JP4062236B2 - ISLAND PROJECT MODIFIED COMPONENT, ITS MANUFACTURING METHOD, AND DEVICE USING THE SAME - Google Patents

Description

  The present invention relates to an island-shaped projection modified part used in a film forming apparatus and a plasma processing apparatus (plasma etching apparatus, plasma cleaning apparatus) in the manufacture of semiconductors and the like, and when used in these apparatuses, degassing from the part is prevented. It provides something that does not generate much dust.

  In the production of semiconductors, etc., CVD parts such as polysilicon, silicon oxide, and silicon nitride are mainly used for glass parts that are excellent in heat resistance and easy to process, such as reaction tubes and bell jars made of quartz glass or heat-resistant glass. It has been. In these film formations, film-like substances are attached not only to the target film formation substrate but also to parts such as reaction tubes and bell jars. As a result, as the film forming operation is repeated, the film-like substance attached to the reaction tube and the bell jar becomes thick, and the reaction tube and the bell jar are cracked or the film-like substance is formed due to the difference in thermal expansion coefficient between the substance and quartz glass. There was a problem that it peeled off to generate dust and contaminated the film formation substrate. In PVD film formation of titanium nitride, tantalum nitride, etc., shield parts made of metal or ceramic are used, and as the film formation operation is repeated, the film-like substance attached to the shield parts becomes thicker and peels off. There was a problem of becoming dust and contaminating the film formation substrate. Also in the plasma etching apparatus and the plasma cleaning apparatus, there is a problem that the film-like substance adhering to the apparatus parts becomes thick, peels off and generates dust, and contaminates the processing substrate.

  As a method for solving such a problem, for example, an apparatus for performing a plasma cleaning by applying a negative bias to an object to be processed has been proposed. (For example, refer to Patent Document 1) However, even in such a plasma cleaning apparatus, particles scattered by etching of the object to be processed adhere to the apparatus in a film shape, and the deposited film-like substance peels off as the number of processes increases. It was a cause of contamination of processed products.

  As a method of improving the retention of the film-like substance, by forming a plasma sprayed film of Mo, W, Al, WC, etc. on the surface of the component, it is possible to disperse the internal stress of the attached film-like substance and increase the adhesion surface. There have been proposed methods for preventing peeling of film-like substances. (For example, refer to Patent Documents 2 and 3) Further, it is disclosed that an insulating film having a higher corrosion resistance against plasma than quartz is applied to the surface of a quartz glass part, and in particular, dense alumina ceramics are formed by explosive spraying. Yes. (For example, refer to Patent Document 4) However, when a quartz glass component is coated with a coating other than quartz glass (Mo, W, Al, WC, alumina, etc.), the coating itself is caused by the difference in thermal expansion coefficient between quartz glass and the coating. There was a problem of easy peeling.

  On the other hand, quartz glass parts roughened by blasting or acid etching after blasting can be used as a method to solve the problem of peeling off film-like substances attached to members of film forming equipment, plasma etching equipment, and plasma cleaning equipment. Proposed quartz glass parts have been proposed (see, for example, Patent Document 5). However, the quartz glass parts processed by the blast method have a problem that microcracks are generated under the processed rough surface, and the fragments become dust (foreign matter) in the apparatus. In addition, the microcracked part has a problem that the mechanical strength is lowered and the life of the part is shortened. Furthermore, there is also a problem that parts are devitrified when impurities enter the microcracks. The problem of dust (foreign matter) due to shards is reduced to some extent by performing acid etching treatment after blast treatment and further performing surface melting treatment with heat, but it has not been sufficient yet (for example, Patent Document 6, 7). Also, quartz glass parts that have been subjected to blasting process will have a rough surface on the surface if they are repeatedly washed with hydrofluoric acid to remove the attached film-like substances. There was a problem that it peeled easily and became particles.

  In addition, there has been proposed a method for forming a rough surface (concave / convex) shape on the surface of a quartz glass component only by chemical treatment without using machining. (For example, refer to Patent Documents 8 and 9) In the chemical treatment method, microcracks do not enter the surface of the component, so there is no contamination resulting from it, but the resulting surface has small irregularities and prevents peeling of the attached film-like substance. Was insufficient. Further, in the chemical treatment method, the performance of the treatment chemical changes with time as the number of treatments increases, and thus it is difficult to stably manufacture the part.

  As a glass surface shape, a glass jig has been proposed in which small protrusions having a width of 70 to 1000 μm and a height of 10 to 100 μm are uniformly distributed on the surface of the glass. (For example, refer to Patent Document 10) As for the surface shape obtained by the method, only the surface of the projection having cracks and the appearance of the small projection on the surface of the large projection was obtained. Since such protrusions were formed by a chemical treatment method of dissolution with an acid containing hydrofluoric acid, the large protrusions themselves tend to be gentle, and are not necessarily sufficient for preventing the attached film-like substance from peeling off. It was. In addition, since minute protrusions on the surface of the protrusions or cracks of the protrusions cause plasma electric field concentration or desorption, they themselves are likely to cause particles. In particular, when the acid is washed after use and reused, the microprojection portion is etched and peeled off, and the problem of generation of particles due to the peeled material increases as the washing is repeated.

US Pat. No. 5,460,689

JP-A-60-120515 JP-A-4-268065 JP-A-8-339895 JP-A-10-59744 JP 09-202630 A JP 2003-212598 A JP-A-11-106225 JP 2002-068766 A Japanese Patent Laid-Open No. 2002-110554

  In the use of a film forming apparatus or a plasma processing apparatus, it is an extremely important issue in the technical field of the present invention to prevent generation of dust (foreign matter) and particles due to peeling of a film-like substance attached to components in the apparatus. It was. The present invention is excellent in prevention of film-like substance peeling and particle generation in film formation and plasma treatment, a part modified with a sprayed film that is less degassed and does not peel off from a substrate by heating, a method for producing the same, and The present invention relates to a device using the.

