JP4604640B2 - Vacuum device parts, manufacturing method thereof, and apparatus using the same - Google Patents

Description

  The present invention relates to a vacuum apparatus component used in a film forming apparatus and a plasma processing apparatus (plasma etching apparatus, plasma cleaning apparatus) in manufacturing semiconductors and the like. The vacuum device component of the present invention prevents dust generation due to peeling of a film-like substance adhering to the component in the device during film formation and plasma treatment, and remarkably increases the durability of the component against the plasma generated in the device. It is to improve.

  In a film forming apparatus or a plasma processing apparatus for forming a product substrate such as a semiconductor or performing plasma processing, a film-like substance adheres to parts used in the apparatus. It is known that when film formation and plasma treatment are continuously performed in such a state, the attached film-like substances become thick and eventually peel off to generate dust in the apparatus, contaminating the apparatus and the product substrate. ing. Further, in the film forming apparatus and the plasma processing apparatus, plasma is generated in the apparatus, but the plasma corrodes the surface of the part, and there is a problem of deterioration of the part and accompanying dust generation. These phenomena are a major problem because they cause a reduction in product substrate quality and yield.

  2. Description of the Related Art Conventionally, as a method for reducing dust generation due to peeling of a film-like deposit, a method is known in which the surface of a component is subjected to a blasting process so that the surface becomes a satin finish to increase the adhesion of the film-like substance. For example, it is known that blasting is applied to improve the adhesion of flying particles to the inner surface of a quartz bell jar, and blasting is applied to the surface to improve the adhesion of film-like substances deposited on a ceramic cylinder. (For example, refer to Patent Document 1). However, a rough surface obtained by blasting quartz glass has a portion with weak strength or a piece that is cracked and peeled off, and there is a problem that a film-like substance is difficult to adhere or is easily peeled off.

  On the other hand, a method of performing an etching treatment with a hydrofluoric acid solution after blasting quartz glass is also disclosed (for example, see Patent Document 2). However, the surface of the blasted quartz glass etched with a hydrofluoric acid solution has a place where the film-like substance is likely to adhere and a place where the film-like substance is not likely to adhere. There was a problem.

  In order to improve the adhesion of film-like substances to parts, the surface of the quartz substrate is blasted and then the plasma gun is controlled by controlling the distance between the substrate etched with an acid containing at least hydrofluoric acid and the plasma gun. It is also known that plasma spraying is performed by adding hydrogen to a gas (see, for example, Patent Document 3). However, even when such a method is used, a certain degree of improvement in the adhesion of the film-like substance can be obtained, but a sufficient effect that can withstand long-term use has not been expected.

US Pat. No. 5,460,689 (column 3) Japanese Patent Publication No. 8-104541 (Claims) Japanese Patent Publication No. 2003-212598 (Example 6)

  For parts used in vacuum devices, there has always been a demand from the market for a technology that can further improve the adhesion of a film-like substance and can continuously perform film formation or plasma treatment for a longer period of time. Therefore, the present invention is superior in that the adhesion of the film-like substance is higher than conventional and can be used continuously for a long time in the parts of the vacuum apparatus used in the deposition of the product substrate such as semiconductor and the plasma processing apparatus. Parts are provided.

  As a result of intensive studies in view of the above situation, the present inventor is a component for a vacuum apparatus in which a ceramic sprayed film is formed on a substrate, and has a diameter of 0.1 to 5 μm on the surface of the sprayed film. In the vacuum device parts in which the protruding particles in which the particles are aggregated are present, the adhesion of the film-like substance to be deposited is found to be further superior to the conventional one, and the present invention has been completed. (First invention). Also, a vacuum device part in which a metal sprayed film is formed on a substrate, wherein projecting particles in which particles having a diameter of 0.1 to 10 μm are gathered are dispersed on the surface of the sprayed film. Has found that the adhesion of the deposited film-like substance is further superior to the conventional one, and has completed the present invention (second invention).

Moreover, it is the component of the vacuum device which formed the ceramic and / or metal sprayed film on the base material, Comprising: On the surface of this sprayed film, width 10-300 micrometers, height 4-600 micrometers, width (W) and height (H ) In the range of 20 / mm ^{2 to} 20000 / mm ^{2, and the} thermal spray film has a porosity of 10% to 40 It was found that the adhesion of the film-like substance to be deposited is even better than the conventional (part 3).

  Further, such protruding particles are formed by causing the sprayed powder to collide with the base material in a semi-molten state, or by forming the sprayed powder so that a material having a low melting point wraps a material having a high melting point. It has been found that a material having a low melting point can be completely melted and a material having a high melting point is impinged on the substrate in an unmelted or semi-molten state. In addition, in the film forming apparatus, plasma etching apparatus, and plasma cleaning apparatus using the vacuum apparatus of the present invention, it has been found that generation of particles is prevented, and the present invention has been completed.

  The present invention will be described in detail below.

  Subsequently, the third invention will be described. The vacuum device component according to the third invention is characterized in that a ceramic and / or metal sprayed film is formed on a substrate, and projecting particles are present on the surface of the sprayed film.

  An example of the protruding particles of the third invention is shown in FIG. The present sprayed film is plasma sprayed using alumina as a raw material. The protruding particles of the present invention have a mountain shape and rounded corners, and preferably have no sharp corners. This is because when the shape of the protrusion is an acute angle, the electric field in the plasma concentrates on the acute angle portion and is selectively etched when used for plasma processing, which causes generation of particles. In the present invention, these protrusions may be independent from each other or may be formed by overlapping several particles. Preferably, in the case of a ceramic sprayed film, the protruding particles are formed by aggregation of particles having a diameter of 0.1 to 5 μm, and in the case of a metal sprayed film, the protruding particles are particles having a diameter of 0.1 to 10 μm. Are formed by aggregation.

  FIG. 6 shows an example of measuring the width and height of the protruding particles of the third invention. For the measurement, an apparatus capable of simultaneously observing an image and measuring the width and height, such as a laser confocal microscope and a scanning electron microscope, can be used. After performing the image observation as shown in FIG. 5, a straight line is drawn so as to cover the top of the protruding particles, and the height profile under the straight line is plotted. A background line of the protruding particles shown on this profile is drawn to obtain the width. Next, the height is obtained by calculating the distance between the line and the peak top point of the protrusion. In this way, the width 22 and height 23 of each protruding particle are calculated, and the ratio of height to width is further calculated. For the measurement of protruding particles, several tens to hundreds of times of photographs are taken, 100 protruding particles are arbitrarily extracted, and values of width and height can be obtained.

