JP4546448B2 - Thermal spray coating coated member having excellent plasma erosion resistance and method for producing the same - Google Patents

Description

The present invention relates to a member used in a thin film forming apparatus or a plasma processing apparatus in a semiconductor processing process and a method for manufacturing the same, and more particularly to a container member used in plasma processing in an environment containing a halogen compound, such as vacuum deposition or ion plating. The present invention relates to a thermal spray coating member having excellent plasma erosion resistance used as a container member used for coating, sputtering, chemical vapor deposition, laser precision processing, plasma sputtering, and the like, and a method for producing the same.
In addition to being excellent in plasma erosion resistance, the thermal spray coating member according to the present invention is a member for semiconductor processing equipment that is required to have excellent particle adhesion, deposition function and re-scattering prevention function, semiconductor precision processing member or these It can be used in the field of structural members (walls of processing chambers).

In the semiconductor processing process, there is a step of forming a thin film of metal, metal oxide, nitride, carbide, boride, silicide or the like. In these processes, a thin film forming apparatus such as a vacuum deposition method, ion plating, sputtering, or plasma CVD is used (for example, Patent Document 1).
When forming a thin film with these apparatuses, the thin film material also adheres to the surfaces of various jigs and members used in the apparatus. The adhesion of the thin film material to the jig or device member is less likely to be a problem when the amount is small. However, as the time for thin film formation increases, the amount of particles adhering to the surface of the jig or member increases, while the temperature change during operation and the mechanical load on the jig or member often fluctuate. I came. As a result, some of the particles that consist mainly of the thin film that adheres to the surface of the jig or member during the thin film formation process peel and scatter, which adheres to the semiconductor wafer and degrades the product quality. There is a problem.

Conventionally, the following method has been proposed as a technique for preventing peeling of particles for forming a thin film attached to the surface of various members used in the apparatus as described above.
For example, in Patent Documents 2 and 3, the surface of a jig or member is sandblasted, and the surface is roughened by honing or knitting, thereby increasing the effective surface area and peeling the attached thin film particles. A technique for preventing scattering is disclosed.

  Patent Document 4 discloses a technique for suppressing peeling of thin film particles by periodically providing U grooves and V grooves at intervals of 5 mm or less on the surfaces of jigs and members.

Patent Documents 5 and 6 disclose a technique for forming a TiN film on the surface of a member, or further forming a hot-dip coating of Al or an Al alloy, and Patent Document 7 uses Ti and Cu materials. After forming the thermal spray coating, only Cu is dissolved and removed by HNO ₃ , thereby enabling the surface structure with a porous and large specific surface area to be extended, while suppressing the scattering of attached thin film particles. Techniques to do this are disclosed.

  One of the inventors also in Japanese Patent Application Laid-Open No. H10-228707 sprays metal with the metal mesh in close contact with the surface of the metal member, or after spraying the metal, the metal is again applied with the metal mesh in close contact therewith. A technique has been proposed in which the specific surface area is increased by applying thermal spraying, and then peeling the wire mesh to form lattice-like irregularities on the surface of the thermal spray coating, thereby allowing a large amount of thin film particles to adhere.

  However, recent semiconductor processing has become more highly accurate, and along with this, the cleanliness of the processing environment has become stricter than before. In particular, when semiconductor processing is performed by plasma sputtering in a halogen gas or a halogen compound gas, corrosion products generated on the surfaces of members and jigs disposed in the apparatus used for this processing, or sputtering Due to the phenomenon, it is necessary to take measures against fine particles generated from the surface of the member.

In other words, in the semiconductor processing process, re-scattering of the thin film particles in the thin film formation process is a problem, and in the plasma etching process, fine particles are generated not only in the semiconductor processing but also in the peripheral members. It has been pointed out that this affects the quality of semiconductor products. As a countermeasure, as disclosed in Patent Document 9, quartz is used as a base material, the surface roughness is 3 to 18 μm, and a sprayed coating of Al ₂ O ₃ and TiO ₂ is directly formed thereon. The surface of this thermal spray coating is recommended to be a rough surface showing a negative value of less than 0.1 in terms of the skewness (Rsk) of the roughness curve.