As a result of intensive studies in view of the above situation, the present inventor is an island-shaped protrusion modified part having an island-shaped protrusion made of glass on a base material, particularly an island-shaped protrusion formed by a plasma spraying method. In the island-shaped projection glass modified parts that are spherical or bell-shaped island-shaped projections, there is little degassing from the projections, there is no peeling from the base material of the projections by heating, there is no generation of particles, It has been found that the retention of the film-like substance deposited on the glass part surface is improved. Further, the present inventors have found that even if the parts are subjected to an acid cleaning treatment after use, the surface protrusion state is maintained, and the generation of particles and the retention effect of the film-like substance are maintained. Moreover, it discovered that such an island-like projection glass modification part was obtained by making the glass raw material supplied by a plasma spraying method into 20 mg / cm < ² > or less with respect to a substrate surface area.

  Further, the present inventor is an island-shaped protrusion modified part made of ceramic and metal on a base material, and is an island-shaped protrusion formed by a thermal spraying method. It has been found that there is little degassing from the protrusions, the protrusions do not peel off from the substrate by heating, no particles are generated, and the retention of the film-like substance deposited on the member surface is improved. In addition, such island-shaped protrusion-modified parts are formed by causing the thermal spray powder to collide with the base material in a semi-molten state, or forming the thermal spray 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 is completely melted, and a material having a high melting point is collided onto the substrate in an unmelted or semi-molten state.

  In addition, in the film forming apparatus, the plasma etching apparatus, and the plasma cleaning apparatus using the island-shaped projection modified part 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.

  The island-shaped protrusion modified component of the present invention is an island characterized by having an island-shaped protrusion on an island-shaped protrusion-modified component having an island-shaped protrusion on a substrate or a substrate on which a glass sprayed film is formed. It is a protrusion-modified part.

  1 and 4 are schematic views of a glass modified part having an island-shaped protrusion made of glass on a base material. The island-shaped protrusion-modified part of the present invention has a spherical glass-shaped protrusion or a bell-shaped protrusion made of glass on a smooth glass substrate 10 or 40. In the present invention, these protrusions are independent from each other in the form of islands, and several island-like protrusions may be overlapped, but a spherical or bell-shaped protrusion is connected to each other to form a film as a whole. There is nothing.

  Here, the spherical island-shaped protrusions are not limited to a strict spherical shape, but indicate a shape lacking a sphere, a hemispherical shape, or a rounded deformed shape shown in FIG. 1, and some of them overlap. Including things. The bell-shaped island-like protrusions also indicate a mountain shape having a hemispherical upper part and a wider bottom part than the upper part, as shown in FIG. Further, in the present invention, these spherical or bell-shaped island-shaped projections may be mixed or overlapped, but it is preferable that there are no cavities closed by overlapping some of these.

  The spherical and bell-shaped island-shaped projections of the present invention are rounded as a whole, and more preferably have no acute angle portion. This is because if the protrusion has an acute angle portion, the electric field in the plasma is concentrated on the acute angle portion and is selectively etched to cause generation of particles.

  The size of each island-like protrusion of the present invention is preferably in the range of 5 to 300 μm in width and 2 to 200 μm in height. In the case of a crushed protrusion having a width of 5 μm and a height of less than 2 μm, the retention of the deposit is reduced. On the other hand, when the width exceeds 300 μm and the height exceeds 200 μm, the retention of deposits is improved, but the portion is partially etched by plasma, and particles are easily generated. In view of the above, the particularly preferable size of the island-shaped protrusion is such that the size per protrusion is in the range of 10 to 150 μm in width and 5 to 100 μm in height, more preferably 10 to 80 μm in width and 5 to 5 in height. The range is 100 μm. Here, the width is the length of the short axis when the island-like protrusion viewed from directly above is regarded as an ellipse. The height is the height from the bottom to the top.

The number of island-shaped protrusions of the present invention is in the range of 20 to 5000 per 1 mm ² unit area, and preferably 50 to 1000 / mm ² . If it is less than 20 pieces / mm ² , the retention of adhered matter is lowered, and if it exceeds 5000 pieces / mm ² , island-like protrusions are overlapped to form a film, and closed pores are easily generated, and thus particles are easily generated.

  Since the protrusions on the surface layer due to the island-shaped protrusions of the present invention have a large difference in height compared to the unevenness obtained by chemical treatment as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-212598 and Japanese Patent Application Laid-Open No. 11-106225, Even if the parts are acid cleaned, the surface irregularities are easily maintained and can be reused without deteriorating the retention of deposits. Protrusions obtained by conventional chemical treatment, for example, Japanese Unexamined Patent Publication No. 2002-68766, etc. have fine small protrusions or cracks, which themselves cause generation of particles. Since the protrusion has no micro protrusion on the surface, generation of particles is remarkably reduced.

  The shape, size, and state of the protrusion surface of the protrusion of the present invention can be confirmed by a scanning electron microscope or the like on the cross section or upper part of the glass-modified part.

  Further, another island-shaped projection modified part of the present invention is obtained by forming a glass underlayer on the surface of a base material, and forming the above-mentioned island-shaped projections thereon. FIG. 7 shows a schematic diagram. A base layer 71 made of glass is formed on the base material 70, and a surface modification layer 72 made of island-shaped protrusions is further formed on the base layer. By forming a glass underlayer on the surface of the substrate in this way, impurity diffusion from the substrate can be prevented, and when the surface of the substrate is damaged, the underlayer is filled and smoothed to form particles. Can be further prevented.