  A method for measuring the porosity of the third invention will be described. The porosity can be measured by polishing the cross section of the sprayed film to finish it in a mirror state and taking a photograph using a scanning electron microscope or the like. At this time, in order to make the grain boundary clear and to easily measure the porosity, the cross section of the sprayed film may be etched. Further, when polishing or the like enters the pores during polishing, the pores may be cleaned using a chemical solution or the like. It is possible to calculate the porosity by calculating the area of the entire sprayed film and the area of the hole portion from a photographic image of several tens to several hundred times, and dividing the area of the hole by the entire area. At this time, a plurality of photographs are taken so that 100 holes are extracted as the number of holes.

  The size of each protruding particle of the third invention is preferably in the range of 10 to 300 μm in width and 4 to 600 μm in height. In the case of a crushed protrusion having a width of 10 μm and a height of less than 4 μm, the retention of the deposit is reduced. On the other hand, even if the width exceeds 300 μm and the height exceeds 600 μm, the interval between the projections and depressions becomes too long, and the retention of the adhered film is lowered, and particles are easily generated. From the above, the size of each protruding particle is 15 to 200 μm in width and 10 to 400 μm in height, more preferably in the range of 20 to 100 μm in width and 15 to 200 μm in height.

  The ratio (H / W) of the width (W) to the height (H) of the protruding particles is preferably 0.4 or more for the reason described above. Moreover, as an average value of ratio (H / W) of width (W) and height (H), it is preferable that it is 0.5-2.0. If it is less than 0.4, the adhesive force is weak because it is too crushed, and if it is larger than 2.0, the adhesive force is weak because it is too sharp. For these reasons, the ratio of width to height is more preferably 0.8 to 1.5 as an average value.

The number of the protruding particles of the third invention is in the range of 20 to 20000 per 1 mm ² unit area, particularly preferably 200 to 10,000 / mm ² . If it is less than 20 pieces / mm ² , the retention of adhered matter is lowered, and if it exceeds 20000 pieces / mm ² , the protruding particles are overlapped, so that the effect as protrusions is reduced and particles are easily generated.

  The porosity of the sprayed film is preferably 10 to 40%. If it is larger than 40%, the bonding force of the particles inside the sprayed film is weak and the sprayed film is easily peeled off, resulting in generation of particles. On the other hand, if it is less than 10%, the sprayed film is difficult to peel off, but the shape of the protruding particles tends to be crushed, so that the retention of the adhered film is lowered. For these reasons, the porosity of the sprayed film is more preferably 15 to 35%.

  At this time, another sprayed film having a different porosity may be formed under the sprayed film, that is, between the base material and the sprayed film having a porosity of 10 to 40%. The intermediate sprayed film has a lower porosity than the upper sprayed film because the sprayed film is less likely to peel off, and is preferably 3% or more and less than 10%.

  In the first invention, the second invention, and the third invention, the thickness of the sprayed film is not particularly limited, but is preferably 50 to 1000 μm. When the thickness is less than 50 μm, the sprayed film containing the protruding particles may not cover the unevenness of the base material, and when the thickness exceeds 1000 μm, the sprayed film itself may be stressed and easily peeled off. For these reasons, the film thickness is more preferably 70 to 500 μm.

  In the first invention, the second invention, and the third invention, the sprayed film can deposit at least a film-like substance on a part for a vacuum apparatus used in a film formation of a product substrate such as a semiconductor or a sputtering target or a plasma processing apparatus. What is necessary is just to form the part with the said film thickness, for example with respect to the part which has property.

  The base material in the first invention, the second invention, and the third invention can be any material such as glass, aluminum, stainless steel, titanium and other metals, alumina, zirconia, mullite and other ceramics. The protruding particles and the base material may be the same material, but may be different materials. An undercoat layer may be formed on the base material so that the sprayed powder is well melted on the base material and the protruding particles are easily formed uniformly. The type, material, and film thickness of the base are not particularly limited. For example, a material of the same material as the base material is formed by a plasma spraying method, or a Ni—Cr alloy layer is formed by a method such as sputtering or electrolytic plating. May be.

  The metal or ceramic material constituting the protruding particles of the third invention may be any material such as Al, Ti, Cu, Mo, W, etc. for metals, and alumina, zirconia, titania, spinel, zircon, etc. for ceramics. The material having a higher melting point is easier to control the ratio of height to width during the thermal spraying process.

  Another projecting particle part according to the third aspect of the present invention is such that the projecting particles have a structure in which a material having a low melting point wraps a material having a high melting point, and thus can have a mountain shape. FIG. 7 shows a schematic diagram. Projected particles 33 having a structure in which a material 32 having a low melting point wraps a material 31 having a high melting point are formed on the substrate 30. The difference in melting point between the material 32 having a low melting point and the material 31 having a high melting point is preferably 400 ° C. or higher, more preferably 1000 ° C. or higher.

  By doing in this way, since the height of the protruding particle 33 can be controlled by the height of the material 31 having a high melting point, the protruding particle can be formed with higher reproducibility. Examples of a combination of a material having a low melting point and a material having a high melting point include Al and Mo, Cu and W in the case of metal, and alumina and zirconia, cordierite and alumina in the case of ceramic. Further, a metal and ceramic may be combined, or a combination such as Al and boron nitride, Co and tungsten carbide may be used.

  Furthermore, the manufacturing method of the vacuum device component of the first invention will be described.

  What is necessary is just to add the sintering adjuvant which suppresses a grain growth in the raw material powder used as a ceramic spraying material for forming a particle | grain with a diameter of 0.1-5 micrometers. By including a sintering aid, it is possible to suppress abnormal grain growth of the particulate projections in the sprayed film, and furthermore, the projection-like particles formed by agglomerating spherical particles are also abnormal. Since the grain growth can be suppressed, a sprayed film having a uniform structure can be obtained.

  As a sintering aid, what is known as a sintering aid for ceramics used as a raw material powder can be used without any particular limitation. For example, when zirconia is used as the raw material powder, 1 to 20% by weight of magnesium oxide, yttrium oxide, cerium oxide or the like may be added as a sintering aid. When alumina is used as the raw material powder, it is oxidized. Magnesium or the like may be added at 0.05 to 10% by weight.

  In order to form the ceramic sprayed film of the first invention, it is particularly preferable to use a high-purity raw material. In particular, it is preferable to use a high-purity product of 99% by weight or more, more preferably 99.9% by weight or more. The thermal spraying raw material powder can be produced by an electromelting pulverization method, a granulation method, or the like, and a spherical powder obtained by sintering granulated granules and densifying them to a relative density of 80% or more may be used.

