JP2005097722A - Corrosion resistant member, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a corrosion resistant glass member which is high in corrosion resistance, less in generation of particles, and easily manufactured, and contains nitrogen, and a method for manufacturing the same. <P>SOLUTION: A corrosion resistance member formed of glass consisting of Si, Al, O, N and elements of group 3a and/or group 2a, and a member with a corrosion resistant thermal spraying film of glass consisting of the composition are high in corrosion resistance and heat-resistant strength against corrosive gas and plasma, less in generation of particles. The corrosion resistant member of glass can be manufactured by mixing, molding, heat-treating silicon nitride, alumina, silica and oxides of elements of group 3a and/or group 2a, or performing thermal spraying on a base material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a member used for a CVD (Chemical Vapor Deposition) apparatus, a plasma processing apparatus (plasma etching apparatus) or the like in the manufacture of a semiconductor or the like, and particularly relates to a member having high corrosion resistance against corrosive gas or plasma.

Corrosive gas is frequently used for plasma etching in the manufacturing process of semiconductors and the like and for cleaning of CVD apparatuses. For these corrosive gases, fluorine-based or chlorine-based gases are used. CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CHF ₃ / CF ₄ , SF _6, etc. are used in the fluorine-based gas (see, for example, Patent Document 1), and in the chlorine-based gas, Cl ₂ , BCl ₃ , CCl ₄ or the like is used (see Non-Patent Document 1). Further, it has been proposed to use HF, F ₂ , or NF ₃ (see, for example, Patent Documents 1, 2, and 3).

  Quartz, alumina, ceramics such as aluminum nitride, and metals such as aluminum and stainless steel are used for the parts that come into contact with the gas or plasma containing the gas, such as containers, inner walls, and components of such corrosive gases. Has been. However, these members have a problem that they react with a fluorine-based gas to generate fluoride to cause generation of particles in the apparatus, and the members are consumed in a short time.

For example, a quartz member reacts with fluorine gas to produce SiF ₄ and sublimates and wears out. Further, in ceramics such as alumina and aluminum nitride, aluminum fluoride AlF ₃ is difficult to sublimate, but corrosion proceeds selectively at the grain boundaries and pores of the member, and particles are generated by dropping of crystal grains.

  As a method for solving such a problem, a sintered body has been proposed in which the surface open porosity of alumina ceramics containing magnesia and silica is 0.3% or less (see, for example, Patent Document 4). However, even in such a sintered body, corrosion of the sintered particles at the crystal grain boundary is unavoidable, and generation of particles due to dropping of the crystal particles is unavoidable.

  As a method of improving the corrosion resistance by eliminating the grain boundaries and suppressing the generation of particles and simultaneously introducing nitrogen, glass composed of Si—Al—O—N elements has been proposed (for example, Patent Document 5). reference). However, since these corrosion-resistant glasses need to be produced in a reducing atmosphere or an inert atmosphere as a production method, members are expensive due to a large-scale production apparatus.

  On the other hand, since a technique for forming a sprayed film on the surface of the base material in order to protect the base material is known, it is conceivable to spray and coat the above-mentioned corrosion-resistant glass on the base material. However, with the conventional thermal spraying technique, it is difficult to form a dense sprayed film of nitrogen-containing glass, and the conventional protective film formation by thermal spraying mainly uses metal or ceramics.

As a prior art for producing a sprayed film containing nitrogen, for example, nitriding by explosive spraying of β sialon and χ sialon powder obtained by heat treatment of a mixed powder of Si ₃ N ₄ , Al ₂ O ₃ , ZrO ₂ , and TiO ₂ What produced the silicon sprayed film is shown (for example, refer nonpatent literature 2).

Also shown is an amorphous layer and a YAG layer produced by spraying a mixed powder of AlN, SiO ₂ and MgO on Si ₃ N ₄ , Al ₂ O ₃ and Y ₂ O ₃ by explosive spraying ( For example, refer nonpatent literature 3). Furthermore, it has been reported that α silicon nitride is produced by plasma spraying for a mixed powder of Si ₃ N ₄ , Al ₂ O ₃ , and Y ₂ O ₃ (see, for example, Non-Patent Document 4).