  The film thickness of the underlying glass layer is 100 to 1000 μm, and it is particularly preferable that the glass layer is dense and has no cavity of 100 μm or more and is smooth. If the smoothness of the underlying surface is low, the height difference formed by the island-shaped protrusions formed thereon may be absorbed by the unevenness of the underlying surface. As the smoothness of the base surface, for example, the surface roughness Ra is preferably in the range of 1 to 5 μm.

  Although the base material in this invention may be glass, a metal, a ceramic, etc. can also be used. In the component of the present invention, in particular, a base layer made of a glass sprayed film is formed on a base material, there is no problem of impurity contamination from the base material, and performance equivalent to that of a glass base material can be exhibited. .

Examples of the glass material used for the island-shaped protrusion modified parts of the present invention include heat-resistant glass such as quartz glass, Vycor (registered trademark), aluminosilicate glass, non-alkali glass such as borosilicate glass, and silica, 2a, 3a group elements, etc. Plasma resistant glass to which is added can be used. In particular, in the technical area where the island-shaped protrusion modified parts of the present invention are used, thermal shock resistance and high purity are required. ^Therefore , a glass having a thermal expansion coefficient of 5 × 10 ⁻⁶ / K or less, or high-purity quartz glass is used. It is preferable.

The island-shaped protrusions, the base layer, and the base material may be the same material, but may be different materials. When different materials are used here, the difference in thermal expansion coefficient between the materials is preferably within 5 × 10 ⁻⁶ / K in order to suppress cracking due to thermal shock.

  Furthermore, the island-shaped projection modified part of the present invention is an island-shaped projection modified part having island-shaped projections made of ceramic and / or metal on a base material, wherein the island-shaped projections are bell-shaped. .

  FIG. 10 shows a schematic diagram of the island-shaped projection modified component of the present invention. The island-shaped projection modified component of the present invention has a bell-shaped projection made of ceramic and / or metal on the base material 100. In the present invention, these protrusions are independent from each other in the form of islands, and several island-like protrusions may overlap, but the bell-shaped protrusions are not connected to each other to form a film. is there. By doing so, it is possible to eliminate almost all the holes closed by the island-shaped protrusions, and therefore, degassing is greatly reduced as compared with the continuous sprayed film. Further, even when heated, the island-shaped protrusions are independent from each other, and therefore, the difference from the linear expansion base material due to heating remains within the range of the size of the island-shaped protrusions, so that it is difficult to peel off from the base material.

  Here, the bell-shaped island-shaped protrusion is a mountain shape whose upper part is hemispherical and whose bottom is wider than the upper part as illustrated in FIG. 10A, and whose upper part is rounded as illustrated in FIG. 10B. It refers to the shape of a mountain that protrudes and has a wider bottom than the top, as well as some of these overlapping.

  In the present invention, the average value of the ratio between the height 104 and the width 103 of the island-shaped protrusions formed of various materials is preferably 0.3 or more and 1.5 or less. If it is less than 0.3, the retention of the deposits is lowered, and if it exceeds 1.5, the adhesion of the island-shaped protrusions to the substrate is lowered. The ratio between the height and the width is a value obtained by averaging in a region including 20 to 200 island-shaped protrusions, and this measurement is performed in three or more regions and averaged. For the measurement, an apparatus such as a laser confocal microscope or a scanning electron microscope capable of simultaneously observing an image and measuring the width and height can be used. Here, the width is the length of the short axis when the island-like protrusion viewed from directly above is regarded as an ellipse. The height is the height from the bottom to the top.

It is preferable that the surface of the base material serving as the base of the island-shaped protrusions of the present invention has a surface roughness Ra of 5 μm or less and a negative roughness skewness. The roughness skewness is measured by measuring the roughness profile of the substrate using a surface roughness meter with a length in accordance with the surface roughness measurement standard of JIS or ANSI, and RMS surface roughness R _q and When the average value in the measurement range of the value obtained by cubeing the difference between the height of each measurement point and the center line height is R _tp , the skewness Rsk is expressed by the following formula 1.

Rsk = R _tp / R _q ³ (Formula 1)
In general, when the skewness is positive, the mountain is narrow and the valley is wide, so that the slipperiness is poor. When the skewness is negative, the mountain portion is wider and gentler than the valley, and the slipperiness is good. FIG. 12 shows a schematic diagram. By making the skewness negative, the sprayed powder melted in the process of spraying spreads smoothly on the base material, and the bell is smooth and disk-shaped around the base. The island-shaped protrusion 121 becomes a shape. When the surface roughness Ra is larger than 5 μm or the skewness is positive, as shown in the schematic diagram of FIG. 13, when the sprayed powder melted in the process of spraying spreads on the base material (132), It tends to be jagged and become island-like protrusions including pores 133.

  As the substrate in the present invention, any material such as glass, metal and ceramic can be used. The island-shaped protrusions and the base material may be the same material, but may be different materials.

  The metal or ceramic material constituting the island-shaped protrusions of the present invention may be any material such as Al, Ti, Cu, Mo, W, etc. for metals, alumina, zirconia, titania, spinel, zircon, etc. for ceramics, A material with a higher melting point is easier to control the height to width ratio during the thermal spraying process.

  In another island-shaped protrusion-modifying part of the present invention, the island-shaped protrusion can be formed into a bell shape by making the island-shaped protrusion have a structure in which a material having a low melting point wraps a material having a high melting point. FIG. 14 shows a schematic diagram. An island-like protrusion 143 having a structure in which a material 142 having a low melting point wraps a material 141 having a high melting point is formed on the substrate 140. The difference in melting point between the material 142 having a low melting point and the material 141 having a high melting point is preferably 400 ° C. or higher. By doing so, the height of the island-shaped protrusions 143 can be controlled by the height of the material 141 having a high melting point, so that the island-shaped protrusions 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.

  Next, the manufacturing method of the glass island-like projection modified part of the present invention will be described.