  Furthermore, the primary particles of the raw material powder preferably have an average particle size of 0.1 to 3 μm, and more preferably 0.2 to 2 μm. The raw material powder having such a primary particle diameter improves the uniformity of the secondary particles formed by agglomeration of the raw material powder, and enables generation of protruding particles formed by aggregation of the particle-shaped protrusions of the present invention. The average particle size of the secondary particles is preferably 5 to 100 μm and more preferably 10 to 60 μm for the reasons described above.

  The spraying method is not particularly limited, and can be selected from flame spraying, arc spraying, explosion spraying, plasma spraying, and the like. For example, when plasma spraying is selected, it is usually performed in argon gas, but hydrogen may be added to argon. By adding hydrogen, the temperature of the plasma flame can be increased, and in particular, a decrease in the plasma temperature at the tip can be suppressed. The addition of hydrogen is preferably in the range of 10 to 50% by volume, particularly 20 to 40% by volume.

  In the case of forming a ceramic sprayed film by plasma spraying, it is preferable to spray the distance between the substrate and the plasma spray gun in the range of 60 mm to 130 mm to manufacture the sprayed film. If the distance between the plasma gun and the ceramic spray coating substrate is shorter than 60 mm, the particles that are plasma sprayed on the substrate are remelted, and thus it becomes difficult to obtain the protruding particles that are the requirements of the invention. On the other hand, if the length is longer than 130 mm, the protruding particles are well dissolved, the adhesion of the sprayed film to the substrate may be lowered, and the adhesion of the film-like substance may be lowered.

  You may heat-process at 1000-1600 degreeC after formation of a ceramic sprayed film. By performing the heat treatment at 1000 ° C. or higher, crystal defects of the ceramic sprayed coating are reduced, and the acid resistance of the ceramic sprayed coating is improved. When the acid resistance of the ceramic sprayed coating is improved, the ceramic sprayed coating itself is not dissolved when the film deposit on the component is removed by acid etching after the vacuum device component is used in a film forming or plasma processing device. The parts can be used over and over again. The reason why the effect of the heat treatment is manifested is that, for example, when the ceramic sprayed film is alumina, the content of γ-alumina in the sprayed film is reduced by performing the heat treatment at 1000 ° C. or higher. Even in the case of other than alumina, the same effect can be obtained by reducing the lattice defects of the crystal. On the other hand, if the heat treatment temperature exceeds 1600 ° C., there is a problem such as cracking of parts, which is not preferable. The heat treatment time is in the range of several minutes to 10 hours and 30 minutes to 3 hours, and the heat treatment atmosphere is preferably carried out in the air or in a pure oxygen atmosphere.

  Next, a manufacturing method of the vacuum device component of the second invention will be described.

  The raw material powder used as a metal spray material for forming particles having a diameter of 0.1 to 10 μm can be used without particular limitation, such as pure metal powder and alloy powder, but an auxiliary agent for suppressing grain growth. It is preferable to add. By including an auxiliary material, abnormal grain growth of particulate projections in the sprayed film can be suppressed, and abnormal grain growth is also possible for projection grains composed of spherical particles. Therefore, it is possible to obtain a sprayed film having a uniform structure.

  As an auxiliary material, it can use without specifically limiting with respect to the metal used as raw material powder. For example, when aluminum is used as the raw material powder, silicon, copper, titanium, nickel, iron, or the like may be added as an auxiliary material in an amount of 1 to 50% by weight.

  In order to form the metal sprayed film of the present invention, it is particularly preferable to use a high-purity raw material. In particular, it is preferable to use a high-purity product of 99% by weight or more, more preferably 99.9% by weight or more. The thermal spray raw material powder can be manufactured by an atomizing method, an electromelting pulverization method, a granulation method, or the like.

  Further, the primary particles of the raw material powder preferably have an average particle size of 0.1 to 10 μm, and more preferably 0.2 to 5 μm. The raw material powder having such a primary particle diameter improves the uniformity of the secondary particles formed by agglomeration of the raw material powder, and enables generation of protruding particles formed by aggregation of the particle-shaped protrusions of the present invention. The average particle size of the secondary particles is preferably 5 to 120 μm and more preferably 10 to 100 μm for the reasons described above.

  The spraying method is not particularly limited, and can be selected from flame spraying, arc spraying, explosion spraying, plasma spraying, and the like. For example, when plasma spraying is selected, it is preferable to form a film at a high speed and with a low frame temperature. By forming the film in this way, only the periphery of the metal powder is slightly melted, and plastic deformation is caused when the metal powder reaches the base material, so that the film can be efficiently formed.

  Next, a method for manufacturing the protruding particle component according to the third invention will be described.

  By spraying the sprayed powder onto the substrate in a semi-molten state at the time of thermal spraying, mountain-shaped protruding particles can be produced. Examples of the spraying method used include plasma spraying method and high-speed flame spraying method. As shown in FIG. 7, by adjusting the spraying powder in a semi-molten state, that is, spraying power, spraying distance, high-speed flame heating power, etc. Further, the vicinity of the center of the powder is unmelted (43) and the periphery is in a molten state (44). When ceramic powder is used as the thermal spraying powder, the thermal spraying power can be lowered to the base material in a semi-molten state by lowering the thermal spraying power using a plasma spraying method. In the case of using a metal powder as the thermal spraying powder, the thermal spraying powder can reach the substrate in a semi-molten state by the same method, but it is preferable to use a plasma spraying method or a high-speed flame spraying method with a high gas flow rate. . By doing so, it becomes possible to cause the semi-molten particles to collide with the substrate at a high speed, and a film having good adhesion can be obtained by plastic deformation. In order to easily melt only the periphery of the sprayed powder, and to form surface protrusions with good adhesion and a large width to height ratio, the shape of the sprayed powder is preferably spherical, for example, gas atomization Powder can be used.

  As another method for producing the protruding particle component of the present invention, the thermal spray powder is formed so that the material having a low melting point wraps the material having a high melting point, and the material having a low melting point is completely melted at the time of thermal spraying. The material is impinged on the substrate in an unmelted or semi-molten state.

  In the present invention, it is preferable to perform spraying twice or more in order to form a sprayed film having a sufficient amount of protruding particles on the substrate.

  Also, the spraying conditions for making the molten powder into a semi-molten state, or the material for melting a material with a low melting point completely, and the material with a high melting point into an unmelted or semi-molten state depend on the spraying powder used. However, it is difficult to define it uniquely, but those skilled in the art can easily determine it by performing a plurality of thermal spray tests.