In addition, Patent Documents 10 to 13 disclose a technique for increasing the adhesion of particles and the deposition capacity, and a technique for reducing the scattering by providing concave protrusions that divide the film of the deposit. Seen in 14th.
JP 50-75370 A JP 58-202535 A Japanese Patent Publication No. 7-35568 JP-A-3-247769 JP-A-4-202660 JP-A-7-102366 JP-A-6-220618 Japanese Patent No. 3076768 JP-T-2004-522281 JP 2000-191370 A JP-A-11-345780 JP 2000-72529 A JP-A-10-330971 JP 2000-228398 A Japanese Patent Laid-Open No. 10-4083 JP 2001-164354 A

The prior art in the semiconductor processing process has the following problems.
(1) Problems in thin film forming process (a) Techniques disclosed in Patent Documents 1 to 8 for preventing adhesion of thin film particles to jigs and apparatus members in the thin film forming process and the phenomenon of scattering thereof, ie, thin film particles Although the method of enlarging the adhesion area by various means has a certain effect on the long-time operation of the thin film formation work and the improvement of the production efficiency by it, eventually the deposited thin film particles are scattered again. It cannot be a fundamental solution.
(B) Since the surface treatment film formed or treated on the surface of a jig or device member on which a large amount of thin film particles are deposited and deposited is a metallic film, when removing the thin film particles with acid or alkali, It dissolves at the same time, so the number of times that it can be regenerated and used is small, which increases the cost of the product.
(C) The measures for expanding the deposition deposition area of the thin film particles in the prior art are only for the purpose of expanding the area, and are not a proposal for a method for preventing scattering of the deposited deposition thin film particles.

(2) Problems in the plasma etching process As disclosed in Patent Document 9, the countermeasure technology for jigs and apparatus members used in the plasma etching process is made of Al ₂ O ₃ and TiO _{2 on} the surface of the quartz substrate. By forming the sprayed coating and controlling the surface roughness of the sprayed coating to a negative value of less than 0.1 of Rsk (skewness of the roughness curve), fine particles generated by the sputtering phenomenon can be reduced. It has been proposed to accept on the surface of the film having a curve. However, TiO ₂ disclosed in this technology is corroded or etched by itself in a plasma etching processing environment containing a halogen gas, and on the contrary, becomes a contamination source and generates a large amount of particles. On the other hand, the thermal spray coating of Al ₂ O ₃ is superior in corrosion resistance and plasma etching resistance to the TiO ₂ coating, but has a short life and a surface shape showing a negative value less than Rsk: 0.1. Has a drawback that the amount of adhesion and deposition of environmental pollutants is small and saturates within a short time, so that the rest becomes a source of particles. Further, the surface-shaped convex part has a problem that it has a large area, and a large amount of particles are likely to be deposited on the convex part, and has a geometric shape that is likely to rescatter.

As disclosed in Patent Document 15, the technique of applying a single crystal of Y ₂ O ₃ as a plasma erosion-resistant material is limited in application because it is difficult to form a film, and Y ₂ The technique of Patent Document 16 that proposes a sprayed coating of O ₃ is excellent in plasma erosion resistance, but does not consider adhesion / deposition of environmental pollutant particles.

The object of the present invention is to provide a surface structure of a sprayed coating that is excellent in plasma erosion resistance, is not only detoxified by adhesion and deposition of particles that cause contamination of the plasma processing atmosphere, and is effective in preventing re-scattering. It is in.
Another object of the present invention is to increase the accuracy of semiconductor processing in a corrosive environment containing halogen gas, and to stably process over a long period of time, and to improve the quality and reduce the cost of semiconductor products. It is in the place which proposes a member and its manufacturing method.

The present invention solves the above-described problems of the prior art by the following technical means.
(1) That is, the present invention comprises a base material and a ceramic sprayed coating covering the surface of the base material, and the ceramic sprayed coating has a skewness above the center line of the roughness curve in the height direction of the outermost layer portion. value (Rsk) only melt, solidifying the portion of the convex portion tinged is rounded to indicate a negative value, the electron beam having a surface shape in which the shape of the recess below the center line of the roughness curve does not change It is a thermal spray coating member excellent in plasma erosion resistance characterized by being an irradiation layer.

