as an upper electrode and a mounting table 4 also serving as a lower electrode are provided to face each other. An exhaust pipe 22 is connected as a vacuum exhaust path communicating with the vacuum exhaust means 21 composed of. In addition, an opening 23 for carrying in / out an object to be processed, for example, a semiconductor wafer W, is formed in the side wall of the vacuum chamber 2, and can be opened and closed by a gate valve G. Outside the side wall portion, for example, ring-shaped permanent magnets 24 and 25 are respectively provided at positions vertically sandwiching the opening portion 23.

  The gas shower head 3 has a large number of holes 31 formed at positions on the mounting table 4 that face the object W to process the flow-controlled or pressure-controlled process gas sent from the upper gas supply pipe 32. It is configured to uniformly supply the surface of the processing target W through the holes 31.

  The mounting table 4 provided below the gas shower head 3 at a distance of about 5 mm to 150 mm is made of, for example, aluminum whose surface is anodized, and is insulated from the vacuum chamber 2 by the insulating member 41a. A pillar-shaped main body 41, an electrostatic chuck 42 provided on the upper surface of the main body 41, an annular focus ring 43 surrounding the periphery of the electrostatic chuck 42, and a space between the focus ring 43 and the main body 41. And an insulating ring 43a, which is an annular insulating member provided in the first embodiment. The focus ring 43 is made of an insulating or conductive material depending on the process, and acts to confine or diffuse reactive ions.

  A high frequency power supply 40 is connected to, for example, the main body 41 of the mounting table 4 via a capacitor C1 and a coil L1, and high frequency power of, for example, 13.56 MHz to 100 MHz is applied.

  Further, inside the mounting table 4, there are provided a temperature adjusting means 55 a such as a cooling jacket and a heat transfer gas supplying means 55 b for supplying, for example, He gas to the back surface of the processing object W. By activating the heat transfer gas supply unit 55b and the heat transfer gas supply unit 55b, the processing surface temperature of the processing target W held on the mounting table 4 can be set to a desired value. The temperature adjusting means 55a has an inlet pipe 56 and a discharge pipe 57 for circulating the refrigerant through the cooling jacket, and the refrigerant adjusted to an appropriate temperature is supplied into the cooling jacket by the inlet pipe 56, The exchanged refrigerant is discharged to the outside by the discharge pipe 57.

  A ring-shaped exhaust plate 44 having a plurality of exhaust holes is disposed between the mounting table 4 and the vacuum chamber 2 and below the surface of the mounting table 4 so as to surround the mounting table 4. You. The exhaust plate 44 regulates the flow of the exhaust flow and optimally confines the plasma between the mounting table 4 and the gas shower head 3. Further, inside the mounting table 4, a plurality of, for example, three lifting pins 51 (only two are illustrated) are lifted and lowered by a lifting member for transferring the workpiece W to and from a transfer arm (not shown) outside. The lifting pin 51 is provided freely, and is configured to be able to be raised and lowered by a driving mechanism 53 via a connecting member 52. Reference numeral 54 denotes a bellows for maintaining airtightness between the through hole of the elevating pin 51 and the atmosphere side.

  In such a plasma etching apparatus, first, the workpiece W is loaded into the vacuum chamber 2 through the gate valve G and the opening 23, placed on the electrostatic chuck 42, and the gate valve G is closed. After that, the inside of the vacuum chamber 2 is evacuated to a predetermined degree of vacuum through the exhaust pipe 22 by the vacuum exhaust means 21. Then, a process gas is supplied into the vacuum chamber 2, and a DC voltage is applied from the DC power supply 47 to the chuck electrode 46 to cause the workpiece W to be electrostatically adsorbed by the electrostatic chuck 42. A high-frequency electric power of a predetermined frequency is applied to the main body 41 of the mounting table 4 from this, thereby generating a high-frequency electric field between the gas shower head 3 and the mounting table 4, turning the process gas into plasma, and The upper workpiece W is subjected to an etching process.

As the process gas, a gas containing a halogen element such as a fluoride such as C ₄ F ₈ or NF ₃ , a chloride such as BCl ₃ or SnCl _4, or a bromide such as HBr is used. For this reason, the inside of the vacuum chamber 2 becomes an extremely strong corrosive environment. For example, the deposition shield 2a, the exhaust plate 44, the focus ring 43, the shower head 3, the mounting table 4, the electrostatic chuck 42, and the inner wall material of the vacuum chamber 2 The members inside the vacuum chamber 2, that is, the members inside the plasma processing vessel, are required to have high plasma resistance.

Hereinafter, the member inside the processing container which is the object of the present invention will be described in detail.
(1) First Embodiment In the case where a member having a sprayed coating formed on a base material is used as such a processing container inner member, the sprayed coating has conventionally been peeled off. According to the results, peeling of the sprayed coating of the inner member of the plasma processing container may be caused by the process gas or the like from the through-holes (micropores) of the sprayed coating, the boundary with the sprayed coating, or the part damaged by plasma or gas. The inventor has conceived that the cleaning liquid invades and reaches the base material, and is generated by corrosion of the base material surface.

  That is, when a member in a processing container subjected to plasma processing using a process gas containing a fluoride is prepared, and a boundary surface (substrate surface) with the thermal spray coating is analyzed, F (fluorine) is confirmed in that portion. From this, it can be said that F reacts with water (OH) to form HF, thereby causing the substrate surface to undergo a corrosion change (corrosion products are generated), leading to peeling of the thermal spray coating. Guessed.

  Therefore, it is important that the interface with the thermal spray coating, that is, the substrate surface, is not exposed to the process gas or the cleaning liquid.

  Based on such findings, in the first embodiment, the deposition shield 2a, the exhaust plate 44, the focus ring 43, the shower head 3, the mounting table 4, the electrostatic chuck 42, and the inner wall material of the vacuum chamber 2 in FIG. In a member in the vacuum chamber 2 such as a member inside the plasma processing container, the member is hardly corroded even when exposed to a process gas or a cleaning liquid at any position from the surface of the sprayed coating to the substrate. A portion having a barrier function that can be prevented from reaching the surface is formed.

