JP4650598B2 - Particles for oxide spraying for semiconductor manufacturing apparatus, manufacturing method thereof, and member for semiconductor manufacturing apparatus - Google Patents

Description

【００４１】
表１に示されるように、実施例１〜８で得られた各酸化物溶射用粒子は、その表面にステアリン酸被膜を有しているため、表面の平滑性に優れており、それぞれ対応する比較例の粒子よりも流動性に優れていることがわかる。特に、平均粒径０．５μｍという超微粉の場合でも、良好な流動性を示していることがわかる（実施例８参照）。
【００４２】
［実施例９］
実施例５で得られた酸化物溶射用粒子を用い、アルミニウム製基材上にアルゴン・水素ガスを用いて該粒子をプラズマ溶射して厚さ２１５μｍの溶射被膜を形成した。
得られた被膜の表面粗さＲａを、ＪＩＳ Ｂ０６０１に準拠した方法により測定したところ、５μｍと極めて平滑であった。
【００４３】
【発明の効果】
以上に述べたように、本発明によれば、表面に脂肪酸被膜および／または脂肪酸化合物被膜を有する酸化物溶射用粒子であるから、粒径が小さい場合であっても流動性を良好なものとすることができる。したがって、該溶射用粒子を基材上に溶射することで、表面研磨加工を施さなくとも、滑らかで凹凸のない溶射被膜を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a particle for oxide spraying for a semiconductor manufacturing apparatus , a manufacturing method thereof, and a member for a semiconductor manufacturing apparatus using the particle.
[0002]
[Background Art and Problems to be Solved by the Invention]
2. Description of the Related Art Conventionally, a coating is formed by spraying a metal oxide on metal, ceramics or the like to impart heat resistance, wear resistance, and corrosion resistance.
As a manufacturing method of the particles for thermal spraying for forming such a thermal spray coating, (1) The raw material is melted in an electric furnace, cooled and solidified, and then pulverized by a pulverizer, and then classified to adjust the particle size. A method of obtaining pulverized powder, (2) A method of obtaining a sintered pulverized powder by adjusting the particle size by pulverizing with a pulverizer after the raw material is sintered, and then classifying, (3) Adding the raw material powder to an organic binder A method of obtaining a granulated powder by adjusting the particle size by slurrying, granulating using a spray-drying type granulator, firing, and optionally classifying, (4) Powder by crystallization precipitation from solution Examples of the method are as follows.
[0003]
In addition, the characteristics required for the particles for thermal spraying are as follows: (1) the material can be stably and quantitatively supplied up to the plasma flame or flame flame during spraying, and (2) during the thermal spraying (in plasma flame or flame flame). ) It is required that the particle shape does not collapse, and (3) the particles are completely melted during spraying (in a plasma flame or flame flame).
[0004]
By the way, since the supply of the above-mentioned spraying particles is supplied to the spraying gun through a thin flow path such as a transfer tube, whether or not the spraying can be stably and quantitatively supplied depends on the powder physical properties of the spraying particles. It will be significantly affected by liquidity.
However, the thermal spray particles produced by the conventional production method generally deteriorate in fluidity as the particle size is reduced. Therefore, when a sprayed coating is formed using the small particle size particles, it is often difficult to supply the powder, and even if the powder can be supplied, the supply is intermittent. Thus, there is a drawback that a film having the above cannot be obtained, and problems arise in corrosion resistance, abrasion resistance, film strength, and the like.
[0005]
Corrosion resistance, wear resistance, strength, etc. of such a sprayed coating are closely related to the substrate as a substrate, but the corrosion resistance is strongly dependent on the surface state of the sprayed coating in particular, so there are few irregularities, A coating having a smooth surface is preferred. For this reason, in general, a surface polishing finish or the like is applied after spraying to smooth the surface.
