WO2007111058A1 - Structural member for plasma treatment system and method for manufacture thereof - Google Patents

Abstract

Disclosed is a structural member for a plasma treatment system, which is excellent in film-forming properties, durability and reliability. The structural member comprises a substrate and a ceramic film provided on the substrate, wherein the ceramic film has a purity of 98% or higher. In the ceramic film, a particle constituting the film has a particle diameter of 50 nm or smaller, and the amount of moisture released from the film is 1019 molecules/cm2 or less.

Description

 Specification

 Plasma processing apparatus member and manufacturing method thereof

 Technical field

 The present invention relates to a member for a plasma processing apparatus for manufacturing an electronic component such as a semiconductor device or a liquid crystal panel, and a manufacturing method thereof.

 Background art

 [0002] As a process for manufacturing a semiconductor device, a liquid crystal panel, etc., there are a film forming process by plasma treatment on a Si wafer or a glass substrate and a dry etching process. Various corrosive gases are used during the plasma treatment. Conventional chamber inner walls are made of metal, and are exposed in the chamber. However, with the recent increase in the degree of integration of semiconductor devices and the like, the allowable amount of metal contamination is becoming extremely low. In addition, the plasma used has been increased in density year by year due to the high quality of plasma processing.

 [0003] For this reason, in a plasma processing apparatus, a ceramic sintered body exhibiting high corrosion resistance against plasma and corrosive gas has been used as a member exposed in a chamber (plasma processing chamber). The electronic component manufacturing apparatus disclosed in Patent Document 1 uses a member using a ceramic sintered body.

 [0004] It has been relatively easy to manufacture a plasma processing chamber of a size corresponding to a 5-inch or 6-inch Si wafer with a member having a ceramic sintered body force. However, it is extremely difficult to manufacture recent large-scale plasma processing chambers that can handle 8-inch and 12-inch Si wafers and large-sized liquid crystal substrates using materials that have a strong ceramic sintered body. This is due to the problem of low yield and high manufacturing costs.

 [0005] Therefore, a member formed by forming a ceramic film on a surface of a metal base material that is low in cost, excellent in workability, and easy to increase in size using a thermal spraying method has been adopted in a plasma processing chamber. . Such a member has the same corrosion resistance as the ceramic sintered body. For example, an electronic component manufacturing apparatus disclosed in Patent Document 2 has a member formed by forming a ceramic film (sprayed film) using a thermal spraying method.

However, the thermal spraying method is a high melting point ceramic powder melted by electricity or gas energy. Since the powder is sprayed onto the base material, the ceramic raw material is likely to be insufficiently melted. When the ceramic raw material is insufficiently melted, open pores and continuous pores are formed in the sprayed film. In addition, countless microcracks are generated in the sprayed film due to the rapid cooling of the molten state. When a corrosive gas or plasma comes into contact with the sprayed film in a plasma processing chamber manufactured using a member with a sprayed film, the corrosive gas penetrates through the continuous pores or microcracks of the sprayed film, causing corrosion of the substrate. To do. Eventually, problems such as peeling of the sprayed film occur. In the spraying method, the sprayed film is formed with a thickness of 100 / zm or more in order to compensate for defects caused by countless pores and microcracks. Thus, the coefficient of linear expansion becomes inconsistent between the thick sprayed film and the metal base material. Due to the mismatch of the linear expansion coefficients, the sprayed film peels off after repeated heating and cooling in the plasma treatment.

 Therefore, it is conceivable to form a ceramic film by PVD or CVD instead of the sprayed film. However, both of these methods require a vacuum environment during film formation, and it is necessary to control the position of the material nozzle at a certain distance from the film formation surface, and it is necessary to heat the substrate to a high temperature. . For this reason, it cannot be said that it is an effective technique as a manufacturing method of a member for a plasma processing apparatus having a large and complicated shape.

 [0008] Alternatively, a method of forming a ceramic film by applying a heat treatment by applying a solution (sol) in which a metal compound or fine powder raw material is dispersed to a surface of a substrate using a simple device such as a spray nozzle Can be considered. Such a method is called a sol-gel method, which is a conventional technique, and can form a ceramic film having excellent film forming properties, durability, and reliability.

 [0009] Patent Document 1: Japanese Patent No. 3103646

 Patent Document 2: JP 2001-164354 A

 Non-patent document 1: "Sintering of ceramics": written by Keisuke Moriyoshi et al., Published by Uchida Oirakuno, December 15, 1995

 Disclosure of the invention

 Problems to be solved by the invention

However, the use of the sol-gel method as a method for forming a ceramic film of a plasma processing apparatus member has the following problems.