  By forming a portion having a barrier function with such a material having excellent corrosion resistance, the surface of the base material is protected against a gas or a cleaning liquid that enters through through pores (micropores) of the thermal spray coating. Is possible. Further, if the portion having the barrier function is brought into contact with the base material, by selecting a material having high adhesion as the material, the process gas from the interface between the portion having the barrier function and the surface of the base material is selected. Alternatively, it is possible to protect the surface of the base material from entering the cleaning liquid.

Hereinafter, a specific configuration in the first embodiment will be described in detail.
First, as shown in FIG. 2, the member in the plasma processing container according to the first example basically includes a base material 71 and a coating 72 formed on the surface thereof. The coating 72 has a main layer 73 formed by thermal spraying, and a barrier coat layer 74 having a barrier function that is hardly corroded even when exposed to a process gas or a cleaning liquid between the base 71 and the main layer. .

  The base material 71 on which the coating film 72 is applied includes various steels including stainless steel (SUS), Al and Al alloys, W and W alloys, Ti and Ti alloys, Mo and Mo alloys, carbon and oxide-based materials. , A non-oxide ceramic sintered body, and a carbonaceous material are preferably used.

The material of the barrier coat layer 74 is preferably a ceramic containing at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd. More specifically, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , At least one ceramic selected from the group consisting of CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ is suitable. For example, “CDC-ZAC” or “Super ZAC” manufactured by Tokaro Corporation can be applied. “CDC-ZAC” is a composite ceramic containing Cr ₂ O ₃ as a main component, and has properties such as porelessness, high hardness, and high adhesion. On the other hand, “Super ZAC” is a composite ceramic containing SiO ₂ and Cr ₂ O ₃ as main components, and is excellent in heat resistance and abrasion resistance in addition to non-porosity, high hardness and high adhesion. This barrier coat layer 74 is preferably formed by a thermal spraying method. The thermal spraying method is a method in which a raw material melted by a heat source such as combustion gas or electricity is sprayed on a base material to form a coating. Further, the barrier coat layer 74 can also be formed by a thin film forming technique such as a PVD method or a CVD method, a dipping method, or a coating method. The PVD method is a method of coating various ceramic films at a low temperature by an ion plating method, while the CVD method is a method of coating a single layer or a multilayer at a high temperature by a thermochemical vapor deposition method. The immersion method is a method in which various materials are immersed in a resin solution and then heat-treated. The coating method is a method in which a resin solution is applied to various materials and heat-treated at a predetermined temperature. The thickness of the barrier coat layer 74 is preferably 50 to 100 μm.

  In this case, at least a part of the barrier coat layer 74, for example, a bonding surface side with the base material 71 or the entirety thereof is preferably subjected to a sealing treatment using a resin. As the resin at that time, a resin selected from the group of SI, PTFE, PI, PAI, PEI, PBI, and PFA is preferable. That is, when the barrier coat layer 74 made of ceramic is formed by the above-described thermal spraying method or the like, the barrier coat layer 74 is formed of a porous material having through-holes (micropores), and at least a part of the micropores of the porous layer is formed of resin. By sealing, the effect of blocking gas or cleaning liquid entering through the fine holes of the main layer 73, which is a thermal spray coating, is enhanced, and the base material 71 can be effectively protected.

  SI is silicone, PTFE is polytetrafluoroethylene, PI is polyimide, PAI is polyamideimide, PEI is polyetherimide, PBI is polybenzimidazole, and PFA is perfluoroalkoxyalkane.

The sealing treatment can be performed by a sol-gel method. The sealing treatment by the sol-gel method is performed by sealing with a sol (colloid solution) in which ceramics is dispersed in an organic solvent and then gelling by heating. Thereby, sealing with ceramics is realized, and the barrier effect can be improved. In this case, it is preferable to use a material selected from elements belonging to Group 3a of the periodic table for the sealing treatment. Among them, Y ₂ O ₃ having high corrosion resistance is preferable.

  Further, as another material of the barrier coat layer 74, engineering plastic can be suitably used. Specifically, it is preferably a resin selected from the group of PTFE, PI, PAI, PEI, PBI, PFA, PPS, and POM, such as "Teflon (registered trademark)" (PTFE) manufactured by DuPont. Can be applied. These resins have excellent adhesiveness, are excellent in chemical resistance, and can sufficiently withstand a cleaning liquid at the time of cleaning.

  In addition, PTFE means polytetrafluoroethylene, PI means polyimide, PAI means polyamideimide, PEI means polyetherimide, PBI means polybenzimidazole, PFA means perfluoroalkoxyalkane, PPS means polyphenylene sulfide, and POM means polyacetal.

  Further, an anodic oxide film 75 may be formed between the base material 71 and the barrier coat layer 74 as shown in FIG. In this case, by forming an anodic oxide film with an organic acid such as oxalic acid, chromic acid, phosphoric acid, nitric acid, formic acid, or sulfonic acid, an oxide film having excellent corrosion resistance compared to the case of anodizing treatment with sulfuric acid is formed. The formation is preferable because corrosion by a process gas or a cleaning liquid can be further suppressed. The thickness of the anodic oxide coating 75 is preferably 10 to 200 μm.

  As described above, when the anodic oxide film 75 is formed between the base material 71 and the barrier coat layer 74, the corrosion resistance can be remarkably improved by sealing the fine holes of the anodic oxide film 75. In this case, the material is immersed in hot water containing a metal salt such as Ni, and the metal salt aqueous solution is hydrolyzed in the fine pores of the oxide film and the hydroxide is precipitated, whereby the metal salt is sealed. Holes and the like can be applied.

  Similar effects can be expected even if the micropores of the anodic oxide coating 75 are sealed with a resin. As the resin in this case, a resin selected from the above-mentioned group of SI, PTFE, PI, PAI, PEI, PBI, and PFA is preferable.