However, when surface polishing is performed, there is a possibility that polishing waste may remain in the voids in the sprayed coating, and thus, for example, there is a problem in applications that require particle free, such as semiconductor manufacturing equipment. Accordingly, there has been a demand for the development of thermal spray particles that can provide a coating film having a smooth surface state without unevenness even without surface polishing.
[0006]
The present invention has been made in view of such circumstances, and is excellent in fluidity even in the case of a small particle diameter, and for a semiconductor manufacturing apparatus that provides a sprayed coating that is smooth and has no irregularities without being subjected to surface polishing . It is an object of the present invention to provide particles for oxide spraying, a method for producing the same, and a member for a semiconductor manufacturing apparatus using the particles.
[0007]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive investigations to achieve the above object, the inventors of the present invention have formed a fatty acid coating and / or a fatty acid compound coating on the surface of the particles for oxide spraying. However, it is excellent in fluidity, and the coating surface formed by spraying the thermal spray particles is found to be smoother and higher in purity than the conventional ones, and has excellent adhesion and corrosion resistance. In doing so, it was found that by controlling the amount of fatty acid to be used within a predetermined range, particles for oxide spraying having a good fatty acid coating and / or fatty acid compound coating were obtained, and the present invention was completed.
[0008]
That is, the present invention provides the following particles for oxide spraying for a semiconductor manufacturing apparatus, a manufacturing method thereof, and a member for a semiconductor manufacturing apparatus.
1. Particles for thermal spraying oxide used for forming the thermal spray coating of a member for a semiconductor manufacturing apparatus formed by forming a thermal spray coating on the surface of a base material, the surface of which has a fatty acid coating and / or a fatty acid compound coating, yttrium oxide , rare earth It is an oxide selected from oxide and yttrium aluminum garnet , the average particle size of the oxide is 1 to 60 μm, and the carbon concentration from the outermost surface of the oxide powder to 100 nm is 0.5 to 50 wt% Oxide spraying particles for semiconductor manufacturing equipment characterized by the above.
2. 1. The oxide spraying particle for semiconductor manufacturing apparatus according to 1, wherein the oxide is yttrium oxide.
3. A method for producing particles for thermal spraying of oxide used for forming a thermal spray coating of a member for a semiconductor manufacturing apparatus in which a thermal spray coating is formed on the surface of a base material, comprising yttrium oxide and rare earth oxide having an average particle size of 1 to 60 μm And the surface of the oxide particles selected from yttrium aluminum garnet are treated with a fatty acid and / or a fatty acid compound to form a fatty acid film on the surface of the oxide particles. Particles for thermal spraying of oxide for semiconductor manufacturing apparatus, characterized in that the carbon concentration from the outermost surface of the oxide powder to 100 nm is 0.5-50 wt% by using 0.05 to 5 wt% Manufacturing method.
4). 3. The method for producing particles for oxide spraying according to 3, wherein 0.1 to 3 wt% of fatty acid is used.
5. After stirring a mixture of oxides and fatty 0.1-2 hours, 3 or 4 method of manufacturing an oxide particles for thermal spraying of, wherein the drying at 20 to 50 ° C..
6). Method of any of the oxide particles for thermal spraying of 3-5, wherein the oxides are yttrium oxide.
7). A member for a semiconductor manufacturing apparatus, comprising: a base material; and a coating formed by spraying one or two particles for oxide spraying on the surface of the base material.
[0009]
Hereinafter, the present invention will be described in more detail.
The particles for oxide spraying according to the present invention have a fatty acid coating and / or a fatty acid compound coating on the surface.
Since such oxide spray particles have a fatty acid film and / or a fatty acid compound film on the surface, they have surface water repellency and can suppress adsorption of moisture in the atmosphere. Therefore, it is possible to prevent a decrease in powder fluidity due to adsorbed water generally found in oxide spray particles and the like, and the film serves as a lubricant and fluidity is improved. .