[0011] The ceramic film of the plasma processing apparatus member is desired to have a purity of 98% or more. Yes. When the sol-gel method is performed using high-purity raw materials, heat treatment at a high temperature (eg, 700 ° C or higher) is required.

 However, as a base material for a member for a plasma processing apparatus, a material having A1 force is often used. Substrates with A1 force are prone to deformation and composition changes when exposed to temperatures above 400 ° C due to the low melting point of A1 (approximately 600 ° C).

 [0013] Alternatively, in order to carry out at a low temperature that can avoid deformation and composition change of A1 by using the sol-gel method, various impurities such as alkali metals and heavy metals are mixed into the sol, or the glass is glassy. A layer must be formed. In this case, a high-purity ceramic film having high corrosion resistance cannot be formed. Furthermore, in a ceramic film formed at a relatively low temperature, the binding force between the component particles is low, so there is a high possibility that particles will be generated.

 That is, conventionally, a member for a plasma processing apparatus having excellent film formability, durability, and reliability is obtained. When a sol-gel method is used as a method for manufacturing a member for a plasma processing apparatus, a high-purity ceramic film is obtained. In addition, there was a problem in avoiding the deformation and composition change of the base material, which is a low melting point metal force.

 [0015] Therefore, an object of the present invention is to solve the problems of the prior art and to provide a member for a plasma processing apparatus that is excellent in film formability, durability, and reliability.

 Another object of the present invention is to provide a method for manufacturing a member for a plasma processing apparatus, which can manufacture the member for a plasma processing apparatus as described above.

 Means for solving the problem

[0017] According to the present invention, at least the following modes (1) to (24) are obtained.

[0018] (1) In a plasma processing apparatus member having a ceramic film having a purity of 98% or more on a substrate, the ceramic film has a particle diameter of particles constituting the film of 50 nm or less, A member for a plasma processing apparatus, wherein the amount of water released from the membrane is 10 ¹⁹ molecules Zcm ² or less.

 [0019] (2) The plasma processing apparatus member according to aspect (1), wherein the ceramic film includes a sol-gel film formed by a sol-gel method.

[0020] (3) The base material is also made of metal, ceramics, glass, or a composite material force thereof. The ceramic film is a film composed of at least one element selected from Group 2 to 6 elements, Group 12 to 14 elements, and rare earth elements in the periodic table (1). (2) A member for a plasma processing apparatus.

[0021] (4) The ceramic film is a film composed of at least one element selected from Mg, Al, Si, Ti, Cr, Zn, Y, Zr, W, and a rare earth element. Aspect (1)

(3) A member for a plasma processing apparatus.

[0022] (5) Aspect (1), wherein the ceramic film has a light-transmitting property with a transmittance of 80% or more in a visible light region having a wavelength of 400 to 800 nm when the film thickness is 3 μm or less. To (4) Plasma processing device components.

 [0023] (6) The plasma processing apparatus member according to any one of aspects (1) to (5), wherein the ceramic film is formed in an oxygen-containing atmosphere at a temperature range of 250 to 1200 ° C.

(7) The member for a plasma processing apparatus according to any one of aspects (1) to (6), wherein the ceramic film has a purity of 99.5% or more.

[0025] (8) The embodiments (1) to (1), wherein the substrate is made of a metal, and has a film formed on the surface of the substrate by passivating the surface of the substrate. 7) A member for a plasma processing apparatus.

[0026] (9) The member for a plasma processing apparatus according to any one of aspects (1) to (7), wherein the base material is made of aluminum and has an anodized film on the surface of the base material. .

[0027] (10) The member for a plasma processing apparatus according to any one of aspects (1) to (7), wherein the base material is made of metal and has a film formed by heat treatment on a surface of the base material.

(11) As the ceramic film, a sprayed film formed on the base material by a spraying method;

And a member for a plasma processing apparatus according to any one of aspects (1) to (10), characterized by having a sol-gel film formed on the sprayed film by a sol-gel method.

[0029] (12) An aspect in which the ceramic film includes a sol-gel film formed on the base material by a sol-gel method and a sprayed film formed on the sol-gel film by a spraying method ( The member for plasma processing apparatus of 1)-(10).

[0030] (13) The member for a plasma processing apparatus according to any one of aspects (1) to (12), wherein the base material has a plate shape, a tubular shape, or a container shape having holes.