In the method of forming island-shaped protrusions on the base material by plasma spraying, the optimum value of the island-shaped protrusion modified part of the present invention varies depending on the type of raw glass used, but the glass raw material supply amount with respect to the surface area of the base material 1 to 20 mg / cm ² .

In the plasma spraying method, when the raw material supply with respect to the surface area of the substrate exceeds 20 mg / cm ² , island-shaped protrusions overlap and a film different from the shape of the present invention is easily formed. On the other hand, when the raw material is supplied at a concentration of less than 1 mg / cm ² , the island-like protrusions obtained are small and the formation speed is slow, which is not preferable. As the raw material feed is preferably in the range particularly 5 to 10 mg / cm ^2.

  The formation of the island-shaped protrusions can be performed by spraying several times on the base material, but it is preferable to form by one spraying. When spraying several times, island-like protrusions overlap and easily form a film. Therefore, it is necessary to lower the powder supply rate than in the case of once. On the other hand, after forming the island-shaped protrusions, the surface of the substrate is irradiated with a plasma jet without supplying raw materials in order to remove adhered fine particles on the surface or to improve the adhesion of the island-shaped protrusions to the substrate. It is preferable to do.

  Formation of island-like projections of the island-like projection modified part in the present invention can be performed by various spraying methods such as flame spraying and plasma spraying, but the plasma spraying method is used, and the substrate or glass on the substrate by plasma jet is used. It is preferable to manufacture under the condition that the surface of the underlayer is melted. By supplying the raw material powder and performing thermal spraying while melting the surface of the base material or the glass underlayer, the adhesion of the island-shaped protrusions to the base material or the glass underlayer can be improved. In addition, once the island-shaped protrusions are formed and subsequently the surface is melted by irradiating the plasma jet, there is an effect of improving the adhesion of the island-shaped protrusions to the base material.

  The distance between the plasma gun that irradiates the plasma jet onto the substrate and the substrate differs depending on the apparatus used. For example, in the case of a normal plasma spraying apparatus as shown in FIG. Examples of the conditions include a spraying distance of about 50 mm and a spraying power of 35 kW or more. On the other hand, if the reduced pressure plasma spraying method is used, the shape of the plasma jet becomes long, so the distance between the substrate and the spray gun may be 100 mm or more.

  In particular, when manufacturing large glass-modified parts, among other plasma spraying methods, refer to the double torch type plasma spraying apparatus (Japanese Patent Publication No. 6-22719, spraying technology Vol. 11, No. 1, p. 1-8 (1991), etc.) ) Is preferably used for thermal spraying with a laminar plasma jet. FIG. 9 shows an outline of a double torch type plasma spraying apparatus. In the double torch type plasma spraying apparatus, a laminar flow plasma having a length of several hundred mm (usually about 50 mm in a turbulent state) can be formed, so that the island-like projections of the present invention can be formed even when the spraying distance is 100 mm or more. I can do it.

  The particle diameter of the powder of glass, ceramics, metal, or the like used for manufacturing the island-shaped protrusions is preferably an average particle diameter of 10 μm to 100 μm, and more preferably an average particle diameter of 10 μm to 50 μm. If the average particle size is less than 10 μm, it is difficult to uniformly introduce the raw material into the plasma because the raw material powder itself does not have sufficient fluidity. On the other hand, when the average particle size exceeds 100 μm, the sprayed particles are not uniformly melted, and the adhesion of the obtained island-shaped protrusions to the base material tends to deteriorate. Further, the size of the particles used for thermal spraying is as uniform as possible, so that the shape of the island-shaped protrusions can be made uniform and the retention of the adhesion film can be improved.

  In the present invention, it is preferable to preheat the temperature of the substrate surface in advance. Preheating the substrate surface in advance is effective for obtaining island-like protrusions with high adhesion to the substrate. If the substrate is not preheated, the adhesion strength of the island-shaped protrusions is lowered, and the island-shaped protrusions are easily peeled off when the deposit is removed with an acid etching solution after use. Although the preheating temperature varies depending on the type of the substrate used, for example, in the case of a quartz glass substrate, a range of 700 to 1500 ° C., particularly 800 to 1200 ° C. is preferable. An excessively high preheating temperature is not preferable because the glass crystallizes and devitrifies or changes its shape.

  The island-shaped protrusion-modified component of the present invention may be a glass base layer formed on a substrate. The base material on which the glass underlayer is formed may be not only a glass base material but also a metal or ceramic base material. A method for forming such an underlayer is not particularly limited, but a plasma spraying method can also be applied here.

As a method for forming the underlayer by the plasma spraying method, for example, with the apparatus and conditions illustrated in FIG. 8 or FIG. 9, the supply amount of the raw material powder is set to 20 mg / cm ² or more and the spraying is repeated several times. It can be formed under the same thermal spraying conditions as the formation of island-shaped protrusions. Since the surface of the underlayer is preferably smooth, it is preferable that after forming the underlayer, the surface of the underlayer is melted by irradiation with a plasma jet without supplying the raw material powder.

  Further, as a method for forming island-shaped protrusions, a sol-gel method using a silicon alkoxide solution and a plasma spraying method may be combined. For example, by preliminarily forming a silica underlayer and island-shaped protrusions by dispersing silica particles of several to several hundred μm in a silicon alkoxide solution, the surface is irradiated with a plasma jet of a plasma spraying method, Similar glass modified surfaces can be obtained. When square silica particles are used, it is essential to perform irradiation by plasma spraying. This is because, without irradiation, the spherical or bell-shaped island-shaped projections characteristic of the present invention, that is, the projections themselves are not rounded and the projections are not acute angles. Even when spherical silica particles are used, the adhesion of the island-shaped protrusions to the base material can be made sufficiently high by irradiation by plasma spraying.