  Further, as the anodic oxide film 75 formed on the surface of the base material 71, an anodic oxide film having a porous ceramic layer (KEPLA-COAT: registered trademark) may be used.

  The anodic oxide film (KEPLA-COAT) is formed by immersing the base material as an anode in an alkaline organic electrolyte and discharging oxygen plasma in the alkaline organic electrolyte.

The main layer 73, which is a thermal spray coating, preferably contains at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd. Include B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce _At least one ceramic selected from ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ is preferred. In this case, the main layer 73 preferably has a thickness of 10 μm to 500 μm.

When manufacturing the inner member of the plasma processing container having such a structure, first, the surface of the base material 71 is subjected to a blast process of spraying particles such as Al ₂ O ₃ , SiC or sand, and the surface is microscopically uneven. It is preferable to improve the adhesion to the barrier coat layer 74 and the anodic oxide film 75 to be formed thereon. Further, the method for making the surface uneven is not limited to the above blast treatment, and for example, the surface may be etched by being immersed in a predetermined chemical solution.

  Next, the above-described barrier coat layer 74 is formed on the substrate 71 directly or via the anodic oxide film 75 by an appropriate method such as a thermal spraying method. If necessary, the above-described sealing treatment is performed. In the sealing treatment, the above resin or ceramic sol is applied to the surface of the barrier coat layer 74, or the base material 71 with the barrier coat layer 74 is immersed in a resin sealing agent or ceramic sol. . When the pores are sealed with a ceramic sol, they are then heated and gelled.

After forming the barrier coat layer 74, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , and YF are successively formed thereon. ₃ , a main layer 73 which is a thermal spray coating made of at least one ceramic selected from the group consisting of ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ . The barrier coat layer 74 is selected from those having excellent adhesion. However, in order to further improve the adhesion with the main layer 73, the surface of the barrier coat layer 74 may be subjected to blast treatment or the like.

  As described above, in this example, the barrier coat layer 74 made of a material having excellent corrosion resistance to a process gas or a cleaning liquid containing a halogen element is formed between the main layer 73 which is a thermal spray coating and the base material 71. Since the surface of the substrate 71 is configured not to be exposed to the process gas (halogen element) or the cleaning solution, corrosion products are generated on the surface of the substrate 71, so that the thermal spray coating 72 on the substrate 71 is formed. The problem of peeling can be solved.

Next, a second example will be described.
In the second example, as shown in FIGS. 4A, 4B, and 4C, a coating 76 is formed on the surface of the substrate 71 by spraying ceramics, and at least a portion of the coating 76 is sealed. The processing section 76a is formed. In the example of FIG. 4A, the sealing portion 76a is formed on the base material 71 side of the coating 76. In the example of FIG. 4B, the sealing portion 76a is formed on the surface side of the coating 76. In the example of FIG. 4C, the entire coating 76 is used as the sealing portion 76a.

Coating 76, B, is intended to include the Mg, Al, Si, Ca, Cr, Y, Zr, Ta, at least one element selected from the group consisting of Ce and Nd, specifically, _{B 4} C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , CeF _At least one ceramic selected from the group consisting of ₃ and Nd ₂ O ₃ is preferred. In this case, the thickness of the coating 76 is preferably 50 to 300 μm. Note that the same material as in the first example can be used as the base material 71.

  The sealing portion 76a can be formed by completely the same resin sealing or sol-gel sealing as that performed on the barrier layer 74 of the first example described above. By providing the sealing portion 76a in this manner, gas or a cleaning liquid that enters through the fine holes of the coating 76 that is a thermal spray coating can be effectively prevented, and the base material 71 can be sufficiently protected. it can. Since the sealing section 76a is for preventing the gas or the cleaning liquid from reaching the base material 71 as described above, the effect is exhibited in any of (a) to (c) of FIG. be able to. However, as shown in FIG. 4A, it is desirable to form a sealing portion 76a on the base material 71 side of the coating film 76. That is, when a member in a processing vessel in which a thermal spray coating is subjected to sealing treatment is used in a plasma atmosphere in which high-frequency power is applied in a high vacuum region (for example, 13.3 Pa), the diluted organic solvent in the sealing agent ( For example, pores (micropores) may be formed again in the thermal spray coating due to evaporation of the ethyl acetate) or corrosion of the sealing agent by plasma or process gas. The pores may change the surface state (temperature, adhesion state of products, and the like) of the agent inside the processing container over time, which may adversely affect processes in the processing container. Therefore, if the sealing treatment is not performed on the surface side of the coating 76 as shown in FIG. 4A, the surface modification of the coating 76 can be suppressed and the process can be stably performed. The sealing section 76a is not limited to the positions shown in FIGS. 4A to 4C, but may be formed at an intermediate position of the coating 76, for example. The thickness of the sealing portion 76a is preferably 50 to 100 μm.

  Also in this example, as shown in FIG. 5, an anodic oxide film 75 exactly the same as in the first example described above may be formed between the base material 71 and the film 76. Also in this case, it is preferable that the anodic oxide film 75 is sealed. As the sealing process, the same metal salt sealing as described above can be applied.

Next, a third example will be described.
In the third example, as shown in FIGS. 6A and 6B, a coating 77 is formed on the surface of the base material 71 by spraying ceramics, and the coating 77 is formed on the first ceramic layer 78 and the first ceramic layer 78. The two ceramic layers 79 have a two-layer structure, and a sealing portion is formed in at least a part of at least one of the two ceramic layers. In the example of FIG. 6A, the sealing portion 78a is formed in the first ceramic layer 78 on the front side, and in FIG. 6B, the second ceramic layer 79 on the base material 71 side is shown. A sealing processing part 79a is formed.

Each of the first ceramic layer 78 and the second ceramic layer 79 constituting the coating 77 is selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd. It contains at least one element, specifically, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , At least one ceramic selected from the group consisting of YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O ₃ is suitable. In this case, the thickness of the coating 77 is preferably 50 to 300 μm. Note that the same material as in the first example can be used as the base material 71.