  However, these sprayed films are crystalline and at the same time, the bonding between the individual particles of the sprayed film is weak and the density is low due to the large number of pores. Therefore, during plasma etching, they are selectively corroded at the grain boundaries and pores of the sprayed film. Progresses and particles are generated due to the drop of crystal particles. Further, when explosive spraying is used, the apparatus is expensive, the deposition efficiency of the sprayed film is poor, and a metal substrate such as aluminum may be deformed by the wind pressure at the time of explosion, which is not general.

  In other words, there is no conventional technique for producing a glass sprayed film in which individual particles are well-bonded with a dense nitrogen-containing material using a general spraying method, and the sprayed film becomes crystalline, and crystal particles are formed during plasma etching. Since particles are generated due to dropping off, the sprayed film of nitrogen-containing glass cannot be used as a corrosion-resistant member against corrosive gas or plasma.

JP 2000-223430 A

JP 2000-248363 A JP 05-090180 A JP 11-278919 A JP-A-11-228172 L. Peters, “Plasma Etch Chemistry: The United Story,” Semi. Intl. , 15 (6), 66 (1992). B. G. Seong, S.M. Y. Hwang and J.H. M.M. Park “Sialon Coating From Sintered Mixtures of Silicon Nitride and Oxides”, Thermal Spray 2003: Advanced the Science & Applying the Technology. Moreau and B.M. Marple, Publicized by ASM International, Materials Park, Ohio, USA, 2003, 719 (2003) R. B. Heimann, S .; Thiele, L.M. M.M. Berger, M.M. Herrmann, M.M. Nebelung, B.M. Wielage, T.W. M.M. Schnick, P.A. Vuoristo, “Thermally Sprayed Silicon Nitride-Based Coatings on Steel for Application in Severe Operation Environments: Preliminary Results Vs. 26,389 (1998) Y. Bao, D.C. T. T. et al. Gawne, T .; Zhang “The Inflation of Matrix Phase Visibility on the Plasma-Spray Deposition of Silicon-Nitride Composite Coatings,” (Ed.) Moreau and B.M. Marple, Publicized by ASM International, Materials Park, Ohio, USA, 2003, 263 (2003)

As described above, in the process using a corrosive gas or plasma in the semiconductor manufacturing process, there are problems such as generation of particles due to corrosion of members, product contamination associated therewith, and yield reduction. Further, a vitreous corrosion-resistant member composed of a Si—Al—O—N element that suppresses such a problem has been proposed, but the vitreous corrosion-resistant member is difficult to manufacture, and the corrosion resistance is not necessarily limited. It was not enough. In addition, it has been difficult to form the Si—Al—O—N glass by thermal spraying on a member that is relatively easily available. On the other hand, although spraying with the Si ₃ N ₄ —Al ₂ O ₃ —Y ₂ O ₃ system is possible, the sprayed film is crystalline, so that there is a problem of particles.

  An object of the present invention is to provide a vitreous corrosion-resistant member having high corrosion resistance, few particles, easy production, and containing nitrogen.

  As a result of intensive studies in view of the above situation, the present inventors have found that corrosion-resistant members made of glass composed of Si, Al, O, N, and Group 3a and / or Group 2a elements are used. The present inventors have found that the corrosion resistance against corrosive gas and plasma containing corrosive gas is high, and the generation of particles is small. In addition, this material is suitable for thermal spraying, and by spraying this material on the base material, the bonding between particles is good, and a dense thermal sprayed film can be formed. As a result, the corrosion resistance of the member is remarkably improved, and particles are generated. As a result, the present invention has been completed.

  That is, the first invention is a corrosion-resistant member made of glass in which a portion exposed to fluorine plasma, chlorine plasma, or corrosive gas is composed of Si, Al, O, N and Group 3a and / or Group 2a elements. It is.