  The island-shaped protrusion-modified part of the present invention may remove attached fine particles by acid cleaning after the formation of the island-shaped protrusion. The island-shaped protrusions of the glass-modified part of the present invention can be formed without any fine protrusions on the surface of the island-shaped protrusions themselves by the plasma spraying operation. Deposits may remain on the surface of the island-like projections. If such minute deposits remain, they may fall off during use of the part, causing particles and foreign matters. Then, after forming island-like protrusions by plasma spraying and washing with acid, such deposits can be completely removed. The acid cleaning is preferably performed with a cleaning solution of hydrofluoric acid or nitric acid.

  Furthermore, the island-shaped protrusion modified parts of the present invention can be manufactured by forming island-shaped protrusions on a substrate by a thermal spraying method. However, for the manufacture of island-shaped protrusions, the island-shaped protrusions do not overlap to form a continuous film. Furthermore, the amount of sprayed powder supplied is less than that of normal spraying. Further, by causing the sprayed powder to collide with the base material in a semi-molten state at the time of thermal spraying, it is possible to manufacture bell-shaped island-shaped protrusions having a disk-like periphery and a raised central portion. The thermal spraying method to be used includes plasma spraying method, flame spraying method, etc., but during spraying, the thermal spray powder is in a semi-molten state, that is, by adjusting the spraying power, flame power, etc., as shown in FIG. Is not melted (153) and the surroundings are in a molten state (154). Here, when the thermal spray power and the flame thermal power are increased, the entire thermal spray powder is melted to form the disk-shaped island-shaped projections 111 as shown in FIG. 11, and the retention of the adhesion film is lowered.

  As another method for manufacturing the island-shaped projection modified part of the present invention, the sprayed 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 during spraying. Larger material is impinged on the substrate in an unmelted or semi-molten state.

  As described above, it is preferable that the surface of the base material serving as the base of the island-shaped protrusions of the present invention has a surface roughness Ra of 5 μm or less and a negative skewness. In order to make the skewness negative when the surface roughness Ra is 5 μm or less, a rough abrasive is used to grind with a grinder, a grinder, etc., or a smooth ground substrate is lightly formed using a blast method Alternatively, it is achieved by forming the irregularities using the blast method, and then lightly polishing with a grinder, a polishing machine or the like in order to eliminate the protrusions protruding significantly from the center line.

  The rougher the surface roughness of the base material, the better the adhesion of the island-shaped protrusions to the base material. However, as described above, when the sprayed powder melted during the thermal spraying process spreads over the base material, It tends to become island-like projections containing pores. By preheating the substrate surface in advance, the sprayed powder melted in the process of spraying tends to spread smoothly, and the adhesion of the island-shaped protrusions to the substrate is also increased. The preheating temperature varies depending on the type of base material used and the thermal spray material, but for example, when metal is sprayed on a stainless steel base material, a range of 100 to 500 ° C., particularly 200 to 4000 ° C. is preferable. An excessively high preheating temperature is not preferable because the base material may be distorted or cracked.

  It is preferable to heat-treat after forming island-shaped protrusions on the substrate by a thermal spraying method. By doing so, it is possible to manufacture an island-shaped protrusion-modified part having island-shaped protrusions with high adhesion to a smooth base material having a small surface roughness. The heat treatment temperature is preferably as high as possible within a range not exceeding the heat-resistant temperature of the substrate and the melting point of the island-shaped protrusions.

  Furthermore, the present invention proposes a film forming apparatus using the above-described island-shaped protrusion modifying component.

  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 island-shaped protrusion modified 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 apparatus. For example, it can be used as a reaction tube or a bell jar. In particular, in a CVD film forming apparatus for forming polysilicon, silicon oxide, silicon nitride or the like at a high temperature of 600 to 1000 ° C., a quartz reaction tube or bell jar in which the surface modification layer and the underlayer of the present invention are formed of quartz glass is used. If used, there is no cracking or peeling due to the difference in thermal expansion coefficient between the quartz glass of the base material, the base layer, and the modification layer, and there is no generation of particles due to peeling of the attached film-like substance, enabling continuous film formation for a long time. It can be a device.

  In addition, the present invention proposes a plasma etching apparatus and a plasma cleaning apparatus using the island-shaped protrusion modified part having the glass surface modification layer described above. It is preferable to use the island-shaped protrusion-modified component in a site where a film-like substance adheres in these devices or a site where the component surface is easily peeled by contact with plasma. For example, a ring-shaped focus component or a bell jar It can be used as.

  Furthermore, as a method for using the island-shaped projection modified 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 apparatus. For example, it can be used as a bell jar or a shield. In particular, in tungsten or titanium CVD film deposition equipment or titanium nitride sputtering equipment, if the island-like protrusion modification layer of the present invention is used for a bell jar or shield, there is no cracking or peeling due to the difference in thermal expansion coefficient between the base material and the modification layer. 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 island-shaped protrusion modifying part having the island-shaped protrusion modifying layer described above. It is preferable to use the island-shaped protrusion-modified part in a part where a film-like substance adheres in these devices, or a part where the part surface is easily peeled by contact with plasma. For example, a ring-shaped clamp part or shield It can be used as.

  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. is there. 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 device using the island-shaped protrusion modified parts of the present invention does not generate initial particles, improves the retention of deposits deposited by plasma treatment, reduces particles due to peeling of the deposits, and extends the continuous use period of the device. I can do it.

The island-shaped projection modified part of the present invention and the apparatus using the same have the following effects.
(1) Since the deposits deposited on the parts are highly retained, there is no peeling of the deposits and no generation of dust or particles when used in a film forming apparatus or a plasma processing apparatus.
(2) Since the island-shaped protrusions on the part are spherical or bell-shaped, when used in a film forming apparatus or a plasma processing apparatus, there is no generation of particles due to plasma electric field concentration on the part.
(3) Since there are no micro-projections on the glass island-like projections on the glass component, there is no generation of particles due to peeling of the projections on the surface even after acid cleaning of the component, and the shape is easily maintained, and many times Can be used repeatedly.
(4) Since the island-like protrusions on the part are isolated on the base material, when a thermal load is applied to the part, the stress due to the difference in thermal expansion coefficient between the island-like protrusions and the base material is small and does not peel off. Also, since there are almost no closed pores, there is little degassing.