  The sealing portions 78a and 79a can be formed by completely the same resin sealing or sol-gel sealing as that applied to the barrier coat layer 74 of the first example described above. By providing the sealing portions 78a and 79a in this manner, it is possible to effectively prevent gas or cleaning liquid that enters through the fine holes of the first and second ceramic layers 78 and 79, which are the thermal spray coating. In addition, the base material 71 can be sufficiently protected. Since the sealing portions 78a and 79a are for preventing the gas or the cleaning liquid from reaching the base material 71 as described above, the positions of the sealing portions 78a and 79a are as long as their functions can be exhibited. It is not limited, and the entire layer may be used as a sealing treatment section. In addition, a sealing portion may be formed on both the first and second ceramic layers 78 and 79. The thickness of the sealing portions 78a and 79a is preferably 50 to 100 μm.

Thus, by forming the coating 77 formed on the base material 71 into a two-layer structure, the materials of these two layers can be appropriately set in accordance with the required corrosion resistance and barrier properties, and can be formed at desired positions. By applying the sealing treatment, an extremely flexible application is possible. For example, Y ₂ O ₃ is used as the first ceramic layer 78 on the front surface side, YF ₃ or Al ₂ O ₃ is used as the second ceramic layer 79 on the base material 71 side, and at least one of the second ceramic layers 79 is used. If the part is subjected to a sealing treatment, the corrosion resistance and the barrier property can be made extremely high.

  Also in this example, as shown in FIG. 7, an anodic oxide film 75 exactly the same as in the first example described above may be formed between the base material 71 and the film 77. Also in this case, it is preferable that the anodic oxide film 75 is sealed. As the sealing process, the same metal salt sealing as described above can be applied.

In order to confirm the effect of the present embodiment, Sample 1 in which a thermal sprayed coating of Y ₂ O ₃ was formed on an Al alloy substrate, and Y on a Al alloy substrate via a resin (PTFE) barrier coat layer. Sample 2 on which a thermal spray coating of ₂ O ₃ was formed and Sample _{3 on which} a thermal spray coating of Y ₂ O ₃ was formed on an Al alloy base material and a part thereof was sealed with a resin were prepared. The hydrofluoric acid (HF) solution was dropped on the surfaces of Nos. 1 to 3, and the surface states of the sprayed coatings when placed in a plasma environment were compared. More specifically, 10 μL of a 38% hydrofluoric acid solution was dropped on the surface of each sample, heated at 50 ° C. for 3 hours, and then left for 3 minutes in a CF-based gas plasma atmosphere. As a result, in Sample 1 in which no measures were taken against peeling of the thermal spray coating, cracks occurred on the entire surface, whereas Sample 2 in which a barrier coat layer was formed between the base material and the thermal spray coating, Sample 3 in which a part was sealed with a resin did not have any cracks, indicating that the intrusion of the hydrofluoric acid solution was prevented and the surface of the base material was protected.

(2) Second Embodiment In the case where Al ₂ O ₃ or Y ₂ O ₃ is used for the wall material of the plasma processing container or other members inside the plasma processing container, the reactivity with the moisture in the air is high. When the vacuum chamber, which is a processing container, is opened to the atmosphere or when the vacuum chamber is wet-cleaned, a large amount of water is taken in, causing various problems. According to the results of studies by the present inventors, Y ₂ O ₃ It has been found that such inconvenience is solved by subjecting a ceramic containing an element belonging to Group 3a of the periodic table to hydration treatment or forming a hydroxide containing these elements.

  Based on such knowledge, in the second embodiment, the deposit shield 2a, the exhaust plate 44, the focus ring 43, the shower head 3, the mounting table 4, the electrostatic chuck 42, and the inner wall material of the vacuum chamber 2 in FIG. In a member in the vacuum chamber 2, such as a member in the plasma processing vessel, a portion obtained by subjecting a ceramic containing an element belonging to Group 3a of the periodic table to a hydration treatment is formed, or at least a part of the portion includes the element. A hydroxide was used.

  By doing so, it is possible to obtain a structure in which moisture is hardly adsorbed and hardly desorbed, so that it is possible to obtain a member in the plasma processing vessel in which water is hardly desorbed during the plasma processing.

  First, in the first example, as shown in FIG. 8, a film 82 made of a ceramic containing an element belonging to Group 3a of the periodic table is formed on a base material 81, and for example, hydration is performed on at least the surface portion thereof. The processing section 82a is formed.

  As the base material 81, similarly to the base material 71, various steels including stainless steel (SUS), Al and Al alloys, W and W alloys, Ti and Ti alloys, Mo and Mo alloys, carbon and oxide-based materials, A non-oxide ceramic sintered body, a carbonaceous material, and the like are preferably used.

The coating 82 may be made of a ceramic containing an element belonging to Group 3a of the periodic table, but is preferably an oxide containing an element belonging to Group 3a of the periodic table. Among these, Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ are preferable, and among them, Y ₂ O ₃ is particularly preferable because it has been widely used and has high corrosion resistance. .

  This film 82 can be suitably formed by a thin film forming technique such as a thermal spraying method, a PVD method or a CVD method. In addition, it can also be formed by a method such as a dipping method or a coating method.

The hydration treatment section 82a can be formed, for example, by causing a hydration reaction by reacting the coating 82 with steam or high-temperature water. When Y ₂ O ₃ is used as ceramics, a reaction such as the following equation (1) occurs.
Y ₂ O ₃ + H ₂ O → Y ₂ O _3. (H ₂ O) _n → 2 (YOOH) → Y (OH) ₃ (1)
However, the above equation (1) does not consider the valence.
As shown in the formula (1), the hydration treatment finally forms a hydroxide of Y. In the case of other elements belonging to Group 3a of the periodic table, such a hydroxide is formed by a substantially similar reaction. As such a hydroxide, Y (OH) ₃ , Ce (OH) ₃ , and Nd (OH) ₃ are preferable.