  Hereinafter, the corrosion-resistant member of the present invention will be described in detail.

  The corrosion-resistant member of the present invention is glass, in other words, amorphous. This is because, when the corrosion-resistant member is crystalline, crystal grain boundaries are selectively etched in a corrosive gas atmosphere, and the generation of particles is caused by dropping of crystal grains. Whether or not the corrosion-resistant member is amorphous is confirmed by whether or not an amorphous halo pattern and a crystalline diffraction peak are observed when the corrosion-resistant glass is evaluated by X-ray diffraction. I can do it.

Such a glass can be produced by melting AlN, SiO ₂ , Y ₂ O ₃ mixed powder in an inert atmosphere. Loehman, “Preparation and Properties of Yttrium-Silicon-Aluminum Oxynitride Glasses,” Journal of American Ceramic Society. 62 (9-10), 491 (1979).

  Further, the production of the group 2a-containing glass by the same method is described in, for example, R.A. Pastuszak and P.M. Verdier, J .; Non-Cryst. Solids, 56 (1973) 141.

  The glass composition of the corrosion-resistant member in the present invention contains at least one element selected from the group consisting of Si, Al, O, N and elements of Group 3a and / or Group 2a of the Periodic Table of Elements. The 3a group mentioned here is Sc, Y and lanthanoid elements, and the 2a group is Be, Mg, Ca, Sr, Ba. Glass containing Al and elements of Group 3a and / or Group 2a has low reactivity with corrosive gas or plasma thereof, and even if it reacts with fluorine in corrosive gas, what is generated is a high-boiling compound And has the effect of suppressing etching by plasma or corrosive gas. On the other hand, if a corrosion-resistant member is made of only elements of Si, Al, O, and N, the melting point is high, so that it is difficult to vitrify and crystallize, causing generation of particles. By adding an element, the melting point is lowered, and vitrification is promoted to increase the density and simultaneously reduce the particles.

  The composition of the corrosion-resistant member of the present invention has a Si: Al atomic ratio in the range of 99.9: 0.1 to 30:70, and an O: N atomic ratio of 99.9: 0.1 to 60. : 40, and the atomic number ratio of Al + Si: 3a group element is preferably 95: 5 to 40:60. In this case, when a group 3a element is introduced as an oxide, oxygen contained in the oxide is not included. More preferably, the Si: Al atomic ratio is in the range of 99.9: 0.1 to 35:65, and the O: N atomic ratio is in the range of 99.9: 0.1 to 65:35. Yes, the atomic ratio of Al + Si: 3a group element is 95: 5 to 40:60.

  When the group 2a element is added, the Si: Al atomic ratio is in the range of 99.9: 0.1 to 30:70, and the O: N atomic ratio is 99.9: 0.1 to 60:40. The atomic ratio of the Al + Si: 2a group element is preferably 95: 5 to 50:50. In this case, when the group 2a element is introduced as an oxide, oxygen contained in the oxide is not included.

In this composition, the phase diagram of the AlN—Si ₃ N ₄ —SiO ₂ —Al ₂ O ₃ system for the range of Si—Al—O—N elements excluding group 3a is shown in FIG. In the composition range (A + B region in FIG. 1), it is a glass stable region, hardly crystallized, and a more preferable composition range is a portion indicated by a lattice indicated by “A”. On the other hand, if the composition is out of these ranges, the glass is likely to crystallize, grain boundaries and pores are formed, and corrosion proceeds from there to easily cause generation of particles.

  The second invention is a glass sprayed film in which the part exposed to fluorine plasma or chlorine plasma or corrosive gas is composed of Si, Al, O, N and Group 3a and / or Group 2a elements. It is characterized by being.

  When a glass sprayed coating is used, it will vitrify and at the same time improve the bonding between particles, so it will be densified. By coating this corrosion-resistant glass on the substrate as a sprayed coating, a material that is inexpensive and has excellent corrosion resistance is provided. can do.