  The particle size (secondary particle size) of the thermal spray powder used for the production of the particulate protrusions is preferably 5 to 100 μm in average particle size, and more preferably 10 to 60 μm in average particle size. If the average particle size is less than 5 μm, it is difficult to uniformly introduce the raw material into the frame because the raw material powder itself does not have sufficient fluidity. On the other hand, when the average particle diameter exceeds 100 μm, the sprayed particles are not uniformly melted, and the adhesion of the obtained protruding particles to the substrate tends to be deteriorated. Further, the size of the particles used for thermal spraying is as uniform as possible, so that the shape of the protruding particles can be made uniform and the retention of the adhesion film can be improved.

  The vacuum device parts according to the first, second, or third invention obtained by the above-described methods are further subjected to ultrasonic cleaning using ultrapure water after forming a sprayed film, and then dried. Just do it. Prior to the final ultrasonic cleaning, the thermal spray coating surface may be cleaned by immersing the vacuum device parts in a weak acid such as nitric acid.

  Furthermore, the present invention proposes a film forming apparatus using the vacuum device parts described above. The film forming method of the film forming apparatus in the present invention is not limited, but examples thereof include a CVD method (Chemical Vapor Deposition), a sputtering method, and the like. As a method of using the vacuum device component, it is preferable to use it as a component used for a portion where a film-like substance is deposited other than a product substrate on which film formation is performed in the device. For example, it can be used as a bell jar or a shield. In particular, in tungsten and titanium CVD film deposition equipment and titanium nitride sputtering equipment, if the vacuum device parts of the present invention are used for bell jars and shields, there is no cracking or peeling due to the difference in thermal expansion coefficient between the base material and the protruding particles. Thus, there is no generation of particles due to separation of the attached film-like substance, and the apparatus can be used for continuous film formation for a long time.

  Further, the present invention proposes a plasma etching apparatus and a plasma cleaning apparatus using the vacuum device parts described above. It is preferable to use the vacuum device component in a site where the film-like substance adheres in these devices, or a site where the surface of the component is easily peeled by contact with plasma, for example, as a ring-shaped clamp component or shield. Use.

  A plasma etching apparatus or a plasma cleaning apparatus is an apparatus that irradiates a product installed in the apparatus with plasma and peels or cleans the surface of the product.

  Here, the part where the film is deposited in the plasma etching apparatus is the part where the peeled material scatters and adheres to the apparatus when the product surface is irradiated with plasma in the plasma etching apparatus and the product surface is peeled off. It is. The portion etched by plasma in the present invention refers to a portion etched by contact with plasma in a portion other than the product in the apparatus. Originally, these devices irradiate the product with plasma and peel off the surface of the product. However, it is difficult to selectively irradiate only the product with the plasma. The plasma comes into contact and the surface of the part is peeled off. If the component of the present invention is used for such a part, it is difficult to perform etching by plasma and the generation of particles is small.

  Next, the part where the film is deposited in the plasma cleaning device is the device in which plasma is irradiated to the product in the plasma cleaning device and reverse sputtering, that is, when the product surface is cleaned, the material removed by the cleaning is scattered. It is the part that adheres inside. Here, in both the plasma cleaning apparatus and the plasma etching apparatus, the principle of peeling the product surface with plasma is basically the same. The portion reversely sputtered by plasma cleaning in the present invention refers to a portion that is reverse sputtered (cleaned by etching) when plasma comes into contact with a part other than the product. Originally, these devices are intended to clean the product surface by irradiating the product with plasma, but it is difficult to selectively irradiate only the product with the plasma. The plasma comes into contact and the surface of the part is also cleaned.

  The present invention also proposes a sputtering target on which a sprayed film composed of the above-mentioned protruding particles is formed as a vacuum device component. Thus, when the sputtered particles fly on the target or the backing plate, the sputtered particles (re-deposited powder) that cause the generation of particles can be efficiently attached on the surface of the sprayed film. The material for forming the sprayed film is not particularly limited, but it is preferable to use the same material as the target material in order to prevent contamination in the sputtering apparatus.

  In the sputtering target, the portion where the sprayed film of the present invention is formed is preferably a portion (non-erosion portion) where the target surface is not sputtered. At this time, the sprayed coating of the present invention can be applied to the entire surface or a part of the non-erosion portion in accordance with the amount of redeposited powder generated. When the redeposited powder is generated not only on the target but also on the backing plate, the sprayed film of the present invention may be formed on the surface of the backing plate. When forming a sprayed film on the backing plate, the material on which the sprayed film is formed is not particularly limited. For example, powder such as copper, aluminum, and titanium can be used for the backing plate made of oxygen-free copper. Furthermore, when the redeposited powder is also generated on the side surface portion of the target or the backing plate, the sprayed film of the present invention may be applied to the side surface portion according to the generation amount.

  The vacuum device parts of the present invention have better adhesion of film-like substances than conventional parts, so when used in film-forming devices and pre-cleaning devices, product contamination due to dust generation due to peeling of the film-like substances It can be used continuously for a long time.

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

Example 1
The inner surface of the quartz bell jar was blasted with white alumina grit WA # 60 at a pressure of 0.5 MPa, ultrasonically cleaned with pure water, and dried in an oven. Thereafter, a zirconia sprayed film was formed on the inner surface of the quartz bell jar by plasma spraying with a flow ratio of Ar and H ₂ of 80:20 and an input power of 35 kW. As a raw material powder, stabilized zirconia granule powder (primary average particle size 0.2 μm, average particle size 50 μm, purity: 99.9%) to which 5 wt% yttrium oxide (purity: 99.9%) was added was used. used. The distance between the plasma gun and the quartz bell jar was 70 mm. After spraying, immersed in a 5% by weight nitric acid aqueous solution maintained at a temperature of 40 ° C. for 1 hour, ultrasonically cleaned with ultrapure water, dried in a clean oven, and a quartz bell jar whose ceramic sprayed coating is partially stabilized zirconia completed.

A zirconia sprayed film was produced on a 5-inch square quartz substrate under the same conditions as the product bell jar. When a sample was cut out from the substrate and observed by SEM on the surface, the presence of protruding particles composed of fine spherical particles in the range of 0.2 to 4.0 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 200 times, the average size was 20 μm. Further, when the number of protruding particles measured from 10 photographs taken at 200 times was measured, the average number was 950 / mm ² .

  The quartz bell jar manufactured by the method described above was used by being attached to a pre-cleaning apparatus. Even after 220 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 2
In Example 1, a quartz bell jar product and a 5-inch square zirconia sprayed film were manufactured under the same conditions as in Example 1 except that the distance between the plasma gun and the quartz bell jar was 120 mm. When a sample was cut out from the substrate and observed by SEM on the surface, the presence of protruding particles composed of fine spherical particles in the range of 0.2 to 3.6 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 200 times, the average size was 32 μm. Furthermore, when the number of protruding particles measured from 10 photographs taken at 200 times was measured, the average number was 400 / mm ² .