(2) Further, according to the present invention, a metallic undercoat is formed on the surface of the substrate, and a top coat of a ceramic sprayed coating is formed thereon, and the outermost layer portion of the top coat is in the height direction. A thermal spray coating member excellent in plasma erosion resistance is proposed, which is an electron beam irradiation layer having a surface shape in which the skewness value (Rsk) of the roughness curve is negative.

(3) Further, in the present invention, after applying a metallic undercoat directly on the surface of the base material or first on the surface of the base material, a thermal spray comprising a ceramic having a particle diameter of 5 to 80 μm as a top coat thereon. The powder material is sprayed to form a ceramic sprayed coating, and the surface of the ceramic sprayed coating is subjected to electron beam irradiation treatment to melt and solidify the outermost layer portion of the coating, and the center of the roughness curve in the height direction. skewness values above the line (Rsk) and is shows a negative value molten only portions of the convex portions rounded, solidifying, the surface shape of the concave portion below the center line of the roughness curve does not change The present invention proposes a method for producing a thermal spray coating member having excellent plasma erosion resistance, characterized by forming an electron beam irradiation layer having a shape.

In the present invention (1), (2), (3), the ceramic sprayed coating forming the electron beam irradiation layer is made of Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ composite. It is an oxide ceramic sprayed coating made of oxide, the ceramic sprayed coating has a thickness of 50 to 2000 μm, and the electron beam irradiation layer is composed of a layer in which the crystal structure of the sprayed ceramic particles is changed. Can be an effective means.

  The thermal spray coating member according to the present invention has excellent plasma erosion resistance, so that it does not become a source of particles that cause atmospheric contamination, and more particles are adsorbed on the coating surface. In addition to being excellent in detoxifying properties by increasing the amount deposited, it is also excellent in preventing re-scattering of adhered and deposited particles.

  Furthermore, when the member of the present invention is employed, high environmental cleanliness is required, and at the same time, the processing accuracy of a semiconductor processed product performed in a severe corrosive environment containing a halogen compound can be increased. In addition, when such a member is used, continuous operation over a long period of time is possible, and the quality of semiconductor products to be precision processed can be improved and the product cost can be reduced.

  As an example of a preferred embodiment of the present invention, ceramic (hereinafter, described as an example of “oxide ceramics”) is sprayed on a surface of an apparatus member used in a process such as a thin film formation process or a plasma etching process. An example of forming a film will be described.

(1) Formation of oxide ceramic sprayed coating Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ as a top coat directly on the surface of the substrate or on the metallic undercoat formed on the surface of the substrate. the thermal spray coating of oxide ceramics consisting of -Y ₂ O ₃ composite oxide is formed to a thickness of 50 to 2000 m. If the film thickness of this thermal spray coating is less than 50 μm, the life as a top coat is shortened. On the other hand, if it is greater than 2000 μm, the residual stress resulting from thermal shrinkage generated during thermal spray deposition increases and the impact resistance of the coating increases. And adhesion to the substrate are reduced.

  Moreover, the thermal spraying powder material used for formation of these oxide ceramic sprayed coatings should have a particle size of 5 to 80 μm, and if the particle size is smaller than 5 μm, it is difficult to supply the spraying gun continuously and evenly. For this reason, the thickness of the film tends to be uneven. On the other hand, if the particle size is larger than 80 μm, the film is formed in a so-called unmelted state without being completely melted in the thermal spraying heat source. Formation of a sprayed coating becomes difficult.

  Ni and its alloy, Mo and its alloy, Al and its alloy, Mg alloy, etc. are suitable for the metallic undercoat formed on the surface of the substrate prior to the formation of the top coat made of the oxide ceramic sprayed coating. The film thickness is preferably in the range of 50 to 500 μm. The reason is that if the film thickness is less than 50 μm, the substrate is not sufficiently protected, whereas if the film thickness is more than 500 μm, the effect as an undercoat is saturated, which is not economical.

  In addition to metals such as Al and Al alloys, Ti and Ti alloys, stainless steel, and Ni-based alloys, the base material is quartz, glass, plastic (polymer material), sintered member (oxide, carbide, boride, Silicides, nitrides, and mixtures thereof), or those obtained by forming a plating film or vapor deposition film on the surface of the substrate.