[0010]
Further, as a result of having the coating film, the carbon concentration on the surface becomes higher than the carbon concentration inside the particle, but the carbon concentration from the outermost surface of the oxide spraying particle to 100 nm is 0.5 to 50 wt%, particularly 1 to 30 wt. % Is preferred. This carbon concentration can be appropriately adjusted by setting the amount of fatty acid used in the range of 0.05 to 5 wt% with respect to the oxide weight in the production method described in detail later.
In addition, the said carbon concentration can be measured by analyzing and quantifying, for example, etching with XPS etc.
[0011]
As the oxide constituting the particles for thermal spraying in the present invention, one or more oxides selected from Y 2 , rare earth elements and yttrium aluminum garnet , or composite oxides of these elements can be used. In particular, it is preferable to use oxides of Y or rare earth elements such as Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, or composite oxides thereof.
The shape of the oxide is not particularly limited, and for example, a spherical shape, a square shape, or a scale shape can be used.
[0012]
Moreover, the average particle diameter of the particles for oxide spraying is not particularly limited. For example, those having a particle diameter of 0.1 to 100 μm can be suitably used. Since the particles for oxide spraying of the present invention are characterized by excellent fluidity even when the particle size is small, it is particularly preferable to use particles having an average particle size of 1 to 60 μm.
[0013]
There is no limitation in particular as a fatty acid which comprises the said fatty-acid film, For example, a C5-C20 fatty acid can be used. Considering workability and fluidity, it is preferable to use a fatty acid having 10 to 20 carbon atoms. Among these, saturated fatty acids are particularly preferable, and for example, stearic acid, lauric acid, and the like can be suitably used. These fatty acids can be used individually by 1 type or in mixture of 2 or more. Examples of the fatty acid compound include salts of the fatty acid.
It is preferable that the fatty acid does not contain an alkali metal element or an alkaline earth metal element.
[0014]
In addition, the oxide spray particles take into consideration that the coating formed by spraying the spray particles has high purity, prevents the occurrence of colored spots, and provides sufficient corrosion resistance to the sprayed member having the coating. Then, the total amount of iron group elements (Fe, Ni, Co, etc.), alkali metal elements (Na, K, etc.), and alkaline earth metal elements (Mg, Ca, etc.) is preferably 20 ppm or less in terms of oxides. .
The iron group element, alkali metal element, and alkaline earth metal element were measured by ICP spectroscopic analysis (inductively coupled high-frequency plasma spectroscopic analysis) after acid-decomposing the oxide spray particles.
[0015]
The method for producing the particles for oxide spraying is not particularly limited. (1) A method in which the raw material oxide particles are directly treated with a fatty acid to form a fatty acid film and / or a fatty acid compound film, (2) ▼ After mixing a solution obtained by dissolving a fatty acid in an organic solvent and the oxide particles, the method of forming a fatty acid film and / or a fatty acid compound film on the surface of the oxide particles by distilling off the organic solvent is used. Can do.
At this time, it is preferable to use a fatty acid in an amount of 0.05 to 5 wt%, particularly 0.1 to 3 wt% with respect to the weight of the oxide particles.
In addition, about the oxide which comprises a fatty acid and an oxide particle, the thing similar to what was described previously can be used.
[0016]
Here, if the amount of fatty acid is less than 0.05%, the fluidity of the obtained thermal spraying particles may be lowered, and the surface of the thermal spray coating using the particles may be inferior in smoothness. In the case of a small particle size of 10 μm or less, the feeder may not be applied. On the other hand, if the amount of fatty acid exceeds 5 wt%, surplus carbon remains in the coating, which may deteriorate the corrosion resistance, and carbon may remain and spots may occur on the sprayed coating.
[0017]
When employing the above method (2), the organic solvent that can be used is not particularly limited as long as it can dissolve fatty acids. For example, alcohol solvents such as methanol and ethanol, fats such as hexane, and the like. Aromatic hydrocarbon solvents such as aromatic hydrocarbon solvents and toluene can be used.