  The substrate used in the present invention is not particularly limited, and examples thereof include heat-resistant glass such as quartz glass, metals such as aluminum and stainless steel, ceramics such as alumina and mullite, and the like.

  The surface of the substrate to be used preferably has a surface roughness Ra of 1 to 50 μm. By setting the surface roughness to 1 to 50 μm, the adhesion between the corrosion-resistant glass sprayed film and the substrate is improved. When the surface roughness Ra is less than 1 μm, the substrate and the corrosion-resistant glass sprayed film may be easily peeled off, and it may be difficult to uniformly coat the corrosion-resistant glass sprayed film on the substrate. On the other hand, when the surface roughness Ra exceeds 50 μm, it is difficult to smooth the surface of the corrosion-resistant glass sprayed film, and it may be difficult to suppress etching by plasma or corrosive gas.

  The thickness of the vitreous corrosion-resistant sprayed film according to the present invention is not limited, but is preferably 0.01 mm to 3 mm, particularly preferably 0.01 to 0.5 mm. When the thickness of the glassy corrosion-resistant sprayed film exceeds 3 mm, the corrosion-resistant glass sprayed film tends to crack and peel off due to the difference in thermal expansion coefficient with the base material. It may be insufficient. The thickness of the corrosion-resistant glass sprayed film can be confirmed by observing the cross section of the member with a microscope or by analyzing the composition of constituent elements using an EPMA (X-ray microanalyzer).

  The surface roughness Ra of the glassy corrosion-resistant sprayed film according to the present invention is preferably 0.01 to 10 μm, particularly preferably 8 μm or less. If the surface smoothness of the corrosion-resistant glass sprayed film is poor and rough, the protrusions formed on the surface of the corrosion-resistant glass sprayed film surface are selectively etched by plasma or corrosive gas, especially the edges. It is easy to generate.

The corrosion-resistant glass sprayed film of the present invention is preferably one using an inert gas such as N ₂ or Ar or a reducing gas such as H ₂ as the spray gas. In the thermal spraying of a nitrogen-containing substance, if oxygen is contained in the plasma gas, it is oxidized during the thermal spraying, and the corrosion resistance is lowered by the disappearance of nitrogen from the sprayed film. Regarding the nitrogen content in the sprayed film, perform X-ray fluorescence analysis or EPMA analysis on the surface of the sprayed film, or measure the thermal conductivity of nitrogen gas generated after cracking a small amount of the sprayed film in a furnace. Analyze by using a nitrogen analyzer to measure in

  When producing the corrosion-resistant glass sprayed coating of the present invention, the spraying distance, which is the distance between the tip of the spraying gun and the substrate under normal pressure, is preferably 40 to 150 mm. If the spraying distance exceeds 150 mm, the sprayed material will cool down before adhering to the substrate, and the sprayed film may not be deposited on the substrate. If the spraying distance is shorter than 40 mm, the temperature of both the substrate and the sprayed film will rise. As a result, the disappearance of nitrogen may occur due to the decomposition of the nitride, which is the thermal spray material, and the corrosion resistance may decrease.

  In the production of the corrosion-resistant glass sprayed film of the present invention, in the case of plasma spraying using an inert gas or a reducing gas under atmospheric pressure, the substrate temperature is preferably 100 to 800 ° C. When the substrate temperature is lower than 100 ° C., the sprayed material is cooled when adhering to the substrate, and the film quality of the sprayed film on the substrate is poor. On the other hand, if the substrate temperature is higher than 800 ° C., the disappearance of nitrogen occurs due to the decomposition of the nitride, which is the thermal spray material, and the corrosion resistance decreases.

  In the case of plasma spraying using an inert gas or a reducing gas under an inert gas pressurization, the substrate temperature is preferably 100 to 1200 ° C. When the substrate temperature is lower than 100 ° C., the sprayed material is cooled when adhering to the substrate, and the film quality of the sprayed film on the substrate is poor. On the other hand, when the substrate temperature is higher than 1200 ° C., the disappearance of nitrogen occurs due to the decomposition of the nitride, which is the thermal spray material, and the corrosion resistance decreases. In thermal spraying under pressure, compared to thermal spraying at normal pressure, generation of nitrogen due to decomposition of nitrogen can be suppressed, so that thermal spraying can be performed at a temperature higher than normal pressure.