In the present invention, any one of Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ double oxide is sprayed on the surface of the substrate as the oxide ceramic sprayed coating (top coat). The reason is that these oxide ceramics are superior in corrosion resistance and plasma erosion resistance compared to other oxide ceramics such as TiO ₂ , MgO, ZrO ₂ , NiO, Cr ₂ O _{3 and the} like. is there.

  The top coat and undercoat formed on the substrate surface are preferably formed by employing an atmospheric plasma spraying method, a low pressure plasma spraying method, a water plasma spraying method, a high-speed and low-speed flame spraying method, or an explosion spraying method.

(2) Surface shape of oxide ceramic sprayed coating (optimal roughness)
In the present invention, the oxide ceramic sprayed coating formed directly on the surface of the substrate or after applying a metallic undercoat has a surface shape, that is, a surface roughness, particularly a roughness curve in the height direction. As described below.
In general, a member having a large surface area is used as a member such as a jig used in a semiconductor device, for example, a plasma processing apparatus. The reason for this is to maintain as long as possible the deposition of environmental contaminants such as thin film particles and particles generated in the processing atmosphere by plasma etching, while adhering (adsorbing) them to the surface of the member, and at the same time, This is to prevent the adhering and deposited environmental pollutants from re-scattering from the substrate surface.

  In the present invention, for such a purpose, the surface shape of the sprayed coating formed as a top coat on the substrate surface, that is, the surface roughness curve of the coating shows a roughness indicating the distortion in the coating thickness (height) direction. The skewness value (Rsk) of the curve is specified.

  In the present invention, as a means for specifying the surface shape of the oxide ceramic sprayed coating, the skewness value (Rsk) adopted is the geometric property specification of JIS B0601 (2001), surface properties: contour curve method, terms and definitions, and It is specified in the surface property parameter. As shown in FIG. 1, the skewness value has a distribution in which the probability density function is biased toward the valley in the case of a wide roughness curve in the valley (concave) portion with respect to the peak (convex portion).

This Rsk is defined as the average of the cube of the height (Z (x)) at the reference length (lr) divided by the cube of the root mean square (Rq ³ ).

This skewness value is controlled by controlling the particle size of the sprayed powder material and spraying conditions, specifically, using a mixed gas of Ar and H ₂ as a plasma gas and setting the spray angle to 90 ° to 55 ° with respect to the substrate. If it is applied at a temperature, a film having a stable surface shape can be obtained.

  More specifically, in order to obtain the above-described surface shape of the sprayed coating, that is, a coating having a roughened surface having a predetermined roughness curve, ceramic powder having a particle size of 5 to 80 μm is continuously in units of tens of thousands. This is realized by supplying the heat source. In this case, all the thermal spray powder materials are distributed not only in the center (in the frame) of the heat source having a high temperature but also in the periphery (outside the frame) of the heat source having a relatively low temperature, Even if the sprayed powder particles fly through the center of the heat source, the degree of heating and melting varies depending on the size of the particle size. Since the thermal spray coating is composed of ceramic particles having different thermal histories and particle diameters, particles having different flatness are deposited randomly. Therefore, the surface roughness of the thermal spray coating is formed as a result of depositing such uneven particles, and the oxide having a particle size of 5 to 80 μm as the thermal spray powder material under a predetermined thermal spraying condition. Thermal spraying ceramic spray powder material.

In the present invention, in order to improve plasma erosion characteristics, the surface of the sprayed coating of Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ composite oxide is subjected to electron beam irradiation treatment to spray particles. the melt - solidifying, portions of the outermost layer (0.5 to 5 [mu] m) of the solution morphism film, i.e., the shape of the convex portion rounded above the center line of the skewness value indicated by the roughness curve, As shown in FIG. 2, it was changed to a trapezoidal convex part.

  When the surface of the oxide ceramic sprayed coating is irradiated with an electron beam, the irradiated portion suppresses the generation of particles that cause further excellent contamination in the atmosphere, and at the same time, without reducing its adhesion capacity and deposition capacity. Re-scattering can be suppressed, and the sprayed coating itself exhibits a good plasma erosion resistance effect. Therefore, when the thermal spray coating is irradiated with an electron beam, the disadvantages of the prior art, which is the source of environmental pollution particles by itself, are eliminated.