Further, the method for distilling off the organic solvent is not particularly limited, and various known solvent distilling methods can be used, for example, a method of volatilizing at room temperature to about 100 ° C., a method of distillation at normal pressure or reduced pressure Spray drying method, fluidized bed drying method and the like can be used.
[0018]
As a specific example of the method (2), an amount of fatty acid such as stearic acid in the range of 0.05 to 5 wt% with respect to the weight of the oxide particles (for example, 0.05 to 5 g) is added to ethanol. Oxide particles (for example, 100 g) are added to a solution mixed and dissolved in an organic solvent. The obtained mixed solution is stirred for 0.1 to 2 hours and then dried at 20 to 50 ° C. to distill off the organic solvent to obtain oxide spray particles having a fatty acid film and / or a fatty acid compound film on the surface. be able to.
[0019]
The thermal spray member according to the present invention includes a base material and a coating formed by spraying the above-described oxide spray particles on the surface of the base material.
Here, the substrate is not particularly limited, and metals, alloys, ceramics, glass and the like can be used. Specifically, Al, Ni, Cr, Zn, Zr, and alloys thereof, alumina, nitriding Aluminum, silicon nitride, silicon carbide, quartz glass, zirconia, and the like can be given.
[0020]
The thickness of the thermal spray coating on the substrate surface is preferably 50 to 500 μm, more preferably 150 to 300 μm. When the thickness of the coating is less than 50 μm, when a thermal spray member having the coating is used as a corrosion-resistant member, it may be necessary to replace it with a slight corrosion. On the other hand, when the thickness of the coating exceeds 500 μm, there is a possibility that peeling inside the coating tends to occur because it is too thick.
[0021]
Moreover, although it changes with uses of a thermal spray member, it is preferable that the surface roughness of a film is 60 micrometers or less, More preferably, it is 40 micrometers or less. If the surface roughness exceeds 60 μm, it may cause dust generation when the sprayed member is used. For example, when used for a plasma process member in a semiconductor manufacturing process, the plasma contact area increases. Corrosion resistance may be deteriorated, and particles may be generated due to the progress of corrosion.
That is, when the surface roughness of the coating is 60 μm or less, good corrosion resistance is obtained and particles attached to the film surface are reduced. Therefore, corrosion hardly occurs even in a corrosive gas atmosphere, and the sprayed member can be suitably used as a corrosion-resistant member.
[0022]
The thermal spray member of the present invention can be obtained by forming a film on the surface of the substrate by plasma spraying or reduced pressure plasma spraying of the above-mentioned oxide spraying particles. Here, the plasma gas is not particularly limited, and nitrogen / hydrogen, argon / hydrogen, argon / helium, argon / nitrogen, or the like can be used.
The spraying conditions and the like are not particularly limited, and may be set as appropriate according to the specific material such as the base material and oxide spray particles, the use of the obtained sprayed member, and the like.
[0023]
Also in the thermal spray member of the present invention, the total amount of the iron group element, alkali metal element, and alkaline earth metal element in the coating is preferably 20 ppm or less in terms of oxide, but this is because the total amount of each element described above is 20 ppm. This can be achieved by using the following particles for oxide spraying.
That is, when a coating is formed using thermal spraying particles in which the total amount of iron group elements, alkali metal elements, and alkaline earth metal elements is 20 ppm or more in terms of oxides, the coating is mixed with thermal spraying particles. Although only iron group elements, alkali metal elements, and alkaline earth metal elements are mixed as they are, such problems are not caused by using the above-mentioned particles for oxide spraying.
[0024]
In addition, if the total amount of each metal element in the coating of the thermal spray member is 20 ppm or less in terms of oxide, the contamination is less, so that the thermal spray member can be used without any problem for an apparatus that is required to have high purity. can do. Specifically, it can be suitably used as a member for a liquid crystal manufacturing apparatus, a member for a semiconductor manufacturing apparatus, or the like.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
[0026]
[ Reference Example 1]
100 g of aluminum oxide powder (average particle size 50 μm) is added to a solution obtained by mixing and dissolving 0.5 g of stearic acid in 200 ml of ethanol, stirred for 20 minutes, and then dried at 50 ° C. to have a stearic acid film on the surface. Oxide spray particles were obtained.