  The corrosion-resistant glass member of the present invention preferably has an intermediate layer composed of a material having a thermal conductivity of 10 W / m · K or less between the substrate and the corrosion-resistant glass sprayed film. If an intermediate layer with low thermal conductivity is inserted between the substrate and the corrosion-resistant glass sprayed film, the cooling rate after spraying becomes slow, and the sprayed film melts well, so that a dense sprayed film with few pores can be obtained. . Among these intermediate layers, zirconia, ceria, hafnia and the like are particularly preferable. With materials exceeding 10 W / m · K, the cooling rate is not slow, and it may be difficult to obtain a dense sprayed film.

  Next, the manufacturing method of the corrosion-resistant member of this invention is demonstrated.

  The method for producing a corrosion-resistant member of the present invention includes, for example, silica, alumina, aluminum nitride, silicon nitride, 3a group and 2a group so as to contain Si, Al, O, N and 3a and / or 2a group elements. There is a method of preparing a glass ingot by mixing a powder selected from oxide powders at a predetermined ratio and melting the mixture in a reducing atmosphere under pressure or normal pressure.

  The corrosion-resistant member by the glass sprayed film of the present invention can be manufactured by forming a corrosion-resistant glass sprayed film by spraying.

  The thermal spraying raw material used in the present invention is a raw material having a glass composition containing Si, Al, O, N and Group 3a and / or Group 2a elements, and it is preferable to use a powdery raw material. As such a raw material, a granule mixture of each oxide and each nitride powder as described above, or a mixture of each of the above oxides and each nitride powder in a predetermined ratio, and a reducing atmosphere under pressure or normal pressure. A glass ingot melted below can be prepared, and then prepared by pulverization. Furthermore, each oxide and each nitride powder mentioned above can be made into a slurry, and the mixed slurry can be obtained by a method of forming granules by a spray drying method and then sintering the granules. In each method described above, an acrylic binder or the like may be added as necessary.

  The particle size of the raw material powder used for thermal spraying is not limited, but the average particle size is preferably 10 to 100 μm. If the average particle size is less than 10 μm, the raw material powder itself does not have sufficient fluidity, and it may be difficult to uniformly supply the raw material into the thermal spray frame. On the other hand, if the average particle size exceeds 100 μm, the sprayed particles may not be melted uniformly, and the adhesion of the resulting sprayed film to the substrate may be likely to deteriorate.

  In the present invention, when forming the corrosion-resistant glass sprayed coating, it is preferable that the temperature of the substrate surface is preheated and sprayed in advance. Preheating the substrate surface in advance is effective for preventing cracking of the substrate due to heat shock and obtaining a corrosion-resistant glass sprayed film having high adhesion during thermal spraying. The preheating temperature varies depending on the type of substrate used, but for example, a range of 100 to 800 ° C. for a quartz glass substrate and a range of 50 to 500 ° C. for an aluminum substrate are preferable.

  An excessively high preheating temperature is not preferable because nitrogen in the sprayed film is decomposed and crystallization of the glass proceeds. Preheating may be performed by heating the substrate with an external heater, or irradiating the substrate with a thermal spray frame without supplying raw materials. The preheating temperature can be measured with a thermocouple from the back surface of the substrate or with a non-contact radiation thermometer.

  The thermal spraying method used in the present invention is preferably plasma spraying. FIG. 2 shows a general plasma spraying apparatus. The plasma spraying apparatus melts the thermal spray powder 23 by using a plasma jet formed by the plasma gas 22 flowing between the anode 21 and the cathode 20 as arc discharge as a heat source, and the melted thermal spray powder has a flow velocity of the plasma gas. In this case, the bumps are deposited on the substrate 25.