[0031] (14) A plasma having a step of forming a ceramic film having a purity of 98% or more on a substrate The method of manufacturing a Ma processor member, in the ceramic film formation process, the particle size of the particles constituting the film is not less 50nm or less, and the amount of moisture released from the film and a 10 ^{1 9} molecule ZCM ² below A method for producing a member for a plasma processing apparatus, characterized by comprising:

 [0032] (15) The method for producing a member for a plasma processing apparatus according to aspect (14), wherein a sol-gel film is formed as the ceramic film by a sol-gel method.

 [0033] (16) A step of forming the base material made of metal, ceramics, glass, or a composite material thereof, and as the ceramic film, Group 2-6 elements, Group 12-14 elements of the periodic table, and And a step of forming a film composed of at least one element of rare earth elements. A method for manufacturing a member for a plasma processing apparatus according to aspect (14) or (15), wherein:

 (17) A step of forming, as the ceramic film, a film composed of at least one element selected from Mg, Al, Si, Ti, Cr, Zn, Y, Zr, W, and a rare earth element. A method for producing a member for a plasma processing apparatus according to any one of aspects (14) to (16), comprising:

 [0035] (18) Manufacture of a member for a plasma processing apparatus according to aspects (14) to (17), wherein the ceramic film is formed in an oxygen-containing atmosphere at a temperature range of 250 to 1200 ° C. Method

[0036] (19) Aspects (14) to (14) are characterized in that the ceramic film has a purity of 99.5% or more.

18) A method for producing a member for a plasma processing apparatus.

 [0037] (20) The method includes the step of forming the base material made of a metal, and the step of forming a film formed by passivating the surface of the base material on the surface of the base material. Embodiments (14) to (

19) A method for producing a member for a plasma processing apparatus.

 [0038] (21) Aspects (14) to (19) including a step of forming the base material made of an aluminum cover and a step of forming an anodized film on the surface of the base material. ) For manufacturing a member for a plasma processing apparatus.

[0039] (22) A mode (14) comprising the step of forming the base material made of metal and the step of forming a film formed by heat treatment on the surface of the base material (19) A method for manufacturing a member for a plasma processing apparatus. [0040] (23) The ceramic film forming step includes a step of forming a sprayed film on the base material by a spraying method and a step of forming a sol-gel film on the sprayed film by a sol-gel method. A method for producing a member for a plasma processing apparatus according to any one of aspects (14) to (22).

 [0041] (24) The ceramic film forming step includes a step of forming a sol-gel film on the substrate by a sol-gel method, and a step of forming a sprayed film on the sol-gel film by a spraying method. A method for producing a member for a plasma processing apparatus according to embodiments (14) to (19)

 [0042] The member for a plasma processing apparatus according to the present invention is excellent in film formability, durability, and reliability!

[0043] The sol-gel film of the present invention has high plasma resistance in a high-density plasma environment because it is highly dense and smooth. In addition, even in a corrosive gas environment or a chemical solution environment, the film is highly dense and can protect the substrate, and thus exhibits high gas resistance and chemical solution resistance.

 [0044] In addition, the conventional technique cannot form a uniform film on a complicated shape or the inner surface of a tube. However, according to the present invention, a film can be easily formed by pouring or dipping a liquid sol. This is possible.

 [0045] Furthermore, by forming a highly dense sol-gel film on the surface of the sprayed film, it is possible to suppress the generation of a partition from the sprayed film.

[0046] In addition, when a composite film having a ground coating surface treatment, a surface treatment, or a sandwich structure is exposed to a corrosive gas, the dense sol-gel film blocks the corrosive gas and suppresses the peeling of the sprayed film. be able to.

 Brief Description of Drawings

 [0047] FIG. 1 is a graph for explaining the characteristics of a member for a plasma processing apparatus according to Example 1 of the present invention, and shows measurement data of the amount of water released from a Y 2 O film.

 twenty three

 FIG. 2 is a graph for explaining the characteristics of a member for a plasma processing apparatus according to Example 1 of the present invention, and shows the amount of moisture released at each temperature rising stage.

FIG. 3 is a graph for explaining the characteristics of the plasma processing apparatus member according to Example 1 of the present invention, and shows the relationship between the firing temperature and the amount of moisture released when the temperature is raised to 500 ° C. . FIG. 4 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 2 of the present invention.

 FIG. 5 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 3 of the present invention.

 FIG. 6 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 4 of the present invention.

 FIG. 7 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 5 of the present invention.

 FIG. 8 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 6 of the present invention.

 FIG. 9 is a schematic cross-sectional view showing a member for a plasma processing apparatus according to Example 7 of the present invention.

 FIG. 10 is a table showing the evaluation results of the plasma processing apparatus member according to the present invention together with the evaluation results of the comparative example.