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

Example 1
Using a multiple torch type plasma spraying apparatus as shown in FIG. 9, 5 SLM (Standard Litter per Minute) is flowed as the plasma gas 92, the spraying distance 94 is set to 80 mm without supplying the powder 93, and the spraying gun. Was moved at a speed of 80 mm / sec, thermal plasma was generated at a power of 20 kW, and the smooth quartz glass substrate surface 95 was preheated once. Here, the length of the thermal plasma was about 300 mm, and the plasma was in a laminar flow state. The preheating temperature immediately after plasma heating was 820 ° C. Next, a surface layer having island-shaped projections is sprayed once while the spraying gun is moved at a speed of 100 mm / second and a pitch of 4 mm with a powder supply amount of quartz glass powder having an average particle size of 50 μm being 1 g / min. Formed. In this case, the amount of raw material powder supplied to the substrate surface was equivalent to 5 mg / cm ² . After that, a spray gun is sprayed once at a speed of 120 mm / second without supplying quartz glass powder onto the formed island-shaped projections, the island-shaped projections and the substrate surface are melted, and the deposits on the island-shaped projections are re-applied. Improved adhesion of fused and island-like protrusions to the quartz glass substrate. Next, it was immersed in an aqueous solution of 5% hydrofluoric acid for 30 minutes, then washed with ultrapure water and dried in a clean oven. As a result of observing the surface with a microscope, spherical island-like protrusions were observed on the surface layer as shown in FIG. 2 and FIG. 3, and the size per protrusion was 5 to 50 μm in width and 5 to 60 μm in height. The average value of the ratio of height to width was 1.0, and the number of protrusions was 180 / mm ² . The surface roughness Ra measured by a stylus type surface roughness meter was 12 μm.

Example 2
The same conditions as in Example 1 were used except that quartz glass powder having an average particle size of 20 μm was used. As a result of observing the surface with a microscope, spherical surface protrusions were observed on the surface layer, the size per protrusion was 5 to 20 μm in width, the height was 2 to 40 μm, and the number of protrusions was 3000 / mm. ² . The surface roughness Ra measured with a stylus type surface roughness meter was 5 μm.

Example 3
After pre-heating the ground quartz glass substrate to 850 ° C, the quartz glass powder is supplied at a rate of 2 g / min, the spraying distance is 80 mm, the speed is 80 mm / sec, the spray gun is moved at a pitch of 4 mm, and repeated 6 times. By spraying, an underlayer of a quartz glass sprayed film was formed on the quartz glass substrate.

  Next, the spray gun was sprayed once without supplying quartz glass powder at a speed of 80 mm / second, and the surface of the underlayer was remelted to obtain a quartz sprayed film having a smooth surface and a film thickness of about 300 μm. On this smooth underlayer, the same amount as that of Example 1 except that the powder supply rate was 2 g / min and the spray gun was run at a speed of 100 mm / second as the remelting condition after the surface layer spraying. A surface layer having protrusions was formed.

In this case, the amount of the raw material powder supplied to the substrate surface was equivalent to 60 mg / cm ² for the underlayer formation and 10 mg / cm ² for the island-shaped protrusion formation. As a result of observing the surface with a microscope, as shown in FIGS. 5 and 6, a surface layer in which a large number of spherical and bell-shaped protrusions are mixed is recognized in the surface layer, and the size per protrusion is 10 to 150 μm in width. The height was 10 to 100 μm, the average value of the ratio of height to width was 0.6, and the number of protrusions was 150 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 20 μm.

Example 4
A quartz glass underlayer and island-shaped protrusions were formed in the same manner as in Example 3 except that zircon (ZrO ₂ · SiO ₂ ) was used as the substrate. As a result of observing the surface with a microscope, the film thickness of the underlayer was 280 μm. In addition, a surface layer in which a large number of spherical and bell-shaped protrusions are mixed is observed in the surface layer, and the size per protrusion is 10 to 150 μm in width and 10 to 100 μm in height, and the average ratio of height to width is The value was 0.7, and the number of protrusions was 170 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 25 μm.

Example 5
A quartz glass underlayer and island projections were formed in the same manner as in Example 3 except that a stainless steel plate was used as the substrate. As a result of observing the surface with a microscope, the film thickness of the base was 320 μm. In addition, a surface layer in which a large number of spherical and bell-shaped protrusions are mixed is observed in the surface layer, the size per protrusion is 20 to 160 μm, the height is 20 to 100 μm, and the average ratio of the height to the width The value was 0.6, and the number of protrusions was 200 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 23 μm.

Example 6
The same conditions as in Example 1 were used except that Vycor glass was used as the glass substrate and the thermal spray powder material. As a result of observing the surface with a microscope, spherical island-like protrusions were observed on the surface layer, the size per protrusion was 5 to 50 μm in width, the height was 5 to 55 μm, and the average value of the ratio of height to width 1.1 and the number of protrusions was 200 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 10 μm.

Example 7
Using aluminosilicate glass as the glass substrate and thermal spray powder material, as the thermal spraying condition of the surface layer, without supplying powder, the spraying distance is 120 mm, the speed is 100 mm / second, and the spray gun is moved at a pitch of 4 mm. Thermal plasma was generated with a power of 20 kW, and the smooth aluminosilicate glass substrate surface was preheated once. The preheating temperature immediately after plasma heating was 500 ° C.