In the plasma spraying apparatus, an inert gas such as N ₂ or Ar, a reducing gas such as H _2, or a mixed gas thereof can be used as the plasma gas. In the thermal spraying of nitrogen-containing materials, if oxygen is contained in the plasma gas, it will be oxidized during thermal spraying, and the corrosion resistance will be reduced by the disappearance of nitrogen from the sprayed film, so an inert gas or reducing gas is used as the plasma gas. A plasma spraying method that can be used is preferable.

  In addition to the plasma spraying method, there are flame spraying and high-speed flame spraying as general spraying methods. However, it is preferable to perform spraying in a flame in a reducing atmosphere in which fuel is excessive with respect to oxygen or the like.

  In the thermal spraying of the present invention, the thermal spraying power applied when spraying the thermal spraying frame onto the base material varies depending on the apparatus used. For example, in the case of a plasma thermal spraying apparatus as shown in FIG. 2, the thermal spraying power is set to 20 kW or more. Conditions can be exemplified.

  When producing corrosion-resistant glass by thermal spraying, it is preferable to use a substrate having a surface roughness Ra of 1 to 50 μm. When a substrate having a smooth surface is used, the deposition efficiency of the sprayed film is poor, and the adhesion between the substrate and the glassy corrosion-resistant sprayed film tends to be deteriorated.

  As a method of setting the surface roughness Ra of the substrate surface to 1 to 50 μm, a method in which a sprayed film having such a surface roughness is sprayed on the substrate in advance, or the substrate itself is blasted or blasted and hydrofluoric acid, etc. It is possible to exemplify the chemical etching by the above.

  The corrosion-resistant member of the present invention can be used for a container or a part of a film forming apparatus or a plasma processing apparatus. As a method of using the corrosion-resistant member, it can be used in a part that comes into contact with corrosive gas or plasma in these apparatuses, and more specifically, it can be used as a ring-shaped member or a bell jar.

  The film forming apparatus here is, for example, a CVD apparatus or a PVD (Physical Vapor Deposition) apparatus. The reaction tubes and bell jars of these devices are cleaned with fluorine-based gas for cleaning after use, and corrosion due to the cleaning and the generation of particles due to the cleaning have been a problem. Those problems are solved by using.

  The plasma processing apparatus here is, for example, a plasma etching apparatus or a plasma cleaning apparatus, and refers to an apparatus that irradiates a product placed in the apparatus with plasma and peels or cleans the surface of the product. Since the ring-shaped focus ring or bell jar of these apparatuses is also etched by fluorine-based plasma, the generation of particles is a problem in the parts in the apparatus that come into contact with corrosive gas or plasma. Similarly, in this case, if the corrosion-resistant member of the present invention is used, it is difficult to corrode and the generation of particles is small.

  Since the corrosion-resistant member of the present invention has the following effects, when used in an apparatus using a corrosive gas or plasma, such as a CVD apparatus or a plasma processing apparatus, it has high corrosion resistance and generates less particles, so that it contaminates products. It is possible to operate continuously with a high product yield.

  The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

Example 1 Production of Bulk Body Silicon nitride, alumina, silica and oxides of the 3a element shown in Table 1 were prepared in Table 1 No. Adjusted, mixed, and molded so as to have a composition of 101, 102, and performed a heat treatment for 4 hours in a carbon crucible under a nitrogen pressure atmosphere at a heat treatment temperature of 1750 ° C. and 0.6 MPa using an atmospheric pressure furnace, A glass bulk body was produced. FIG. 3 illustrates the respective compositions.
2) Preparation of thermal sprayed film 2-1) Preparation of thermal sprayed base material Quartz glass with surface roughness Ra of 10 μm treated with 24% hydrofluoric acid for 1 hour against quartz glass with surface roughness Ra of 6 μm by blasting Base material (base material A), aluminum base material (base material B) whose surface roughness is 7 μm by blasting, mullite base material (base material C) whose surface roughness is 6 μm by blasting, 3 mol% in aluminum substrate An aluminum substrate (base material D) coated with a zirconia sprayed film containing yttrium and having a surface roughness Ra of 8 μm, and an aluminum substrate (substrate E) coated with a ceria sprayed film on the aluminum substrate and having a surface roughness Ra of 9 μm Was prepared.