  Note that if the effect of electron beam irradiation extends below the center line of the surface roughness curve, the recesses suitable for mass adhesion and deposition of particles melt, and the entire coating becomes smooth, so that The unevenness peculiar to the film cannot be used effectively.

  Even in the portion of the sprayed coating surface where the skewness value of the roughness curve shows a surface shape with Rsk <0, there is no effect on the shape of the concave portion appearing below the center line, and the height direction including the rounded convex portion The electron beam irradiation is performed only on the portion above the center line of the roughness curve. In this case, since the convex part above the center line melts and solidifies by electron beam irradiation and changes to the crystal type, the generation of particles from the oxide ceramic sprayed film irradiated with the electron beam is suppressed. Can do.

Further, when the surface of the oxide ceramic sprayed coating is irradiated with an electron beam, the crystal structure of the oxide ceramic, Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ double oxide particles changes, Plasma erosion resistance can be improved as compared with a film before electron beam irradiation. This effect compensates for the disadvantage that the sprayed coating is subjected to the action of plasma erosion and becomes a source of environmental pollution particles.

When the surface of the oxide ceramic sprayed coating is irradiated with an electron beam, the crystal structure of the coating component changes in a more stable direction according to the findings of the inventors. That is, in the case of Al ₂ O ₃ , the crystal structure after coating spraying is the γ phase, but changes to the α phase after electron beam irradiation, and the crystal structure of Y ₂ O ₃ is from cubic and monoclinic crystals. The crystal structure of the cubic crystal and the Al ₂ O ₃ —Y ₂ O ₃ double oxide change so that both the above Al ₂ O ₃ and Y ₂ O ₃ alone change. Plasma erosion property is improved.

As a method for melting the portion above the center line of the skewness value Rsk, it is recommended to control the irradiation output and the number of irradiations in the range of the following conditions.
Irradiation atmosphere: Ar gas irradiation output of 10 to 0.005 Pa: 1.0 to 10 keV
Irradiation speed: 1-20m / s
Other methods of adopting irradiation conditions other than the above irradiation conditions include generating an electron beam with an electron gun, or performing irradiation in a reduced pressure or a reduced inert gas to reduce the fineness of the irradiated layer. Adjustment is possible.

In the present invention, the significance and the advantages of performing the electron beam irradiation treatment on the surface of the oxide ceramic sprayed coating are listed as follows.
a. The oxide ceramic sprayed coating is not limited to these double oxides such as Al ₂ O ₃ , Y ₂ O _3, or Al ₂ O ₃ —Y ₂ O ₃ double oxide, but, for example, 3Al ₂ O _3. Since it can be applied to all ceramic sprayed coatings such as 2SiO ₂ , ZrO ₂ , and Cr ₂ O ₃ , its use is very wide.
b. Regardless of the shape of the roughness curve (skewness value) in the height direction of the sprayed coating surface, the electron beam irradiation treatment is performed on the convex part of each roughness curve, so that the physical and chemical properties of the entire coating are improved. There is no impact.
c. At the projections on the surface of the thermal spray coating irradiated with the electron beam, sharply shaped needle-like projections change to rounded trapezoidal projections by a local melting-solidification reaction, so that plasma etching is effective. In addition to being difficult to receive, the crystal structure also changes to a more stable one, so that the crystal structure level can be improved and the life can be extended.
d. The projections on the surface of the thermal spray coating that has been irradiated with an electron beam have improved plasma erosion resistance due to the effects of changes in the crystal structure associated with the melting-solidification reaction, and do not become a source of particles that cause environmental pollution. Maintaining the environmental cleanliness of the altitude, it is possible to smoothly perform precision processing of semiconductors.

Example 1
In this example, Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O is directly applied to the surface of a SUS304 base material (dimensions: width 40 mm × length 50 mm × thickness 7 mm) by plasma spraying. ₃ After forming a double oxide film to a thickness of 120 μm, the surface was subjected to a roughness curve in the height direction of the film surface using a roughness measuring instrument (SURFCOM 1400D-13 manufactured by Tokyo Seimitsu Co., Ltd.). By measuring the skewness value, an Rsk <0 film was irradiated with an electron beam and an unirradiated test piece was prepared.
These test pieces were examined for the following items using a reactive plasma etching apparatus having a plasma irradiation output of 80 W.