In order to confirm this, a sample having a thermal spray coating of Y ₂ O ₃ formed on a base material was prepared, immersed in high-temperature water at 80 ° C. for 150 hours, hydrated, and then dried at room temperature. An X-ray diffraction measurement was performed on the sample that had been subjected to the above-mentioned treatment and the sample that had not been subjected to such treatment. As a result, as shown in FIGS. 9A and 9B, Y (OH) ₃ was recognized only in the sample subjected to the hydration treatment, and it was confirmed that hydroxide was formed by the hydration treatment. Was done.

  Hydroxides of elements belonging to Group 3a of the periodic table are extremely stable, and have characteristics that chemically adsorbed water is hardly desorbed and water is hardly adsorbed. By forming such a hydroxide, inconvenience due to moisture during the process can be avoided.

In order to confirm the effect of such a hydration treatment, a Y ₂ O ₃ sprayed coating was formed on a substrate to a thickness of about 200 μm, and a sample treated with boiling water for 3 hours and a sample not treated were prepared. And IPA was sprayed on both. It should be noted that IPA has higher adsorptivity than water, and therefore, IPA spraying is an accelerated test. As a result of this test, as shown in FIG. 10, IPA was adsorbed on the sample not subjected to hydration treatment, but was not adsorbed on the sample subjected to hydration treatment. From this, it was confirmed that water absorption was extremely unlikely to occur due to the hydration treatment.

Next, similarly to the above, a Y ₂ O ₃ thermal spray coating was formed on the base material to a thickness of about 200 μm, and a sample treated with boiling water for 3 hours and a sample not treated were prepared. After coating, the section was confirmed by cutting. As a result, as shown in FIGS. 11 (a) and 11 (b), although the surface state is not different between the two, the coating is entirely transparent and the whole is "no treatment" in the case of "no treatment". It is recognized that the resin had permeated, whereas in the case of "treated", only a small part of the surface layer was transparent, the inside was white, and it was confirmed that the resin had hardly penetrated. Was. That is, it was found that the hydration treatment resulted in hydrophobicity. Further, as shown in FIG. 11C, when about 20 μm is removed after the hydration treatment, the portion becomes transparent, and by removing about 20 μm of the hydrated surface layer, the hydrophobicity is reduced. It was confirmed that.

Incidentally, H 2 _O is the impact on the Y ₂ O ₃ surface, Langmuir, Vol.16, Kuroda et al. Pp 6937-6947 of No.17,2000 "Specific Adsorption Behavior of Water on a Y 2 O ₃ Surface ”.

Hereinafter, the hydration treatment will be specifically described.
The hydration treatment can be performed by heat treatment in an environment rich in steam or by treatment in boiling water. As a result, for example, several water molecules can be attracted and bound around the yttria (Y ₂ O ₃ ) molecule to form one stable molecular population. At this time, the partial pressure of steam, heat treatment temperature, heat treatment time, and the like are parameters. For example, a stable hydroxide can be formed by performing heat treatment for about 24 hours in a furnace at about 100 to 300 ° C. in an environment where the relative humidity is 90% or more. If the relative humidity or the heat treatment temperature is low, the treatment time may be extended. In order to carry out the hydration treatment efficiently, it is preferable to carry out the treatment at high temperature and high pressure. The hydration reaction on the yttria surface basically proceeds sufficiently for a long time even at about room temperature, so that the same final state can be obtained under conditions other than the above. In addition, when the hydration treatment is performed, the hydration treatment using water containing ions (alkaline water having a pH of greater than 7) is more excellent in hydrophobicity than the hydration treatment using pure water. Become.

  The method is not limited to the hydration treatment, and other methods may be adopted as long as the hydroxide is finally formed, for example, a hydroxide at the raw material stage. When the coating is manufactured by the thermal spraying method, since the raw material is exposed to a high temperature, there is a concern that when the raw material is converted into a hydroxide at the raw material stage, the hydroxide is converted into an oxide. A hydroxide film can be formed by spraying underneath. Thus, instead of forming the hydration treatment section, a hydroxide may be directly formed by another method.

  Such a hydrated portion or hydroxide layer needs to be formed on the surface of the coating 82 in order to make the coating 82 hardly adsorb moisture and hardly desorb. In this case, the thickness of the hydration treatment section or the hydroxide film is preferably 100 μm or more, and is preferably set to an optimum thickness according to the place of use.

Densification is also promoted by hydrating ceramics containing elements belonging to Group 3a of the periodic table. For example, a Y ₂ O ₃ film formed by thermal spraying, which had a porous state as shown in FIG. It is densified as shown in FIG. With such a densification, a barrier effect as in the first embodiment can be obtained in addition to the above effects.

  From the viewpoint of obtaining only the barrier effect, the hydration-treated portion 82a converted into a hydroxide by the hydration treatment does not necessarily have to be on the surface, but may be formed at any position of the coating film 82. When forming a hydroxide layer converted into a hydroxide by another method, it is preferable to perform the sealing treatment by the resin or the sol-gel method as described above. In this example, as shown in FIG. 13, similarly to the first embodiment, an anodic oxide film 83 exactly the same as in the first embodiment is formed between a base material 81 and a film 82. Is also good. Further, similarly to the first embodiment, it is preferable that the anodic oxide film 83 is subjected to a sealing treatment. As the sealing treatment, the same metal salt sealing as described above can be applied.

Next, a second example will be described.
In the second example, as shown in FIGS. 14A and 14B, a coating 84 is formed on the surface of a base material 81, and the coating 84 is formed by a first ceramic layer 85 and a second ceramic layer. 86, and a hydration treatment part is formed on at least a part of at least one of the two. In the example of FIG. 14A, a hydration treatment portion 85a is formed on the first ceramic layer 85 on the front surface side, and in FIG. 14B, the second ceramic layer 86 on the base material 81 side is formed. The hydration processing part 86a is formed.