  The quartz bell jar manufactured by the method described above was used by being attached to a pre-cleaning apparatus. Even after 250 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 3
The inner surface of the quartz bell jar was blasted with white alumina grit WA # 60 at a pressure of 0.5 MPa, ultrasonically cleaned with pure water, and dried in an oven. Thereafter, an alumina sprayed film was formed on the inner surface of the quartz bell jar by plasma spraying with a flow ratio of Ar and H ₂ of 75:25, a distance between the plasma gun and the quartz glass substrate of 65 mm, and an input power of 35 kW. For the plasma spraying, alumina granule powder (primary average particle size 0.5 μm, average particle size 25 μm, purity: 99.9%) to which 1% by weight of magnesia (purity: 99.9%) was added was used. After spraying, the quartz bell jar was completed by ultrasonic cleaning with ultra pure water and drying in a clean oven.

A magnesia-added alumina sprayed film was produced on a 5-inch square quartz substrate under the same conditions as the product bell jar. When a sample was cut out from the substrate and observed on the surface by SEM, the presence of protruding particles composed of fine spherical particles in the range of 0.5 to 3.5 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 150 times, the average size was 16 μm. Furthermore, when the number of protruding particles measured from 10 photographs taken at 150 times was measured, the average number was 1080 / mm ² .

  The quartz bell jar manufactured by the method described above was used by being attached to a CVD film forming apparatus. Even after 150 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 4
In Example 3, a quartz bell jar product and a 5-inch square magnesia-added alumina sprayed film were produced under the same conditions as in Example 3 except that the distance between the plasma gun and the quartz bell jar was 125 mm. When a sample was cut out from the substrate and observed on the surface by SEM, the presence of protruding particles composed of fine spherical particles in the range of 0.5 to 3.9 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 150 times, the average size was 22 μm. Further, when the number of protruding particles measured from 10 photographs taken at 150 times was measured, the average number was 860 particles / mm ² .

  The quartz bell jar manufactured by the method described above was used by being attached to a CVD film forming apparatus. Even after 180 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 5
The inner surface of the stainless steel donut ring was blasted with white alumina grit WA # 60 at a pressure of 0.5 MPa, ultrasonically washed with pure water, and dried in an oven. Thereafter, the inner surface of the donut ring, using the N ₂ gas as the plasma gas, 75 mm distance of the plasma gun and stainless steel substrate, input power to form a yttria sprayed film by plasma spraying as 40 kW. The raw material powder is 99.9% pure yttria granule powder (primary average particle size 0.3 μm, average particle size 35 μm) and 99.9% pure lanthanum oxide granule powder (primary average particle size 0.3 μm, average particle size 30 μm). ) Was added at 15% by weight. After spraying, it was ultrasonically cleaned with ultrapure water and dried in a clean oven to complete a sputtering shield in which the ceramic sprayed film was yttria-lanthanum oxide.

A yttria-lanthanum oxide sprayed film was produced on a 5-inch square stainless steel substrate under the same conditions as the sputtering shield. When the sample was cut out from the base material and surface SEM observation was carried out, the presence of protruding particles composed of fine spherical particles in the range of 0.3 to 3.2 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 100 times, the average size was 12 μm. Furthermore, when the number of protruding particles measured from 10 photographs taken at 100 times was measured, the average number was 2200 / mm ² .

  The shield manufactured by the method described above was used by being attached to a sputtering apparatus. Even after 140 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 6
In Example 5, a shield product and a 5-inch square yttria-lanthanum oxide sprayed film were manufactured under the same conditions as in Example 5 except that the distance between the plasma gun and the donut-shaped ring was 115 mm. When a sample was cut out from the substrate and observed by SEM on the surface, the presence of protruding particles composed of fine spherical particles in the range of 0.3 to 3.4 μm was confirmed. When 100 protruding particles were arbitrarily extracted from an SEM photograph taken at 100 times, the average size was 14 μm. Further, when the number of protruding particles measured from 10 photographs taken at 100 times was measured, the average number was 1600 / mm ² .

  The shield manufactured by the method described above was used by being attached to a sputtering apparatus. Even after 160 hours had passed since the start of use, particles due to peeling of the film-like substance were not collected inside the apparatus.

Example 7
In Example 5, a shield product and a 5-inch square yttria-lanthanum oxide sprayed film were manufactured under the same conditions as in Example 5 except that the distance between the plasma gun and the donut-shaped ring was 180 mm. When the sample was cut out from the base material and surface SEM observation was performed, the presence of protruding particles composed of fine spherical particles in the range of 0.3 to 4.8 μm was confirmed. When 100 protruding particles were arbitrarily extracted from the SEM photograph taken at 100 times, the average size was 25 μm. Furthermore, when the number of protruding particles measured from 10 photographs taken at a magnification of 100 was measured, the average number was 300 / mm ² .

  The shield manufactured by the method described above was used by being attached to a sputtering apparatus. After 100 hours had elapsed from the start of use, it was observed that the film-like substance was about to peel off inside the apparatus.

Comparative Example 1
The inner surface of the quartz bell jar was blasted with white alumina grit WA # 60 at a pressure of 0.5 MPa, ultrasonically cleaned with pure water, and dried in an oven. Thereafter, an alumina sprayed film was formed on the inner surface of the quartz bell jar by plasma spraying with a flow ratio of Ar and H ₂ of 70:30 and an input power of 40 kW. As the raw material powder, an alumina granule powder (primary average particle size 0.5 μm, average particle size 45 μm) having a purity of 99.99% was used. The distance between the plasma gun and the quartz bell jar was 150 mm. After spraying, it was ultrasonically cleaned with ultrapure water and dried in a clean oven to complete a quartz bell jar with a ceramic spray coating made of high-purity alumina.

  An alumina sprayed coating was produced on a 5-inch square quartz substrate under the same conditions as the product bell jar. When the sample was cut out from the substrate and observed by SEM on the surface, the surface of the sprayed film was composed of well-melted splats, and no protruding particles composed of spherical particles of 5 μm or less were observed.

  The quartz bell jar manufactured by the method described above was used by being attached to a pre-cleaning apparatus. After 70 hours from the start of use, particles due to peeling of the film-like substance were observed inside the apparatus.

Comparative Example 2
A quartz bell jar manufactured by the same method as in Comparative Example 1 was attached to a CVD film forming apparatus. After 70 hours had passed since the start of use, particles due to peeling of the film-like substance were collected inside the apparatus.