2-2) Preparation of raw material powder for thermal spraying After adjusting silicon oxide, alumina, silica and oxides of group 3a and / or 2a elements shown in Table 1 to have the composition shown in Table 1, and mixing a binder with these powders Then, granulated powder having an average particle diameter of 50 μm was obtained by spray drying. The granulated powder was degreased at 500 ° C. for 2 hours and then sintered at 1300 ° C. for 2 hours to obtain a sintered powder having an average particle size of 50 μm.

2-3) Formation of Corrosion Resistant Glass Sprayed Film Using the various substrates prepared in 2-1) and using the plasma spraying apparatus shown in FIG. 2 at normal pressure, nitrogen 40 SLM (Standard Litter per Minute) as plasma gas. ) And hydrogen 12SLM, the spraying distance was 60 mm, the spray gun was moved at a speed of 400 mm / second, plasma was generated at a power of 30 kW, and the substrate was preheated without supplying raw material powder.

  Next, the thermal spraying raw material powder produced in 2-2) is supplied at a rate of 15 g / min, sprayed five times while moving the spray gun at a speed of 400 mm / second, a pitch of 4 mm, and a spray distance of 60 mm to form a corrosion-resistant sprayed film. did. FIG. 3 illustrates the respective compositions.

  Table 2 also shows the thermal spray powder composition at a normal pressure with an atomic ratio of Si: Al ratio of 75:25, O: N ratio of 86:14, and Al + Si: Y ratio of 2: 1. The conditions of the sprayed film formed by the same method as described above except that the spraying distance is changed to 40, 60, 90, 120, and 150 mm, and the conditions of the sprayed film formed by the same method under the pressurization with nitrogen are shown.

3) Performance evaluation (corrosion resistance)
Measurement of surface roughness Ra by contact type surface roughness meter, confirmation of vitrification by X-ray diffractometry, and fluorine-based gas for corrosion-resistant bulk glass and sprayed film of various compositions prepared in 1) and 2) The measurement test of the etching rate and the amount of particles when exposed to the plasma was included. As etching conditions, plasma was generated by applying a high-frequency power of 300 W between the electrode plates using a pressure of 1 torr in the reaction processing chamber, CF ₄ gas as the reaction gas. The etching thickness was measured by using a level difference measuring method, and the generation of particles was evaluated by observing the granular material on the surface of the corrosion-resistant member with a scanning electron microscope. In the confirmation of vitrification by the X-ray diffraction method, the vitrification of all bulk bodies and sprayed films was confirmed. The results of the surface roughness Ra, the etching rate, and the amount of particles are shown in Tables 1 and 2. All of the corrosion-resistant members had an etching rate of 0.3 μm / hr or less, and in most of the examples, it was as small as 0.2 μm / hr, excellent in corrosion resistance, and generating less particles.

  The X-ray diffraction spectrum of the sprayed coating prepared in Example 103 is shown in FIG. An amorphous halo pattern was observed, and no crystalline diffraction peak was observed.

Comparative Example No. 1 in Table 1 was used as a starting material in the same manner as in 2-1). The raw material powder for thermal spraying was prepared with the composition of 112 and 113. The raw material powder for thermal spraying was sprayed on a quartz glass substrate (substrate A) having a surface roughness Ra of 10 μm treated with 24% hydrofluoric acid for 1 hour on quartz glass having a surface roughness Ra of 6 μm by blasting. (No. 112 and 113). A member (No. 114) obtained by spraying Y ₂ O ₃ sprayed powder on the substrate A, an alumina sintered body (No. 115) not sprayed, a quartz glass bulk body (No No) 116) was confirmed for vitrification, and the etching rate and the amount of particles were measured in the same manner as in the examples. Table 2 also shows the thermal spray powder composition at a normal pressure with an atomic ratio of Si: Al ratio of 75:25, O: N ratio of 86:14, and Al + Si: Y ratio of 2: 1. A sprayed film formed by the same method as in 2-2) and a sprayed film formed by the same method under pressure with nitrogen except that the spraying distance is set to 30 mm will be described.