(1) Plasma etching property While flowing a mixed gas of CF ₄ gas (60 ml / min) and O ₂ gas (2 ml / min) in the plasma etching apparatus, the surface of the test sprayed coating is etched for 800 minutes, and then the coating is applied. The surface was observed with an electron microscope to evaluate plasma etching resistance.

Table 1 summarizes the results. Regarding the plasma etching resistance, the Al ₂ O ₃ , Y ₂ O ₃ and Al ₂ O ₃ —Y ₂ O ₃ double oxide films irradiated with the electron beam are all better than the non-irradiated films. Demonstrated sex. Specifically, in the case of Rsk <0 Y ₂ O ₃ coating (No. 4) and Al ₂ O ₃ —Y ₂ O ₃ double oxide coating (No. 6) that have not been subjected to the electron beam irradiation treatment, Al ₂ O Compared to the _three coatings, it exhibits considerably better plasma erosion resistance. However, even with this film, the plasma erosion resistance can be further improved by electron beam irradiation.

When the above results are combined, the shape of the roughness curve of the oxide ceramic sprayed coating surface is slightly different from Rsk <0, but the effect of electron beam irradiation is recognized. By this irradiation treatment, Al ₂ O ₃ , the plasma erosion resistance of the Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ complex oxide film is improved, and it is apparent that the defects that become the source of particles themselves can be solved.

(Example 2)
In this example, 80 mass% Ni-20 mass% Cr as an undercoat is 80 μm on the surface of an Al base (dimension: width 30 mm × length 50 mm × thickness 5 mm), and a topcoat is Al ₂ O ₃ . A film of Y ₂ O ₃ or Al ₃ O ₃ —Y ₂ O ₃ double oxide was formed in a thickness of 250 μm by plasma spraying. Thereafter, the Rsk value of the roughness curved surface was measured on the surface of the sprayed coating using the roughness meter, and each was subjected to an electron beam irradiation treatment.

These sprayed coating specimens are subjected to plasma etching under the following conditions, and the number of particle particles that are scraped and scattered by the etching action depends on the number of particles that adhere to the surface of a 3-inch diameter silicon wafer disposed in the same chamber. Compared. The number of adhered particles was examined by a surface inspection device (magnifying glass), and was generally targeted for particles of 0.2 μm or more.
(1) Atmospheric gas conditions CHF ₃ 80: O ₂ 100: Ar160 (numbers are flow rate cm ³ per minute)
(2) Plasma irradiation output High frequency power: 1300W
Pressure: 4Pa
Temperature: 60 ° C
In this experiment, as a comparative example, an oxide ceramic film of TiO ₂ and 8 mass% Y ₂ O ₃ -92 mass% ZrO ₂ was tested under the same conditions in addition to a film without electron beam irradiation.

Table 2 shows the results of this experiment. As is clear from this result, TiO ₂ (No. 8) of the comparative example is 2.0 hours, and 8 mass% Y ₂ O ₃ -92 mass% ZrO ₂ (No. 10) is 3.5 hours after the plasma irradiation test. It was confirmed that the particle management value exceeded 30 and the plasma erosion resistance was poor. On the other hand, Al ₂ O ₃ , Y ₂ O ₃ or Al ₂ O ₃ —Y ₂ O ₃ double oxide film suitable for the present invention exhibits excellent plasma erosion resistance as compared with the film of the comparative example. I understand that. In particular, the coatings (No. 1, 3, 5) irradiated with an electron beam exhibited much more excellent plasma erosion resistance than the coatings (No. 2, 4, 6) not irradiated with an electron beam.
From the above results, the electron beam irradiation treatment is particularly effective for a coating having a certain level of plasma erosion resistance in the state of a sprayed coating (as Spayed), and the roughness curve of the coating surface is also shown. It has been found that this is an effective treatment method without being greatly affected by the shape (Rsk <0).