Each of the first ceramic layer 85 and the second ceramic layer constituting the coating 84 is made of a ceramic containing an element belonging to Group 3a of the periodic table, as in the first example. An oxide containing an element belonging to Group 3a is preferable, and among these, Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ are preferable, and Y ₂ O ₃ is particularly preferable. Note that the same material as in the first example can be used as the base material 81.

  These first and second ceramic layers 85 and 86 can be suitably formed by a thin film forming technique such as a thermal spraying method, a PVD method, or a CVD method, similarly to the coating 82 in the first example. In addition, it can also be formed by a method such as a dipping method or a coating method.

  The hydration units 85a and 86a can be formed in exactly the same manner as the hydration unit 82a in the first example. As shown in FIG. 14A, in the case where a hydrated portion is provided on the surface of the coating 84, a structure can be obtained in which moisture is hardly adsorbed and hardly desorbed, as shown in FIG. 14B. As described above, when the hydrated portion is present inside the coating 84, the barrier effect can be effectively exhibited. In order to form the hydrated portion 86a inside the coating 84, the second ceramic layer 86 is manufactured on the base material 81, then hydrated, and then the first ceramic layer 85 may be formed. . It is preferable that the thickness of the hydrated parts 85a and 86a be 100 μm or more.

  In this way, by forming the coating 84 formed on the base material 81 into a two-layer structure, the materials of these two layers and the position of the hydration treatment can be appropriately set according to the required characteristics. Application with a high degree of freedom is possible.

  Also in this example, as shown in FIG. 15, an anodic oxide film 83 exactly the same as in the first example may be formed between the base material 81 and the film 84.

Next, a third example will be described.
In the third example, as shown in FIG. 16, a coating 87 is formed on the surface of a base material 81, and the coating 87 is made of a first ceramic made of a ceramic containing at least one element belonging to Group 3a of the periodic table. It has a ceramic layer 88 and a second ceramic layer 89 formed by spraying ceramics, and a hydration treatment section 88 a is formed on the surface of the first ceramic layer 88.

The ceramic containing an element belonging to Group 3a of the periodic table of the first ceramic layer 88 is preferably an oxide containing an element belonging to Group 3a of the periodic table. Among these, Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ are preferred, and Y ₂ O ₃ is particularly preferred. The thickness of the first ceramics layer 88 is preferably 100 to 300 μm. The first ceramics layer 88 can be suitably formed by a thin film forming technique such as a thermal spraying method, a PVD method, or a CVD method, similarly to the coating 82 in the first example. In addition, it can also be formed by a method such as a dipping method or a coating method.

As the second ceramic layer 89, a layer containing at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd is preferable. Specifically, B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , CeO ₂ at least one ceramic selected from the group consisting of _Ce 2 _{O 3,} CeF 3 and _Nd 2 _{O 3} is preferred. The thickness of the second ceramic layer 89 is preferably 50 to 300 μm. In addition, as the base material 81, the same material as in the first example can be used.

  The hydration processing section 88a can be formed in exactly the same way as the hydration processing section 82a in the first example. Since the hydrated portion is formed on the surface of the coating 87 as described above, it is possible to obtain a structure in which moisture is hardly adsorbed and hardly desorbed. In addition, the hydration treatment part 88a can be formed inside the first ceramics layer 88 to exert a barrier effect. The thickness of the hydrated portion 88a is preferably 100 μm or more.

  As shown in FIG. 17, it is preferable to form a sealing portion 89a in the second ceramic layer 89. The sealing processing section 89a can be formed by completely the same resin sealing or the sol-gel sealing as described in the first embodiment. As described above, by providing the sealing processing portion 89a, gas or cleaning liquid that enters through the fine holes of the second ceramics layer 89, which is a thermal spray coating, can be effectively prevented, and the base material 81 can be sufficiently protected. Can be protected. The sealing section 89a can be formed at an arbitrary position on the second ceramic layer 89.

  With the structure as shown in FIGS. 16 and 17, it is possible to obtain a structure that is excellent in corrosion resistance and hardly adsorbs moisture and hardly desorbs by the hydration treatment portion 88 a of the first ceramics layer 88. Moreover, the base material 81 can be effectively protected by the barrier effect of the second ceramic layer 89. In particular, in the structure of FIG. 17, the barrier effect can be further enhanced by the presence of the sealing section 89a.

  Note that, as shown in FIG. 18, the first ceramic layer 88 and the second ceramic layer 89 may be reversed. In this case, a barrier effect is effectively exerted in the hydration treatment portion 88a of the first ceramics layer 88 on the base material 81 side, and the protection effect of the base material 81 can be enhanced.

  Also in this example, as shown in FIG. 19, an anodic oxide film 83 exactly the same as in the first example may be formed between the base material 81 and the film 87.

Next, a third embodiment will be described.
As shown in FIG. 20, in the plasma processing container inner member according to this embodiment, a hydrated portion 91 is formed on the surface of a ceramic sintered body 90 containing an element belonging to Group 3a of the periodic table. The hydration treatment section 91 can be formed in exactly the same manner as in the second embodiment, and a hydroxide containing an element belonging to Group 3a of the periodic table is formed by hydration treatment.

  By forming the hydration treatment section 91 on the surface in this way, a structure can be provided in which moisture is hardly adsorbed and desorbed. In this case, the thickness of the hydration treatment section 91 or the hydroxide film is preferably 100 μm or more.

Also in the present embodiment, as in the second embodiment, it is preferable to use a ceramic containing an element belonging to Group 3a of the periodic table and an oxide containing an element belonging to Group 3a of the periodic table. Among them, Y ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , and Nd ₂ O ₃ are preferable, and Y ₂ O ₃ is particularly preferable.