 FIG. 11 is a drawing for explaining the characteristics of a member for a plasma processing apparatus according to an example of the present invention, and shows the transmittance of sample 10 as an example at a wavelength of visible light of 400 to 800 nm.

 FIG. 12 is a drawing for explaining the characteristics of a member for a plasma processing apparatus according to an example of the present invention, and shows the transmittance of sample 11 as an example at a wavelength of visible light of 400 to 800 nm.

 FIG. 13 is a drawing for explaining the characteristics of a member for a plasma processing apparatus according to an example of the present invention, and shows the transmittance of sample 12 as an example at a wavelength of visible light of 400 to 800 nm.

 FIG. 14 is a drawing for explaining the characteristics of a member for a plasma processing apparatus according to an example of the present invention, and shows the transmittance of sample 37 as a comparative example at a wavelength of visible light of 400 to 800 nm. BEST MODE FOR CARRYING OUT THE INVENTION

[0048] The member for a plasma processing apparatus according to the present invention has a ceramic film having a purity of 98% or more formed by a sol-gel method and having plasma corrosion resistance and corrosion gas corrosion resistance.

[0049] In addition, the method for producing a member for a plasma processing apparatus according to the present invention is a method of producing a Sorge ceramic film having a purity of 98% or more and having plasma corrosion resistance and corrosion gas corrosion resistance on a substrate. A step of forming by a method.

 [0050] That is, in the present invention, a material generally used as a structural material of metal, ceramics, and glass is used as a base material, and the surface thereof is formed from a 2-6 group element, a 12-14 group element, or a rare earth element. Or a plasma processing apparatus member coated with a ceramic film made of a composite oxide formed from two or more of the above elements. In this method, the oxide ceramics can be obtained by applying the sol-gel method, applying it to the substrate using the spray method, dipping method, etc., and heat-treating it in an oxygen-containing atmosphere of 250 ° C or higher. It is.

 [0051] The spray method recommends the use of a nozzle with a special design and optimization, but it is also possible to obtain a similar film using a commercially available airbrush or spray gun. is there. The dipping method is a method in which a uniform sol film is applied to the surface of a substrate by immersing the substrate in a solution and then pulling it up at a low speed (10 to 50 mm / min) and at a constant speed.

 [0052] As heat treatment conditions, it is necessary to heat at a firing temperature of 250 to 1200 ° C for 1 to 5 hours using an oven or an electric furnace.

[0053] Further, it has a feature that a high-purity ceramic thin film of 98% to 99.99% can be obtained at a low temperature of 250 ° C.

 [0054] In addition to direct film formation on a substrate, composite by surface coating on a sprayed film, composite by applying a sprayed film after film formation of a sol-gel film on the substrate, and anodized film It can also be applied as a composite film by forming a film such as a fluoride film on the passive material treatment of a base material.

[0055] The particle size of the sol-gel film in the present invention was observed using a field emission scanning electron microscope (JEM-6700F, manufactured by JEOL Ltd.). As a result, it was confirmed that the particle sizes constituting the film were all 50 nm or less. In contrast to the conventional film formation method, the ceramic film has a particle diameter of lOOnm or more. In the present invention, the particle diameter is 50 nm, so that high purity (98% or more) and low temperature film formation from 250 ° C can be achieved. It has become possible. This is because when the particle size of the sol-gel film is made finer to 50 nm or less, the sintering temperature is drastically lowered and sintering is started at about 250 ° C. According to Non-Patent Document 1, the grain boundary diffusion and volume diffusion contributing to sintering increase relatively as the particles become smaller, and this relationship is extremely effective when sintering materials with high vapor pressures that are difficult to densify. The smaller the particle size, It is described that the number of contact points per unit volume increases, and the generation and disappearance locations of atoms related to mass transfer increase, leading to a favorable situation for densification. Therefore, it was possible to achieve high purity only by the sol-gel method, despite the processing temperature of less than 700 ° C!

 Example

 Hereinafter, a member for a plasma processing apparatus and a method for manufacturing the member for a plasma processing apparatus according to an embodiment of the present invention will be described with reference to the drawings.

[0057] Samples 31 to 37 as comparative examples were produced together with samples 1 to 29 as examples of the present invention.

Several characteristics were verified and evaluated for these samples. The results are shown in the table in Fig. 10.