Next, the powder supply amount of the aluminosilicate glass powder having an average particle size of 50 μm was set to 1 g / min, and sprayed once while moving the spray gun at a speed of 120 mm / sec to form island-shaped projections. Thereafter, the spray gun was sprayed once without supplying the aluminosilicate glass powder at a speed of 140 mm / sec, and the surfaces of the base material and the island-shaped protrusions were remelted. Next, it was immersed in an aqueous solution of 5% hydrofluoric acid for 30 minutes, then washed with ultrapure water, and dried in a clean oven. As a result of observing the surface with a microscope, a surface layer in which spherical and bell-shaped protrusions are mixed is recognized in the surface layer, and the size per protrusion is 5 to 30 μm in width and 5 to 40 μm in height. The average value of the width ratio was 1.0, and the number of protrusions was 140/1 mm ² . The surface roughness Ra measured by a stylus type surface roughness meter was 8 μm.

Example 8
Island-like projections were preformed by a sol-gel method on a smooth quartz glass substrate surface and heated and melted by a plasma spraying method, and the preformed projections were made into a smooth spherical shape or bell shape. First, a mixed solution of silicon alkoxide-Si (OC ₂ H ₅ ) ₄ , alcohol-C ₂ H ₅ OH, water-H ₂ O, and hydrochloric acid-HCl was prepared. To this mixed solution, 5% by weight of the quartz powder having an average particle diameter of 30 μm with respect to the weight of the solution was well mixed and stirred and allowed to stand. When the viscosity reached 15 centipoise, the mixture was further stirred to disperse the quartz powder uniformly. Next, the quartz glass substrate was immersed in this solution and pulled up and dried at a rate of 2 mm / second. On the surface of the base material, the quartz powder adhered in an evenly dispersed state. Using the same plasma spraying device, the surface of the base material is heated at a power of 20 kW while the spraying distance is 80 mm, the spray gun speed is 100 mm / second, and the pitch is 4 mm without supplying powder. The quartz glass substrate surface was irradiated twice. Next, it was immersed in an aqueous solution of 5% hydrofluoric acid for 30 minutes, then washed with ultrapure water, and dried in a clean oven. The film thickness of the surface layer was 40 μm. As a result of observing the surface with a microscope, a surface layer in which a large number of spherical and bell-shaped protrusions were mixed was observed on the surface, the size per protrusion was 5 to 50 μm, the height was 5 to 40 μm, and the height was high. The average ratio of width to width was 0.9, and the number per 1 mm ² unit area was 250. The surface roughness Ra measured by a stylus type surface roughness meter was 8 μm.

Comparative Example 1
The surface of the polished quartz glass substrate was blasted with white alumina # 60 grit at a pressure of 0.5 MPa, then immersed in an aqueous solution of 5% hydrofluoric acid for 30 minutes, washed with ultrapure water, and dried in a clean oven. . As a result of observing the surface with a microscope, an angular rough surface was confirmed, and a number of micro-cullers were observed in the cross-sectional observation. The surface roughness Ra measured with a stylus type surface roughness meter was 13 μm.

Comparative Example 2
The same conditions as in Comparative Example 1 were used except that Vycor glass and aluminosilicate glass were used as the glass substrate. As a result of observing the surface with a microscope, an angular rough surface and a micro-culler similar to Comparative Example 1 were confirmed. The surface roughness Ra measured by a stylus type surface roughness meter was 15 μm.

Comparative Example 3
A quartz glass substrate whose surface was ground was immersed in a treatment liquid in which an aqueous hydrogen fluoride solution, an ammonium fluoride solution, and an acetic acid aqueous solution were mixed. The surface roughness Ra of the quartz glass treated with the chemical solution was 1.5 μm. As a result of observing the surface, no microcracks were observed.

Example 9
Next, in order to evaluate the retention of the obtained sample against the deposit, a silicon nitride film was directly formed on the samples of Examples 1 to 8 and Comparative Examples 1 to 3 using a sputtering method, and the adhesion was tested. 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 150 μm was formed at room temperature. . After film formation, the sample was returned to the atmosphere and allowed to stand for one day. Each sample was examined under a microscope. No peeling or particle generation was observed in Examples 1 to 8, but peeling was not observed in the samples of Comparative Examples 1 to 3. Admitted.

Example 10
The quartz tube inner wall of the LPCVD film forming apparatus to which the deposited film adheres, the focus ring of the plasma etching apparatus, and the quartz of the plasma cleaning apparatus under the conditions of Examples 1 to 3, Examples 6 to 8, and Comparative Examples 1 to 3. A prototype bell jar was made and used for film formation and plasma treatment. In the case of using a bell jar that was prototyped under the conditions of Comparative Examples 1 to 3, particles were observed from the beginning of the treatment, and in particular, in Comparative Example 3, peeling of deposits was observed during use. On the other hand, in the conditions of Examples 1 to 3 and 6 to 8, no delamination of particles and generation of particles were observed even after continuous use for 200 hours or more.

Example 11
The samples of Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated for acid resistance cleaning. The samples of Examples 1 to 3 and Comparative Examples 1 to 3 were immersed in a nitric hydrofluoric acid cleaning solution in which nitric acid (concentration 61%) and hydrofluoric acid (concentration 46%) were mixed 1: 1. After 3 hours, in the samples of Examples 1 to 3, the surface of the sprayed film was etched mainly, but the unevenness on the surface was kept at the same level as before the immersion. The samples of Comparative Examples 1 and 2 had a smooth surface. In the sample of Comparative Example 3, the surface roughness Ra was lowered to 1.0 μm.

  Next, the quartz tube, focus ring, and quartz bell jar treated under the same conditions were actually used as the quartz tube inner wall of the LPCVD film forming apparatus, the focus ring of the plasma etching apparatus, and the quartz bell jar of the plasma cleaning apparatus. In the samples prepared under the conditions of Comparative Examples 1 and 2, particles were observed from the beginning, and under the conditions of Comparative Example 3, the retention of the adhered material was reduced at the portion where the adhered material was deposited, and particles due to peeling were observed. Under the conditions of Examples 1 to 3, no peeling of deposits or generation of particles was observed even during continuous use for 200 hours or more.