  The present invention is not limited to the above-described embodiment, but can be variously modified. For example, in the above-described embodiment, the deposition shield 2a, the exhaust plate 44, the focus ring 43, the shower head, and the inner members of the plasma processing container of the magnetron type parallel plate type plasma etching apparatus using the permanent magnet shown in FIG. 3, the case where the present invention is applied to the mounting table 4, the electrostatic chuck 42, and the inner wall material of the vacuum chamber 2 has been described as an example. However, the present invention is not limited to the apparatus having such a configuration. A parallel plate type plasma etching apparatus not used, another plasma etching apparatus such as an inductive coupling type, and an apparatus for performing not only the etching apparatus but also various plasma processings other than the etching such as the ashing processing and the film forming processing, and the like. , Plasma processing equipment that processes not only semiconductor wafers but also glass substrates for LCDs It is applicable to the members of all the processing vessel.

  The inner member of the plasma processing container according to the present invention is particularly suitable for processing by plasma in a highly corrosive atmosphere because the coating formed on the substrate is made of a highly corrosion-resistant ceramic and a portion functioning as a barrier is provided. is there. In addition, since ceramics containing an element belonging to Group 3a of the periodic table are subjected to hydration treatment to obtain a structure that is stable against water, the ceramics are suitable as members in a plasma processing container in which moisture is a problem.

FIG. 1 is a longitudinal sectional view showing a plasma etching apparatus on which a member inside a plasma processing container according to an embodiment of the present invention is mounted. FIG. 2 is a cross-sectional view illustrating a layer configuration of a first example of a member inside the plasma processing container according to the first embodiment of the present invention. Sectional drawing which shows the example which added the anodic oxide film to the structure of FIG. FIG. 4 is a cross-sectional view illustrating a layer configuration of a second example of the member inside the plasma processing container according to the first embodiment of the present invention. FIG. 5 is a sectional view showing an example in which an anodic oxide film is added to the configuration of FIG. 4. FIG. 4 is a sectional view showing a layer configuration of a third example of the plasma processing container inner member according to the first embodiment of the present invention. FIG. 7 is a sectional view showing an example in which an anodic oxide film is added to the configuration of FIG. 6. FIG. 6 is a sectional view showing a layer configuration of a first example of a member inside a plasma processing container according to a second embodiment of the present invention. The figure which shows the case where the hydration process is performed to the Y2O3 film | membrane, and the case where it does not perform and shows an X-ray analysis pattern in comparison. The figure which shows comparison of the adsorption | suction of IPA in the case where a hydration process is performed to the Y2O3 film | membrane, and the case where it is not performed. FIG. 4 is a diagram showing a comparison of resin penetration between a case where a hydration treatment is performed on a Y2O3 coating and a case where a hydration treatment is not performed. The scanning electron micrograph which shows the layer state before and after a hydration process in comparison, and shows it. FIG. 9 is a sectional view showing an example in which an anodic oxide film is added to the configuration of FIG. 8. FIG. 9 is a sectional view showing a layer configuration of a second example of the plasma processing container inner member according to the second embodiment of the present invention. FIG. 15 is a sectional view showing an example in which an anodic oxide film is added to the configuration of FIG. 14. FIG. 13 is a sectional view showing a layer configuration of a third example of the member inside the plasma processing container according to the second embodiment of the present invention. FIG. 13 is a sectional view showing a layer configuration of a third example of the member inside the plasma processing container according to the second embodiment of the present invention. FIG. 13 is a sectional view showing a layer configuration of a third example of the member inside the plasma processing container according to the second embodiment of the present invention. FIG. 17 is a sectional view showing an example in which an anodic oxide film is added to the configuration of FIG. 16. FIG. 9 is a schematic diagram illustrating a member inside a plasma processing container according to a third embodiment of the present invention. The figure which shows typically the state which the thermal spray coating (top coat layer) peels in the conventional member in a plasma processing container.

Explanation of reference numerals

2, vacuum chamber 2a; deposit shield 3, gas shower head 4, mounting table 42, electrostatic chuck 43, focus ring 44, exhaust plate 71, 81, base material 72, 76, 77, 82, 84, 87; Barrier coating layers 75, 83; anodic oxide coatings 76a, 78a, 79a; sealing treatment parts 82a, 86a, 88a, 91;

Claims (35)