 [0058] Samples 1 to 29, which are examples of the present invention, are films containing at least a sol-gel method on a 50 to 200 mm square substrate surface that has various material strengths shown in the substrate column in the table. A ceramics film is formed by this method. The apparatus used for the formation of the ceramic film by the sol-gel method formed the film by spraying the sol as a raw material onto the substrate by a spray nozzle. An electric furnace was used for heat treatment.

 [0059] [Example 1]

 As a measurement of the basic physical properties of the ceramic film of the present invention, the amount of water released from the ceramic film formed on the Si substrate was investigated. The amount of water released was measured with an atmospheric pressure ionization mass spectrometer (APIMS: UG-302P manufactured by Renesas East Japan Semiconductor Co., Ltd.).

[0060] The sample was placed in a reactor tube made of 1 / 2-inch SUS316L electrolytic polishing tube, and high-purity Ar gas with an impurity concentration of lppb or less was used as the carrier gas. This is a system that allows Ar gas to pass through the sample at a flow rate of 1.2 LZmin and measures the moisture released from the sample with A PIMS.

 [0061] The temperature profile at the time of measuring the amount of moisture released from the ceramic film was set as follows. Hold at 25 ° C for 10 hours, then heat up to 100 ° C in 10 minutes, hold at 100 ° C for 1 hour and 50 minutes, and then step up to 100 ° C to 500 ° C and release The amount of water was measured.

[0062] FIG. 1 shows measurement data of the amount of water released from the YO membrane. The horizontal axis is measured by APIMS. The fixed time and the vertical axis represent the number of water molecules released from the unit area. Samples were sol-geled and fired in air at 300 ° C, 600 ° C, and 900 ° C, respectively, to a thickness of 1 µm.

[0063] FIG. C, 100. C, 200. C, 300. C, 400. C, 500. A graph plotting the amount of water released at each temperature increase stage against the reciprocal temperature of C (ΐΖΚ) is shown. It was confirmed that the activity energy Ea of water desorption was 0.055 eV regardless of the firing temperature. This suggests that only the effective surface area, which does not change the surface film quality, has decreased. Also, the amount of water released at a temperature up to 500 ° C is 300 ° C calcined sample: 4.23 x 10 ¹⁸ molecules / cm ² , 600. C calcined sample: 1.75 x 10 ¹⁸ molecules / cm ² , 900. C-fired sample: 6. 31 X 10 ¹⁷ molecules Zcm ² was confirmed.

 FIG. 3 shows the relationship between the firing temperature and the amount of water released when the temperature is raised to 500 ° C. As the calcination temperature increases, the bonding strength at the grain boundaries between the Y 2 O crystal grains increases, and the execution table

 twenty three

From the fact that the area is getting smaller, it can be seen that the amount of water released is greatly reduced. In addition, if the firing temperature is 300 ° C or higher, the amount of water released from the film is 10 ¹⁹ molecules Zcm ² or less.

 [0065] [Example 2]

 For Samples 1 to 14, which are Example 2 of the present invention, as shown in FIG. 4, only sol-gel films were formed on various substrates and evaluated.

 [0066] [Example 3]

 For Samples 15 to 29, which are Embodiment 3 of the present invention, as shown in FIG. 5, a passivated film or the like is formed on the surface of a substrate made of aluminum (A1) or stainless steel (SUS). Then, a sol-gel film was formed on the base and evaluated. In the SUS base material of Sample 15, the substrate surface is treated with a passivating treatment made of Cr 2 O, and further on it.

 twenty three

A sol-gel film was formed and evaluated. For the A1 metal substrates of Samples 16 and 17, the anodized film whose surface was oxidized by electric field treatment in the solution was used as the base, and a sol-gel film was further formed for evaluation. Carried out. For the A1 metal base material of Sample 18, an evaluation was performed by forming a fluorinated MgF film on the base material surface and further forming a sol-gel film. [0067] [Example 4]

 In the composite of the sprayed film and the sol-gel film of Samples 19 to 23, which is Example 4 of the present invention, as shown in FIG. 6, the composite in the case where the sol-gel film is formed on the surface after forming the sprayed film as shown in FIG. The membrane was evaluated.

[Example 5]

 In the composite of the sol-gel film, the sprayed film, and the further sol-gel film of Samples 24 and 25, which is Example 5 of the present invention, as shown in FIG. 7, the sprayed film was formed on the sol-gel film as a base. The composite membrane was evaluated.

[0069] [Example 6]

 In the composite film of Samples 26 and 27, which is Example 6 of the present invention, with a sprayed film, as shown in FIG. 8, a sprayed film is formed on the sol-gel film as a base, and the sol-gel is further formed on the surface. The composite film in the case of a sandwich structure in which the film was formed was evaluated.