(Example 3)
In this example, a thermal shock test was performed on all test pieces provided for the plasma erosion resistance test of Example 2. That is, the thermal spray coating specimen provided for the test of Example 2 was subjected to a plasma erosion test in a corrosive environment containing a halogen gas, and during this period, the corrosive halogen gas was passed through the topcoat pores. There is a possibility that it penetrates into the inside of the film, corrodes the undercoat, and the topcoat is easily peeled off.
In the thermal shock test, the sample was allowed to stand in an electric furnace at 300 ° C for 15 minutes and heated, and then this was cooled for 20 minutes in air at 24 ° C. After 10 cycles, the change in the topcoat was visually observed. did. As a result, it was confirmed that the top coat of all the thermal spray test pieces listed in Table 2 had no cracking or peeling of the film and maintained good thermal shock resistance.

  The technology of the present invention is a member used in the technical field of semiconductor processing devices such as vacuum vessel members used for vacuum deposition, ion plating, sputtering, chemical vapor deposition, laser precision processing, plasma sputtering, etc., and thin film forming devices. Can be applied.

It is a schematic diagram which shows the skewness value (Rsk) of the roughness curve of the height direction of this thermal spray coating surface. It is a schematic diagram of the roughness curve of the sprayed coating surface after an electron beam irradiation process. The hatched portion in the drawing indicates a portion melted and solidified by electron beam irradiation.

Claims (9)

It consists of a base material and a ceramic sprayed coating that covers the surface of the base material. The ceramic sprayed coating has a negative skewness value (Rsk) above the center line of the roughness curve in the height direction of the outermost layer part. shown to melt only portions of the convex portions rounded, solidifying, characterized in that an electron beam irradiation layer having a surface shape in which the shape of the recess of the lower unchanged from the center line of the roughness curve Thermal spray coating coated member with excellent plasma erosion resistance.   A metallic undercoat is formed on the surface of the substrate, and a top coat of a ceramic sprayed coating is formed thereon, and the topmost layer portion of the top coat has a skewness value (Rsk) of a roughness curve in the height direction. ) Is an electron beam irradiation layer having a surface shape showing a negative value. A thermal spray coating member excellent in plasma erosion resistance. The ceramic spray coating, according to claim 1 or 2, characterized in that an oxide ceramic sprayed coating consisting of _{Al 2 O 3, Y 2 O} 3 or Al ₂ O ₃ -Y ₂ O ₃ composite oxide Thermal spray coating coated member with excellent plasma erosion resistance.   The thermal spray coating member having excellent plasma erosion resistance according to any one of claims 1 to 3, wherein the ceramic thermal spray coating has a thickness of 50 to 2000 µm.   The thermal spray coating coated member having excellent plasma erosion resistance according to any one of claims 1 to 4, wherein the electron beam irradiation layer comprises a layer in which the crystal structure of the thermal spray ceramic particles is changed. First, a metallic undercoat is first applied to the surface of the base material, and then a thermal spray powder material made of a ceramic having a particle size of 5 to 80 μm is sprayed thereon as a top coat. And the surface of the ceramic sprayed coating is subjected to electron beam irradiation treatment to melt and solidify the outermost layer portion of the coating, and the skewness value (Rsk) above the center line of the roughness curve in the height direction. There melt only portions of the convex portions rounded to indicate a negative value, solidifying, form an electron beam irradiation layer having a surface shape in which the shape of the concave portion below the center line of the roughness curve does not change A method for producing a thermal spray coating member having excellent plasma erosion resistance. The ceramic spray coating, plasma-resistant according to claim 6, characterized in that the oxide ceramic sprayed coating consisting of _{Al 2 O 3, Y 2 O} 3 or Al ₂ O ₃ -Y ₂ O ₃ composite oxide A method for producing a thermal spray coating member having excellent erosion properties.   The method for producing a thermal spray coating member having excellent plasma erosion resistance according to claim 6 or 7, wherein the ceramic thermal spray coating has a thickness of 50 to 2000 µm.   The said electron beam irradiation layer consists of a layer which changed the crystal structure of the thermal spraying ceramic particle, The manufacture of the thermal spraying coating | coated member excellent in the plasma erosion resistance of any one of Claims 6-8 characterized by the above-mentioned. Method.

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