A member in a plasma processing vessel having a base material and a coating formed on the surface by spraying ceramics,
The ceramic constituting the coating contains at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce, and Nd, at least a portion of which is made of resin. An inner member of a plasma processing container, which is subjected to a sealing process. A member in a plasma processing vessel having a base material and a coating formed on the surface by spraying ceramics,
A first ceramic layer made of a ceramic containing at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd; A second ceramic layer made of a ceramic containing at least one element selected from the group consisting of Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce, and Nd; 2. An inner member of a plasma processing container, wherein at least a part of at least one of the ceramic layers is sealed with a resin.   3. The member according to claim 1, wherein the resin is selected from the group consisting of SI, PTFE, PI, PAI, PEI, PBI, and PFA. 4. A member in a plasma processing vessel having a base material and a coating formed on the surface by spraying ceramics,
The ceramic constituting the coating contains at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd, at least a part of which is a sol-gel method. An inner member of a plasma processing container, wherein the inner member has been subjected to a sealing process. A member in a plasma processing vessel having a base material and a coating formed on the surface by spraying ceramics,
A first ceramic layer made of a ceramic containing at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd; A second ceramic layer made of a ceramic containing at least one element selected from the group consisting of Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce, and Nd; 2. An inner member for a plasma processing container, wherein at least a part of at least one of the ceramic layers is subjected to a sealing treatment by a sol-gel method.   The member according to claim 4, wherein the sealing is performed using an element selected from elements belonging to Group 3a of the periodic table. The _{ceramics, B 4 C, MgO, Al} 2 O 3, SiC, Si 3 N 4, SiO 2, CaF 2, Cr 2 O 3, Y 2 O 3, YF 3, ZrO 2, TaO 2, CeO 2, characterized in that it is a ce ₂ O _3, CeF ₃ and _Nd 2 _{O 3,} at least one member selected from the group consisting of a plasma processing chamber member according to any one of claims 1 to 6 . A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The coating comprises a main layer formed by spraying ceramics, and a barrier made of ceramics containing an element selected from the group consisting of B, Mg, Al, Si, Ca, Cr, Y, Zr, Ta, Ce and Nd. A member in a plasma processing container, comprising: a coating layer. The barrier coating _{layer, B 4 C, MgO, Al} 2 O 3, SiC, Si 3 N 4, SiO 2, CaF 2, Cr 2 O 3, Y 2 O 3, YF 3, ZrO 2, TaO 2, CeO 9. The member according to claim 8, wherein the member is made of at least one ceramic selected from the group consisting of ₂ , ₂ , Ce ₂ O ₃ , CeF _3, and Nd ₂ O ₃ .   10. The plasma processing container inner member according to claim 8, wherein the barrier coat layer is a thermal sprayed coating at least part of which is sealed with a resin.   The member according to claim 10, wherein the resin is selected from the group consisting of SI, PTFE, PI, PAI, PEI, PBI, and PFA.   The plasma processing container inner member according to claim 8 or 9, wherein the barrier coat layer is a thermal spray coating that is at least partially sealed by a sol-gel method.   The member according to claim 12, wherein the sealing treatment is performed using an element selected from elements belonging to Group 3a of the periodic table. A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The member in the plasma processing container, wherein the coating has a main layer formed by spraying ceramics, and a barrier coat layer made of engineering plastic formed between the base material and the main layer. .   The member according to claim 14, wherein the engineering plastic is a plastic selected from the group consisting of PTFE, PI, PAI, PEI, PBI, PFA, PPS, and POM. The main _{layer, B 4 C, MgO, Al} 2 O 3, SiC, Si 3 N 4, SiO 2, CaF 2, Cr 2 O 3, Y 2 O 3, YF 3, ZrO 2, TaO 2, CeO 2 , characterized in that it is composed of at least one ceramics selected from the group consisting of _Ce 2 _{O 3,} CeF 3 and _Nd 2 _{O 3,} according to any one of claims 15 claim 11 Of the plasma processing vessel. A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The inside of the plasma processing vessel, wherein the coating is made of a ceramic containing at least one element belonging to Group 3a of the periodic table, and at least a part of the coating is hydrated with steam or high-temperature water. Wood. A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The coating is a first ceramic layer made of a ceramic containing at least one element belonging to Group 3a of the periodic table, and a second ceramic layer made of a ceramic containing at least one element belonging to Group 3a of the periodic table. Wherein at least a part of at least one of the first and second ceramic layers has been hydrated with steam or high-temperature water.   The member according to claim 17 or 18, wherein the coating is a thermal spray coating formed by thermal spraying or a thin film formed by a thin film forming technique. Ceramics constituting the _coating, Y ₂ O _3, from _{CeO 2, Ce 2 O 3,} Nd 2 O 3 claim 17, characterized in that one selected from any one of claims 19 The member in the plasma processing vessel described in the above. A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The coating has a first ceramics layer made of ceramics containing at least one element belonging to Group 3a of the periodic table, and a second ceramics layer formed by spraying ceramics. An inner member of a plasma processing container, wherein at least a part thereof is hydrated by steam or high-temperature water.   22. The member according to claim 21, wherein the first ceramics layer is a thermal spray coating formed by thermal spraying or a thin film formed by a thin film forming technique. The ceramics constituting the first ceramic _layer, according to _{Y 2 O 3, CeO 2,} Ce 2 O 3, Nd 2 claim 21 or claim 22, characterized in that the _{O 3} are those selected Inside member of plasma processing vessel. The second ceramic layer is made of B ₄ C, MgO, Al ₂ O ₃ , SiC, Si ₃ N ₄ , SiO ₂ , CaF ₂ , Cr ₂ O ₃ , Y ₂ O ₃ , YF ₃ , ZrO ₂ , TaO ₂ , 24. The method according to claim 21, wherein the ceramic is made of at least one ceramic selected from the group consisting of CeO ₂ , Ce ₂ O ₃ , CeF ₃ and Nd ₂ O _3. The member in the plasma processing vessel described in the above. A substrate, a member inside the plasma processing container having a coating formed on the surface thereof,
The member in a plasma processing container, wherein the coating has a hydroxide layer made of a hydroxide containing at least one element belonging to Group 3a of the periodic table.   26. The member according to claim 25, wherein the hydroxide layer is a thermal spray coating formed by thermal spraying or a thin film formed by a thin film forming technique. The hydroxide constituting the hydroxide layer is selected from Y (OH) ₃ , Ce (OH) ₃ , and Nd (OH) ₃ , wherein the hydroxide is selected from the group consisting of Y (OH) ₃ , Ce (OH) ₃ and Nd (OH) _3. The member in the plasma processing container according to item 1.   28. The plasma processing container inner member according to claim 25, wherein at least a part of the hydroxide layer is subjected to a sealing treatment.   The member according to any one of claims 1 to 28, further comprising an anodic oxide film between the substrate and the film.   30. The plasma processing container inner member according to claim 29, wherein the anodic oxide coating is sealed with a metal salt aqueous solution.   The plasma processing container according to claim 29, wherein the anodic oxide coating is sealed with a resin selected from the group consisting of SI, PTFE, PI, PAI, PEI, PBI, and PFA. Internal member.   A member in a plasma processing container, comprising a ceramic sintered body containing at least one element belonging to Group 3a of the periodic table, at least a part of which is hydrated with steam or high-temperature water. The ceramic sintered _body, a plasma treatment according to _{Y 2 O 3, CeO 2,} Ce 2 O 3, Nd 2 claim _{32 O 3} selected ceramics from, characterized in that obtained by hydration treatment Container inner member.   An inner member for a plasma processing container, comprising a ceramic sintered body containing a hydroxide containing at least one element belonging to Group 3a of the periodic table. The plasma according to claim 34, wherein the hydroxide contained in the ceramic sintered body is selected from Y (OH) ₃ , Ce (OH) ₃ , and Nd (OH) _3. Processing container internal member.

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