[0070] [Example 7]

 In the composite film of Samples 28 and 29, which is Example 7 of the present invention, with a sprayed film, as shown in FIG. 9, a sprayed film is formed with an anodized film as a base, and a sol-gel film is further formed on the surface. The composite film when the film was formed was evaluated.

[0071] [Comparative Example]

 On the other hand, each sample 31 to 37 as a comparative example was made of various base materials shown in the table of FIG. 10, and a ceramic film was formed using a thermal spraying method, a thermal CVD method, or a conventional sol-gel method. Here, the conventional sol-gel method is a method in which the structure and purity of the ceramic film are outside the scope of the present invention.

 [0072] Hereinafter, verification and evaluation results of Samples 1 to 29, which are examples of the present invention, and Samples 31 to 37, which are comparative examples, will be described.

[0073] (Membrane purity)

 Purity analysis was performed on each ceramic film. The analysis method was GDMS (Glow Discharge Mass Spectrometry), and VG9000 made by FI. Elemental was used as the analyzer.

[0074] With the miniaturization of printed wiring and the like, the plasma processing apparatus requires a more severe impurity control. Therefore, in order to improve the yield of electronic parts, Degree of ceramic film is required.

 [0075] The sol-gel films in Samples 1 to 29, which are examples of the present invention, have a purity of 99% or more.

 [0076] In contrast, the conventional sol-gel films in Comparative Samples 31 and 32 contain a large amount of alkali metal in order to technically enable low-temperature film formation, so the purity is about 85%. Yes, less than 98%. The sprayed film in the comparative samples 33 and 34 has a purity of 99%, and the CVD film in the comparative samples 35 to 37 has a purity of 95%.

 [0077] (Etching rate)

 A parallel plate type RIE etching chamber is equipped with a 6-inch silicon wafer and a mirror-polished specimen, and CF +0 plasma for 10 hours.

 4 2

 Corrosion test by exposure was conducted. At that time, a part of the polished surface was masked with a polyimide tape and a silicon wafer, and the step between the portion with and without the mask was measured by a stylus method to calculate the etching rate.

 [0078] Since the ceramic used as an example this time is an oxide that is relatively resistant to plasma, the etching amount on the surface is very small.

[0079] On the other hand, for samples 31 to 34 as comparative examples, the same Y 2 O 2

 Even though it is 2 3 and Al 2 O 3 2, there is a variation in the film formed by the CVD method of Comparative Samples 35 to 37.

 [0080] (Number of particles)

 For the silicon wafer after the plasma test, the number of particles having a size of 0.5 microns or more was measured using a particle counter (Surfscan 6420 manufactured by Tencor).

[0081] The sol-gel film, which is a dense and flat film, has better results than other film forming methods. However, the samples 19 to 23, which are examples of the present invention, have a sprayed film on the outermost surface, so that the number of particles is increased as in the samples 33 and 34, which are comparative examples. However, samples 19 to 23 and 26 and 27, which are examples of the present invention in which a sol-gel film is formed on the surface of the sprayed film, have an increased number of particles compared to the sol-gel alone film, but only the sprayed film. The number of particles is about 1/3 compared to Decrease in degrees. Therefore, a particle reduction effect was obtained by applying a sol-gel film.

 [0082] (Chlorine gas exposure)

 Among the electronic component manufacturing equipment, in the equipment for manufacturing semiconductor devices, the environment is always exposed to corrosive gas in each process. Therefore, the membrane in each example was changed to C1 gas.

 2 The exposure to corrosion gas was evaluated.

[0083] As an evaluation method, a test piece was installed in a cell for sample installation, C1 gas 100%, 0.3 MPa

 2

 A 24-hour gas exposure test was conducted in a stream of pressure. The temperature inside the cell was 100 ° C. The surface condition after gas exposure was confirmed, and the presence or absence of surface corrosion or peeling was used as the evaluation standard.

 [0084] Samples 1 to 29, which are examples of the present invention on which a sol-gel film was formed,

 2 Even after exposure, no peeling occurred, and no change was observed in the surface condition. Therefore, C1

 2 Low gas resistance! ヽ Even when an A1 metal substrate is used as a substrate, a dense sol-gel film is formed to prevent corrosion of the substrate, and durability and reliability as a member for plasma processing equipment are reduced. It was confirmed that there was an improvement.

On the other hand, in the conventional sol-gel films and sprayed monolayer films of Samples 31 to 34, which are comparative examples, film peeling occurred. The reason for this is thought to be that the film peeled off because the C1 gas that passed through the continuous pores directly corroded the A1 metal substrate due to the large number of pores in the film itself.