Example 8
Using a plasma spraying apparatus as shown in FIG. 8, the flow rate of argon and hydrogen is set to 80:20 as the plasma gas 51, the spraying distance 54 is set to 100 mm, the spraying gun is set to a speed of 600 mm / sec, and the spraying gun is set at a pitch of 5 mm. While moving, the amount of alumina powder having an average particle diameter of 40 μm was sprayed twice at a power of 25 kW at a powder supply rate of 20 g / min, and a surface layer having protruding particles was formed on quartz as a base material.

  The sprayed substrate was cut out to a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 100 μm, The presence of mountain-shaped protruding particles was observed. An electron micrograph of the surface layer is shown in FIG.

As a result of arbitrarily extracting and measuring 100 protruding particles, the size per protrusion is 10 to 70 μm in width and 5 to 100 μm in height, and the average value of the ratio of height to width (H / W) Was 1.2 and the number of protrusions was 1000 / mm ² .

  The cross section of the sprayed film was polished and finished to a mirror surface, and when the porosity was measured by taking an electron micrograph, the porosity was 25%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Comparative Example 3
A surface layer was formed by thermal spraying under the same conditions as in Example 8 except that the thermal spraying power was 35 kW. The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 120 μm, and the surface layer was The presence of mountain-shaped protruding particles was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 20 to 200 μm in width and 4 to 100 μm in height. Flat particles having a height ratio of 0.3 were observed. The cross section of the sprayed film was polished and finished to a mirror surface, and when the porosity was measured by taking an electron micrograph, the porosity was 3%. When the cross section of the flat particles was polished and observed with a polarizing microscope, it was found that even the center of the particles was melted.

Example 9
A sample was prepared under the same conditions as in Example 8 except that the spray power was 30 kW and alumina powder having an average particle size of 60 μm was used. The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 120 μm, and the surface layer was The presence of mountain-shaped protruding particles was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 15 to 100 μm in width, the height is 5 to 85 μm, and the average value of the ratio of height to width is 0.9. The number of protrusions was 730 / mm ² . When the cross section of the sprayed film was polished and finished to a mirror surface, an electron micrograph was taken and the porosity was measured. As a result, the porosity was 18%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 10
A sample was prepared under the same conditions as in Example 8 except that the thermal spraying power was 32 kW and alumina powder having an average particle diameter of 50 μm was used. Further, a sample was prepared on this sprayed film under the same conditions as in Example 8 except that the spraying power was 20 kW and alumina powder having an average particle diameter of 25 μm was used. The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 200 μm, and the surface layer was The existence of mountain-shaped protruding particles formed by assembling fine spherical particles in the range of 0.6 to 3.6 μm was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 10 to 65 μm in width and 6 to 120 μm in height, and the average value of the ratio of height to width (H / W) Was 1.6, and the number of protrusions was 1300 / mm ² . The surface of the sprayed film was polished and finished to a mirror surface, and an electron micrograph was taken to measure the porosity. As a result, the porosity of the upper layer was 32% and the porosity of the lower layer was 8%. It was. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 11
Using a plasma spraying apparatus as shown in FIG. 8, the flow rate of argon and hydrogen is 75:25 as the plasma gas 52, the spraying distance 54 is 100 mm, the spraying gun is set to a speed of 500 mm / sec, and the spraying gun is set at a pitch of 5 mm. While moving, the amount of spherical copper powder having an average particle size of 30 μm was sprayed twice at a power of 20 kW at a powder supply rate of 15 g / min, and a surface layer having protruding particles was formed on the stainless steel substrate.

The sprayed substrate was cut out to a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 100 μm, The presence of mountain-shaped protruding particles was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 15 to 65 μm and the height is 10 to 95 μm, and the average value of the ratio of height to width (H / W) Was 1.3 and the number of protrusions was 1250 pieces / mm ² . When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 12
Using a plasma spraying apparatus as shown in FIG. 8, the gas flow rate was set to 80 SLM, twice that in Example 8. Spherical aluminum powder having an average particle size of 65 μm as the plasma gas 52 with a flow rate ratio of 90:10 between argon and hydrogen, a spraying distance of 100 mm, and a spray gun moving at a speed of 1000 mm / second and a pitch of 5 mm. Was supplied twice at a power of 70 kW, and a surface layer having protruding particles was formed on the stainless steel substrate.

The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 150 μm, The existence of mountain-shaped projecting particles formed by assembling fine spherical particles in the range of 2 to 9 μm was observed. An electron micrograph of the surface layer is shown in FIG. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 20 to 80 μm in width and 25 to 150 μm in height, and the average value of the ratio of height to width (H / W) Was 1.8, and the number of protrusions was 320 / mm ² . The cross section of the sprayed film was polished and finished to a mirror surface. When the porosity was measured by taking an electron micrograph, the porosity was 30%. When the cross section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were seen as nuclei, the periphery of the sprayed powder was slightly melted, and the center was unmelted. It was found that it was sprayed as it was.

Comparative Example 4
A surface layer was formed by thermal spraying under the same conditions as in Example 11 except that the thermal spraying power was 35 kW. The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface of the sprayed film was observed with a laser confocal microscope. The film thickness of the sprayed film was 110 μm and the surface layer was. As a result of arbitrarily extracting and measuring 100 protruding particles, the size per protrusion is 15 to 180 μm in width and 3 to 70 μm in height. Among 100 protruding particles, Flat particles having a height ratio (H / W) of 0.2 were observed. The cross section of the sprayed film was polished and finished to a mirror surface, and when the porosity was measured by taking an electron micrograph, the porosity was 8%. When the cross section of the flat particles was polished and observed with a polarizing microscope, it was found that even the center of the particles was melted.

Example 13
Using a plasma spraying apparatus as shown in FIG. 8, the flow rate of argon and hydrogen is 90:10 as the plasma gas 52, the spraying distance 54 is 80 mm, the spraying gun is set at a speed of 400 mm / second, and the pitch is 5 mm. While being moved, a powder obtained by coating an alumina powder having an average particle diameter of 30 μm at a ratio of 1: 1 around a stabilized zirconia powder having an average particle diameter of 35 μm was supplied at a power of 25 kW with a supply rate of 15 g / min. Thermal spraying was performed to form a surface layer having protruding particles.