Using the measurement sample in which the obtained particles for oxide spraying were embedded in metal In, the carbon concentration from the outermost surface to 100 nm was measured by XPS (AXIS-HSi, manufactured by Shimadzu KRATOS). Specifically, the measurement area of the sample is 200 × 600 μm area, Mg is used as the irradiation X-ray, and the carbon concentration up to 100 μm in depth is obtained while cutting the measurement area of the 200 × 600 μm area with Ar gas from the outermost surface. The average carbon concentration from the outermost surface to 100 μm was calculated. The results are shown in Table 1.
Moreover, about the obtained particle | grains for oxide spraying, fluidity | liquidity was evaluated by the method based on JIS-Z2504-1979. Specifically, the bottom of the funnel is plugged, 50 g of the oxide spray particles are put into the funnel, the bottom plug is removed, and at the same time, vibration is applied at a frequency of 60 Hz and an amplitude of 0.4 mm. The number of seconds required to flow down was measured at n = 5. Table 1 shows the average value of the measurement results.
[0027]
[Example 1 ]
100 g of yttrium oxide granulated powder (average particle size 32 μm) is added to a solution in which 2.0 g of stearic acid is mixed and dissolved in 200 ml of ethanol, stirred for 20 minutes, and then dried at 50 ° C. to form a stearic acid coating on the surface. Oxide spray particles having the following were obtained.
The obtained oxide spray particles were subjected to carbon concentration measurement and fluidity test in the same manner as in Reference Example 1. The results are shown in Table 1.
[0028]
[Example 2 ]
Oxide spray particles having a stearic acid coating on the surface were obtained in the same manner as in Example 1 except that 0.2 g of stearic acid was used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0029]
[Example 3 ]
Oxide spray particles having a stearic acid coating on the surface were obtained in the same manner as in Example 1 except that 0.02 g of stearic acid was used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0030]
[Example 4 ]
100 g of spherical powder of yttrium oxide (average particle size 5 μm) is added to a solution in which 2.0 g of stearic acid is mixed and dissolved in 200 ml of ethanol, stirred for 20 minutes, and then dried at 50 ° C. to form a stearic acid film on the surface. Particles for oxide spraying were obtained.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0031]
[Example 5 ]
Oxide spray particles having a stearic acid coating on the surface were obtained in the same manner as in Example 4 except that 0.2 g of stearic acid was used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0032]
[Example 6 ]
Oxide spray particles having a stearic acid coating on the surface were obtained in the same manner as in Example 4 except that 0.02 g of stearic acid was used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0033]
[Example 7]
Oxide spray particles were obtained in the same manner as in Reference Example 1 except that 100 g of granulated powder (average particle size 40 μm) of yttrium aluminum garnet (YAG) was used.
The obtained oxide spray particles were subjected to carbon concentration measurement and fluidity test in the same manner as in Reference Example 1. The results are shown in Table 1.
[0034]
[Example 8 ]
Oxide spray particles were obtained in the same manner as in Reference Example 1 except that 1.0 g of stearic acid and 50 g of yttrium oxide ultrafine powder (average particle size 0.5 μm) were used.
The obtained oxide spray particles were subjected to a fluidity test in the same manner as in Reference Example 1 except that the amount of particles used was 10 g and the vibration amplitude was 0.8 mm. The results are shown in Table 1.
[0035]
[Comparative Example 1]
Oxide spray particles were obtained in the same manner as in Reference Example 1 except that stearic acid was not used.
The obtained oxide spray particles were subjected to carbon concentration measurement and fluidity test in the same manner as in Reference Example 1. The results are shown in Table 1.