 2

 It is.

 [0086] Regarding the CVD films of Samples 35 to 37, which are comparative examples, film peeling did not occur, but alteration of the film surface was confirmed.

[0087] (Filmability to complex shapes)

 Determining whether or not film formation can be performed on complicated inner shapes such as two or more steps and box-shaped inner surfaces, small-diameter cylindrical inner surfaces (for example, gas piping with an inner diameter of about 5 mm), porous materials, and fibrous filters did.

In Examples 1 to 18, it was possible to easily form a film on two or more steps or a box-shaped inner surface. In the case of the composite film with the sprayed film of Samples 19 to 29, which is an example of the present invention, it depends on the surface on which the sprayed film can be formed. But one It was possible to form a sol-gel film on the entire surface of a complicated shape including a partially sprayed film.

 [0089] On the other hand, in the case of the comparative example, the conventional sol-gel film can be formed flexibly with respect to a relatively complicated shape, but when the film is formed with a corner or a sharp R shape. The film had poor adhesion and delamination. In the case of the sprayed film, it is impossible to form the film on the base material where the shadow is generated because the film is formed only on the portion where the flame in which the spray material is melted can be linearly irradiated. A CVD film is not formed unless the surface on which the film is formed is completely exposed to the supplied source gas, and when both parallel and right-angle surfaces exist on the film formation surface, both of them are formed. Since the film rate changed extremely, uniform film formation was impossible.

 Next, the inner surface of the small-diameter cylinder, the inside of the porous body, and the inside of the fibrous filter were fired after passing through the raw material solution (sol) and drying. By using the sol-gel method, it was possible to form a film on a member having the above-mentioned shape, which was impossible with the prior art. In principle, the thermal spraying method and the CVD method shown in the comparative example were unable to form a film on the entire surface. In addition, when the conventional sol-gel method is used, a film can be formed, but the purity and the viewpoint of particles are difficult to apply to a member for a plasma processing apparatus.

 [0091] (Transparency, transmittance)

 With respect to Samples 10 to 13 which are examples of the present invention and Sample 37 which is a comparative example, since the base material itself shows translucency, transmittance at a wavelength of visible light of 400 to 800 nm was measured. For the measurement, a self-recording spectrophotometer (Hitachi U-3500) was used. The results of transmittance of samples 10 to 12 are shown in FIGS. 11 to 13, respectively. As a comparative example, the transmittance of the CVD film is shown in FIG.

 [0092] When the transmittance in the visible light region is less than 80% by visual observation, the film starts to appear cloudy. Also, when the transmittance is below 60%, the film appears to be cloudy. Therefore, when it is applied to a member that requires translucency, a transmittance of 80% or more is required to obtain good translucency.

[0093] When the prior art is used, the transmittance usually decreases as the film thickness increases. However, the sol-gel film of the present invention has a film thickness of 1 πι as shown in Figs. If it is ˜5 / ζ πι, almost no decrease in transmittance occurs in the visible light region. The transmittance is maintained at about 90% in the entire wavelength range. 4mm thick stone as the base material Considering that the UK transmittance is about 93% over the entire wavelength range, it can be seen that if the transmittance of the film alone is calculated, it will be about 97%.

 On the other hand, as shown in FIG. 14, the transmittance of the CVD film is remarkably reduced to about 50 to 80% at 1 μm. Also, sprayed films and conventional sol-gel films do not show translucency because they contain many pores and are thick.

 [0095] (Overall evaluation)

 The sol-gel monolayer film of Samples 1 to 18 which is an example of the present invention or a multilayer composite film not including a sprayed film, and Samples 31 to 37 which are comparative examples have excellent etching rates of lOnm / min or less. A comprehensive evaluation was given for films that showed plasma corrosion resistance, low dust generation with 50 or fewer particles, and that can be applied to complex shapes. In addition, regarding the composite film with the sol-gel film including the sprayed film of Samples 19 to 29 as an example of the present invention, the film number and the chlorine gas exposure characteristics are improved as compared with the sprayed film alone. Comprehensive evaluation. It was.

 Industrial applicability

The present invention is not limited to electronic component manufacturing apparatuses such as semiconductor elements and liquid crystal panels, but can be applied to members used in all apparatuses that perform plasma processing and the like with corrosive atmospheres, and manufacturing methods thereof. .