The sprayed substrate was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness of the sprayed film was 130 μm, The presence of mountain-shaped protruding particles was observed. As a result of arbitrarily extracting and measuring 100 protruding particles, the size per protrusion was 10 to 90 μm in width and 10 to 130 μm in height, and the average value of the ratio of height to width (H / W) Was 1.2 and the number of protrusions was 1350 / mm ² . The cross section of the sprayed film was polished and finished to a mirror surface, and when the porosity was measured by taking an electron micrograph, the porosity was 20%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the alumina powder present in the periphery of the sprayed powder melted. It was found that the zirconia powder present in the center was sprayed without melting.

Example 14
Next, in order to evaluate the retention of the obtained sample against the deposits, a silicon nitride film was directly formed on the samples of Examples 8 to 13 and Comparative Examples 3 to 4 using a sputtering method to test the adhesion. Went. After evacuating to an ultimate vacuum of 5 × 10 ⁻⁵ Pa, a mixed gas of argon gas and nitrogen gas was introduced to a pressure of 0.3 Pa using a silicon target, and a silicon nitride film thickness of 100 μm was formed at room temperature. . After film formation, the sample was returned to the atmosphere and allowed to stand for 1 day, and then each sample was heated at 600 ° C. for 1 hour. After returning to room temperature and examined with a microscope, no peeling or particle generation was observed in the samples of Examples 8-13. Although it was not, peeling was recognized in the samples of Comparative Examples 3 to 4.

Example 15
The quartz bell jars produced by the methods of Examples 8 to 9 and Comparative Example 3 were used by being attached to a CVD film forming apparatus. In the shields of Examples 8 to 9, particles due to peeling of the film-like substance were not collected inside the apparatus even after 160 hours had elapsed from the start of use. However, in the shield of Comparative Example 3, from the start of use. After 70 hours, particles due to peeling of the film-like substance were observed.

Example 16
The shields produced by the methods of Examples 10 to 13 and Comparative Example 4 were used by being attached to a film forming apparatus by sputtering. In the shields of Examples 10 to 13, particles due to peeling of the film-like substance were not collected inside the apparatus even after 150 hours had elapsed from the start of use. However, in the shield of Comparative Example 4, from the start of use. After 60 hours, particles due to peeling of the film-like substance were observed.

Example 17
Using a plasma spraying apparatus as shown in FIG. 8, the flow rate of argon and hydrogen is set to 95: 5 as the plasma gas 52, the spraying distance 54 is set to 120 mm, the spraying gun is set at a speed of 400 mm / second, and a pitch of 5 mm. While moving, the powder supply rate of ITO powder (indium oxide-tin oxide 10 wt%) with an average particle size of 15 μm was 20 g / min and sprayed twice on the surface of the ITO target (tin oxide 10 wt%) with a power of 25 kW. A surface layer having protruding particles was formed. At this time, it masked so that it might not spray on the erosion part of the ITO target surface, and the ITO sprayed film was formed only in the non-erosion part.

The sprayed target was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness was 130 μm, and the surface layer had a ridge-shaped protrusion. The presence of particle-like particles was observed. As a result of arbitrarily extracting and measuring 100 protruding particles, the size per protrusion is 10 to 140 μm in width and 8 to 120 μm in height, and the average value of the ratio of height to width (H / W) Was 0.9, and the number of protrusions was 1300 / mm ² . When the cross section of the sprayed film was polished and finished to a mirror surface, an electron micrograph was taken and the porosity was measured. As a result, the porosity was 24%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 18
Using a plasma spraying apparatus as shown in FIG. 8, the gas flow rate is 70 SLM as the plasma gas 52, the flow rate ratio of argon and hydrogen is 90:10, the spraying distance 54 is 125 mm, the spray gun is at a speed of 300 mm / second, While moving the spray gun at a pitch of 3 mm, the powder supply amount of spherical chromium powder having an average particle size of 30 μm was set to 15 g / min, and sprayed twice on the surface of the chromium target with a power of 80 kW to form a surface layer having protruding particles. Formed. At this time, masking was performed so as not to spray the erosion portion on the surface of the chromium target, and a chromium sprayed film was formed only on the non-erosion portion.

The sprayed target was cut out to a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness was 150 μm, and the surface layer was 0.8 to Presence of mountain-shaped projecting particles formed by aggregation of fine spherical particles in the range of 6.7 μm was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 12 to 130 μm in width and the height is 10 to 140 μm, and the average value of the ratio of height to width (H / W). Was 1.1, and the number of protrusions was 800 / mm ² . When the cross section of the sprayed film was polished and finished to a mirror surface, an electron micrograph was taken and the porosity was measured to find that the porosity was 22%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 19
Using a plasma spraying apparatus as shown in FIG. 8, the gas flow rate is 90 SLM as the plasma gas 52, the flow rate ratio of argon and hydrogen is 92: 8, the spraying distance 54 is 100 mm, the spray gun is at a speed of 450 mm / second, While moving the spray gun at a pitch of 3.5 mm, the supply amount of spherical aluminum powder having an average particle diameter of 70 μm was set to 8 g / min, and sprayed four times on the surface and side surfaces of the aluminum target with a power of 70 kW. A surface layer was formed. At this time, masking was performed so as not to spray the erosion part on the surface of the aluminum target, and an aluminum sprayed film was formed only on the non-erosion part.

  Further, a surface layer having projection-like particles sprayed four times on the surface and side surfaces of the oxygen-free copper backing plate under the same conditions as the aluminum powder except that a copper-aluminum mixed powder having an average particle size of 55 μm was used. Formed.

The sprayed target was cut into a size that allows microscopic observation, and after ultrasonic cleaning and drying, the surface and cross section of the sprayed film were observed with a laser confocal microscope. The film thickness was 180 μm, and the surface layer was 2.5 to Presence of mountain-shaped projecting particles formed by agglomeration of fine spherical particles in the range of 10 μm was observed. As a result of arbitrarily extracting and measuring 100 protrusion-like particles, the size per protrusion is 25 to 200 μm in width and the height is 16 to 130 μm, and the average value of the ratio of height to width (H / W) Was 0.8, and the number of protrusions was 280 / mm ² . When the cross section of the sprayed film was polished and finished to a mirror surface, an electron micrograph was taken and the porosity was measured. As a result, the porosity was 12%. When the cross-section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were found to have nuclei, and the periphery of the sprayed powder melted and the center was not melted. I found out.