No. The member 112 was confirmed to be glassy, but the etching rate was larger than that of the corrosion-resistant member, and the corrosion resistance was poor. No. In the member No. 113, the etching rate was higher than that of the corrosion-resistant member, and because it was not glassy, the amount of particles was large and the corrosion resistance was poor compared to the glassy corrosion-resistant member of Example. This No. FIG. 5 shows the X-ray diffraction spectrum of the member No. 113, and many crystalline diffraction peaks were observed. The Y ₂ O ₃ sprayed film (No. 114) had a lower etching rate than the quartz glass bulk body, but generated more particles than the vitreous corrosion-resistant member of the example. In the alumina bulk (No. 115), the etching rate was larger than that of the corrosion-resistant member, and the generation of particles was larger than that of the vitreous corrosion-resistant member of Examples. The quartz glass substrate (No. 116) having no vitreous corrosion-resistant sprayed coating had a large etching rate of 6 μm / hr and poor corrosion resistance. FIG. 3 illustrates the respective compositions.

  Moreover, in the base material which made the spraying distance 30 mm, the sprayed film was crystallized. Moreover, since the bubbles in the thermal spray film increased at the same time as the etching rate increased, the film quality deteriorated, many particles were generated, and the corrosion resistance was poor (No. 211, 212). About this sprayed film, when the nitrogen content was measured using a nitrogen analyzer, it was less than 0.1%.

It is a figure which shows the claim of the composition of this patent. It is a figure which shows an example of a plasma spraying apparatus. It is a figure which shows the composition of an Example and a comparative example. No. It is a figure which shows the X-ray-diffraction spectrum of the sprayed film obtained by 103 (Example). No. It is a figure which shows the X-ray-diffraction spectrum of the sprayed film obtained by 113 (comparative example).

Explanation of symbols

20: Cathode 21: Anode 22: Plasma gas 23: Thermal spray powder (supply port)
24: Spraying distance 25: Base material 26: Glass sprayed film 27: Power supply

Claims (7)

A corrosion-resistant member made of glass in which a portion exposed to fluorine plasma, chlorine plasma, or corrosive gas is composed of Si, Al, O, N, and 3a and / or 2a group elements. The corrosion-resistant member according to claim 1, wherein the portion exposed to fluorine plasma, chlorine plasma, or corrosive gas is a sprayed film. In the composition of the corrosion resistant member, the Si: Al atomic ratio is in the range of 99.9: 0.1 to 30:70, and the O: N atomic ratio is in the range of 99.9: 0.1 to 60:40. The corrosion-resistant member according to claim 1, wherein the atomic ratio of Al + Si: 3a group element is 95: 5 to 40:60. The composition of the corrosion resistant member has an Si: Al atomic ratio in the range of 99.9: 0.1 to 30:70 and an O: N atomic ratio in the range of 99.9: 0.1 to 60:40. The corrosion-resistant member according to claim 1, wherein the atomic ratio of the Al + Si: 2a group element is 95: 5 to 50:50. A corrosion-resistant laminated member comprising a heat insulating intermediate layer formed by thermal spraying between a substrate and the corrosion-resistant member according to any one of claims 1 to 4. The atmospheric pressure plasma spraying using a reducing or inert gas is used, the spraying distance is set to 40 to 150 mm, and the substrate temperature during spraying is set to 100 to 800 ° C. The manufacturing method of the corrosion-resistant member of description. 5. Corrosion resistance according to any one of claims 1 to 4, characterized in that the substrate temperature during spraying is set to 100 to 1200 ° C using plasma spraying using reducing or inert gas under pressurized inert gas. A method for manufacturing a structural member.

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