Claims

The scope of the claims  [1] In a member for a plasma processing apparatus having a ceramic film having a purity of 98% or more on a substrate, The ceramic film has a particle diameter of 50 nm or less, and a water content released from the film is 10 ¹⁹ molecules Zcm ² or less.  [2] The member for a plasma processing apparatus according to [1], wherein the ceramic film has a sol-gel film formed by a sol-gel method. [3] The base material is made of metal, ceramics, glass, or a composite material thereof,  The ceramic film is a film composed of at least one element selected from the group consisting of elements 2 to 6 in the periodic table, elements 12 to 14 and rare earth elements. The member for a plasma processing apparatus according to 1. [4] The ceramic film is a film made of at least one element selected from Mg, Al, Si, Ti, Cr, Zn, Y, Zr, W, and rare earth elements. 1. A member for a plasma processing apparatus described in 1. [5] The plasma treatment according to [1], wherein the ceramic film has a light-transmitting property having a transmittance of 80% or more in a visible light region having a wavelength of 400 to 800 nm when the film thickness is 5 μm or less. Device components.  6. The member for a plasma processing apparatus according to claim 1, wherein the ceramic film is formed in a temperature range of 250 to 1200 ° C. in an atmosphere containing oxygen. [7] The member for a plasma processing apparatus according to [1], wherein the ceramic film has a purity of 99.5% or more. [8] The base material is made of metal,  2. The member for a plasma processing apparatus according to claim 1, further comprising a film formed on the surface of the base material by passivating the surface of the base material. [9] The substrate comprises an aluminum force, 2. The member for a plasma processing apparatus according to claim 1, further comprising an anodized film on the surface of the base material. [10] The base material is made of metal,  The surface of the base material has a film formed by heat treatment. The member for a plasma processing apparatus according to 1. 11. The ceramic film according to claim 1, wherein the ceramic film includes a sprayed film formed on the base material by a spraying method and a sol-gel film formed on the sprayed film by a sol-gel method. A member for a plasma processing apparatus. 12. The ceramic film according to claim 1, wherein the ceramic film includes a sol-gel film formed on the base material by a sol-gel method, and a sprayed film formed on the sol-gel film by a thermal spraying method. A member for a plasma processing apparatus. [13] The base material may have a plate shape, a tubular shape, or a container shape having holes. The member for a plasma processing apparatus according to 1. [14] In the method for producing a member for a plasma processing apparatus, comprising a step of forming a ceramic film having a purity of 98% or more on a substrate. In the ceramic film forming step, the film is formed so that the particle diameter of the particles is 50 nm or less and the amount of water released from the film is 10 ¹⁹ molecules Zcm ² or less. A method for producing a characteristic plasma processing apparatus member. 15. The method for manufacturing a member for a plasma processing apparatus according to claim 14, wherein a sol-gel film is formed as the ceramic film by a sol-gel method. [16] forming the base material made of metal, ceramics, glass, or a composite material thereof;  Forming a film composed of at least one element selected from the Group 2 to 6 elements, the Group 12 to 14 elements, and the rare earth elements of the periodic table as the ceramic film. The method for manufacturing a member for a plasma processing apparatus according to claim 14.  [17] The method includes forming a film composed of at least one element of Mg, Al, Si, Ti, Cr, Zn, Y, Zr, W, and a rare earth element as the ceramic film. 15. The method for manufacturing a member for a plasma processing apparatus according to claim 14, which is a feature. 18. The method for manufacturing a member for a plasma processing apparatus according to claim 14, wherein the ceramic film is formed in a temperature range of 250 to 1200 ° C. in an atmosphere containing oxygen. [19] The method for producing a member for a plasma processing apparatus according to [14], wherein the ceramic film has a purity of 99.5% or more. [20] forming the base material made of metal;  15. The method for producing a member for a plasma processing apparatus according to claim 14, further comprising: forming a film formed on the surface of the base material by subjecting the surface of the base material to passivation. [21] forming the base material made of aluminum;  15. The method for manufacturing a member for a plasma processing apparatus according to claim 14, further comprising a step of forming an anodized film on the surface of the base material. [22] forming the base material made of metal;  15. The method for manufacturing a member for a plasma processing apparatus according to claim 14, further comprising: forming a film formed by heat treatment on the surface of the base material. [23] The ceramic film forming step includes a step of forming a sprayed film on the substrate by a spraying method and a step of forming a sol-gel film on the sprayed film by a sol-gel method. The method for manufacturing a member for a plasma processing apparatus according to claim 14. [24] The ceramic film forming step includes a step of forming a sol-gel film on the base material by a sol-gel method and a step of forming a sprayed film on the sol-gel film by a spraying method. Item 15. A method for producing a member for a plasma processing apparatus according to Item 14.