Example 20
Using a high-speed flame spraying apparatus capable of film formation at high speed, propane gas with a pressure of 0.7 MPa is used as the fuel gas, oxygen gas with a pressure of 1.0 MPa is used as the combustion gas, the spraying distance is 140 mm, and the spray gun is 500 mm / While the spray gun was moved at a speed of 5 mm and a pitch of 5 mm, a spherical aluminum powder having an average particle size of 60 μm was supplied at a rate of 10 g / min, and the surface and side surfaces of the aluminum target and the backing plate were sprayed four times. A surface layer having particle-like particles was formed. At this time, masking was done so that the erosion part on the surface of the aluminum target was not sprayed, and an aluminum sprayed film was formed only on the non-erosion part. When the sprayed film surface and cross section were observed with a laser confocal microscope, the film thickness was 200 μm, and the surface layer was a mountain shape in which fine spherical particles in the range of 1.4 to 5.0 μm were assembled. The presence of protruding particles was observed. As a result of arbitrarily extracting and measuring 100 protruding particles, the size per protrusion is 20 to 180 μm in width and 25 to 240 μm in height, and the average value of the ratio of height to width (H / W) Was 1.6, and the number of protrusions was 480 pieces / mm ² . The cross section of the sprayed film was polished and finished to a mirror surface, and when the porosity was measured by taking an electron micrograph, the porosity was 20%. When the cross section of the projecting particles was polished and observed with a polarizing microscope, most of the projecting particles were seen as nuclei, the periphery of the sprayed powder was slightly melted, and the center was unmelted. It was found that it was sprayed as it was.

Example 21
The targets prepared in Examples 17 to 20 were used by being attached to a film forming apparatus by sputtering. When the target surface was observed after 100 hours had elapsed from the start of use, the re-depot powder was firmly attached to the target surface, and was attached to such an extent that it could not be removed even if it was peeled off with bare hands.

Comparative Example 5
The ITO target was attached to a film forming apparatus by sputtering in the same manner as in Example 21 except that the ITO powder was not sprayed on the surface of the ITO target by the same method as in Example 17. When the surface of the target was observed after 50 hours from the start of use, the re-depot powder was peeled off from the non-erosion part of the target, and the re-depot powder was scattered around the erosion part of the target. Was observed.

It is a figure which consists of an electron micrograph which shows an example of the protruding particle | grains of this invention. It is a figure which consists of an electron micrograph which shows an example of the protruding particle | grains of this invention. It is a figure which consists of an electron micrograph which marked the protruding particle | grain part in FIG. It is a figure which shows the surface structure of the components obtained in Example 12. It is a figure which shows the surface structure of the components obtained in Example 8. FIG. It is a figure which shows the width | variety and height of the protruding particle | grains in this invention. It is a figure which shows the protruding particle | grains which have a structure where a material with a low melting | fusing point wraps a material with a high melting | fusing point. It is a figure which shows the manufacturing method of the components for vacuum devices comprised from the protruding particle | grains of this invention. It is a figure which shows the manufacturing method by the plasma spraying of the components for vacuum apparatuses comprised from the protruding particle | grains of this invention.

Explanation of symbols

20: Protruding particle 21: Height profile 22: Protruding particle width 23: Protruding particle height 30: Base material 31: Thermal spray material having a high melting point 32: Thermal spray material having a low melting point 33: Protruding particle 40: Thermal spray gun 41: Thermal spray frame 42: Thermal spray powder 43: Unmelted portion of flying spray particle 44: Melted portion of flying spray particle 45: Nucleus of projecting particle composed of unmelted portion of flying spray particle 46: Melting of sprayed particle Projected particle skin 50: Cathode 51: Anode 52: Plasma gas (supply port)
53: Thermal spray powder (supply port)
54: Thermal spray distance 55: Base material 56: Projection-like particle layer

Claims (10)

A ceramic and / or metal sprayed film is formed on the substrate, and the surface of the sprayed film has a width of 10 to 300 μm, a height of 4 to 600 μm, and a ratio of width (W) to height (H) (H / W). In the range of 20 / mm ^{2 to} 20000 / mm ^{2 in} the range of 20 / mm ^{2 to} 20000 / mm ² , projecting particles having an average value of 0.4 or more remain unmelted at the center, and the porosity of the sprayed film is A vacuum device component, characterized by being 10 to 40%. A ceramic and / or metal sprayed film is formed on the substrate, and the surface of the sprayed film has a width of 10 to 300 μm, a height of 4 to 600 μm, and a ratio of width (W) to height (H) (H / W). Projecting particles having an average value of 0.4 or more is 20 particles / mm ² More than 20,000 pieces / mm ² It exists in the following ranges, the protruding particles are made of materials having different melting points, and a material having a low melting point is formed so as to enclose a material having a high melting point, and the porosity of the sprayed film is 10 to 40%. A vacuum device part characterized by being. A thermal spray powder made of ceramic and / or metal is collided onto a substrate in a semi-molten state, and the substrate surface has a width of 10 to 300 μm, a height of 4 to 600 μm, and a ratio of width (W) to height (H) ( H / W) has an average value of 0.4 or more projecting particles in the range of 20 / mm ^{2 to} 20000 / mm ^{2 and the} porosity of the sprayed film is 10% to 40%. The manufacturing method of the components for vacuum devices characterized by providing the sprayed film which becomes. A thermal spray powder made of ceramic and / or metal is formed so that a material with a low melting point wraps a material with a high melting point, and the material with a low melting point is completely melted during spraying, and the material with a high melting point is in an unmelted or semi-molten state And the substrate surface is 10 to 300 μm wide, 4 to 600 μm high, and the average value of the ratio (H / W) of width (W) to height (H) is 0.4 or more. projecting particles are present at 20 / mm ² or more ～20000 pieces / mm ² or less in the range of vacuum and wherein the porosity of the solution reflection film is provided with a thermally sprayed film consisting of 10% to 40% Method of manufacturing parts. The portion membranous substance that produces a PVD or a CVD process are deposited film forming apparatus formed by using a vacuum device component of claim 1. The portion membranous material produced during the plasma etching process is deposited or etched, a plasma etching apparatus formed by using a vacuum device component of claim 1. The portion membranous material produced during the plasma etching process is deposited or etched, a plasma cleaning device formed by using a vacuum device component of claim 1. A ceramic and / or metal sprayed film is formed on a non-erosion portion on a sputtering target material that is a vacuum device component. The surface of the sprayed film has a width of 10 to 300 μm, a height of 4 to 600 μm, and a width (W ) And the height (H) ratio (H / W) of the average value of 0.4 or more The projecting particles in which the central part remains unmelted are 20 particles / mm ² or more and 20000 particles / mm ² or less. A sputtering target characterized in that the thermal spray film has a porosity of 10% to 40%. The sputtering target according to claim 8 , wherein the target material is bonded to a backing plate. The sputtering target according to claim 9 , wherein the non-erosion part of the sputtering target is at least one part selected from a non-erosion part of the target material, a surface part and a side part of the backing plate.

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