[0036]
[Comparative Example 2]
Oxide spray particles were obtained in the same manner as in Example 1 except that stearic acid was not used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0037]
[Comparative Example 3]
Oxide spray particles were obtained in the same manner as in Example 4 except that stearic acid was not used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0038]
[Comparative Example 4]
Oxide spray particles were obtained in the same manner as in Example 7 except that stearic acid was not used.
The obtained oxide spray particles were subjected to the same fluidity test as in Reference Example 1. The results are shown in Table 1.
[0039]
[Comparative Example 5]
Oxide spray particles were obtained in the same manner as in Example 8 except that stearic acid was not used.
The obtained oxide spray particles were subjected to the same fluidity test as in Example 8 . The results are shown in Table 1.
[0040]
[Table 1]

[0041]
As shown in Table 1, each of the particles for oxide spraying obtained in Examples 1 to 8 has a stearic acid coating on the surface thereof, and thus has excellent surface smoothness and corresponds to each. It can be seen that the fluidity is superior to the particles of the comparative example. In particular, it can be seen that even in the case of an ultrafine powder having an average particle size of 0.5 μm, good fluidity is exhibited (see Example 8 ).
[0042]
[Example 9 ]
Using the particles for oxide spraying obtained in Example 5 , plasma spraying of the particles was performed on an aluminum substrate using argon / hydrogen gas to form a sprayed coating having a thickness of 215 μm.
When the surface roughness Ra of the obtained coating film was measured by a method based on JIS B0601, it was very smooth as 5 μm.
[0043]
【The invention's effect】
As described above, according to the present invention, since the particles are oxide spray particles having a fatty acid coating and / or a fatty acid compound coating on the surface, the fluidity is good even when the particle size is small. can do. Therefore, by spraying the particles for thermal spraying on the base material, it is possible to obtain a sprayed coating that is smooth and has no unevenness without performing surface polishing.

Claims (7)

Particles for thermal spraying oxide used for forming the thermal spray coating of a member for a semiconductor manufacturing apparatus formed by forming a thermal spray coating on the surface of a base material, the surface of which has a fatty acid coating and / or a fatty acid compound coating, yttrium oxide , rare earth It is an oxide selected from oxide and yttrium aluminum garnet , the average particle size of the oxide is 1 to 60 μm, and the carbon concentration from the outermost surface of the oxide powder to 100 nm is 0.5 to 50 wt% Particles for oxide spraying for semiconductor manufacturing equipment characterized by   The oxide spray particles for a semiconductor manufacturing apparatus according to claim 1, wherein the oxide is yttrium oxide. A method for producing particles for thermal spraying oxide used for forming a thermal spray coating of a member for a semiconductor manufacturing apparatus in which a thermal spray coating is formed on the surface of a base material, comprising yttrium oxide and rare earth oxide having an average particle size of 1 to 60 μm The surface of the oxide particles selected from yttrium aluminum garnet is treated with a fatty acid and / or a fatty acid compound to form a fatty acid film on the surface of the oxide particles. Particles for thermal spraying of oxide for semiconductor manufacturing equipment, characterized in that the carbon concentration from the outermost surface of the oxide powder to 100 nm is 0.5 to 50 wt% by using 0.05 to 5 wt% Manufacturing method.   4. The method for producing particles for oxide spraying according to claim 3, wherein 0.1 to 3 wt% of fatty acid is used. Mixed oxides with fatty acids, after stirring for 0.1 to 2 hours, The process according to claim 3 or 4 oxide particles for thermal spraying of, wherein the drying at 20 to 50 ° C.. Method of manufacturing an oxide particles for thermal spraying according to any one of claims 3-5, wherein the oxides are yttrium oxide.   A member for a semiconductor manufacturing apparatus, comprising: a base material; and a coating formed by spraying the oxide spraying particles according to claim 1 on the surface of the base material.