Example 12
Using a plasma spraying apparatus as shown in FIG. 8, 35 SLM (Standard Litter per Minute) is used as the plasma gas 82, 10 SLM is supplied with hydrogen, and the spraying distance 84 is set to 100 mm without supplying the powder 83. While moving the spray gun at a speed of 400 mm / second and a pitch of 4 mm, a thermal plasma was generated with a power of 25 kW, and the surface roughness was adjusted to 0.5 μm and the skewness to −0.3 in advance by polishing. The alumina ceramic substrate 85 was preheated twice. The preheating temperature immediately after plasma heating was 200 ° C. Next, the amount of alumina powder having an average particle diameter of 20 μm was set to 8 g / min, sprayed once at a power of 25 kW while moving the spray gun at a speed of 400 mm / second and a pitch of 4 mm, and island-shaped projections were formed. A surface layer was formed. After spraying, the substrate was placed in a heat treatment furnace and heated at 1300 ° C. for 1 hour. Here, the surface layer was peeled off by pressing with tweezers before the heat treatment, but was not peeled off after the heat treatment and was in good contact. The finished sample was ultrasonically washed with pure water, dried, and then observed on the surface with a microscope. As a result, bell-shaped island-shaped protrusions were observed on the surface layer, and the size per protrusion was 10 to 40 μm in width. The height was 4 to 30 μm, the average value of the ratio of height to width was 0.4, and the number of protrusions was 1800 pieces / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 4 μm. When the cross-section of the island-shaped protrusions was polished and observed with a polarizing microscope, the center of most of the island-shaped protrusions was seen as a nucleus, the periphery of the sprayed powder was melted, and the center was unmelted It was found that it was sprayed as it was.

Comparative Example 4
A surface layer was formed under the same conditions as in Example 12 except that the thermal spraying power was 35 kW and the preheating temperature was 250 ° C. As a result of observing the surface with a microscope, flat island-like protrusions were observed on the surface layer, the size per protrusion was 15 to 80 μm, the height was 2 to 20 μm, and the average value of the ratio of height to width Was 0.1 and the number of protrusions was 3500 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 3 μm. When the cross-section of the island-shaped protrusions was polished and observed with a polarizing microscope, most of the island-shaped protrusions showed no nuclei, and it was found that the sprayed powder was melted and sprayed to the center.

Comparative Example 5
A continuous sprayed film having a thickness of 140 μm was formed by spraying under the same conditions as in Example 12 except that the amount of alumina powder supplied was 30 g / min and sprayed twice at a power of 25 kW. After spraying, the substrate was placed in a heat treatment furnace and heated at 1300 ° C. for 1 hour. As a result, the sprayed film was distorted and large cracks were partially formed.

Example 13
A sample was prepared under the same conditions as in Example 12 except that the spraying power was 30 kW, the preheating temperature was 220 ° C., and alumina powder having an average particle size of 60 μm was used. As a result of observing the surface with a microscope, bell-shaped island-shaped projections were observed on the surface layer, the size of each projection was 30 to 100 μm in width, the height was 20 to 120 μm, and the average ratio of height to width The value was 1.0 and the number of protrusions was 300 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 10 μm. When the cross-section of the island-shaped protrusions is polished and observed with a polarizing microscope, the central part of most island-shaped protrusions is seen as a nucleus, and the center of the sprayed powder is sprayed without being melted. I understood.

Example 14
Example except that a zircon powder having a thermal power of 27 kW, a preheating temperature of 200 ° C., and an average particle size of 30 μm was used on a stainless steel base material having a surface roughness Ra of 1 μm and a skewness of −0.5 by a grinder. A sample was prepared under the same conditions as in No. 12. As a result of observing the surface with a microscope, bell-shaped island-shaped protrusions were observed on the surface layer, the size of each protrusion was 15-60 μm in width, the height was 6-45 μm, and the average ratio of height to width The value was 0.5 and the number of protrusions was 900 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 6 μm. When the cross-section of the island-shaped protrusions is polished and observed with a polarizing microscope, the central part of most island-shaped protrusions is seen as a nucleus, and the center of the sprayed powder is sprayed without being melted. I understood.

Example 15
Using a plasma spraying apparatus as shown in FIG. 8, 50 SLM of argon is flowed as plasma gas 82, powder 83 is not supplied, spraying distance 84 is 100 mm, and spray gun is sprayed at a speed of 400 mm / sec and a pitch of 4 mm. While moving the gun, a thermal plasma was generated with a power of 20 kW, and the stainless steel substrate surface 85 that had been previously polished and adjusted to have a surface roughness of 0.3 μm and a skewness of −0.2 was preheated twice. . The preheating temperature immediately after plasma heating was 170 ° C. Next, the powder supply amount of molybdenum powder having an average particle size of 40 μm is set to 10 g / min, sprayed once at a power of 20 kW while moving the spray gun at a speed of 400 mm / second and a pitch of 4 mm, and the island-shaped projections are formed. A surface layer was formed. After spraying, the substrate was placed in a heat treatment furnace and heated at 600 ° C. for 1 hour. The finished sample was ultrasonically cleaned with pure water, dried, and observed on the surface with a microscope. As a result, bell-shaped island-shaped protrusions were observed on the surface layer, and the size per protrusion was 30 to 80 μm, The height was 10 to 70 μm, the average value of the ratio of height to width was 0.7, and the number of protrusions was 800 pieces / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 6 μm. When the cross-section of the island-shaped protrusions is polished and observed with a polarizing microscope, the central part of most island-shaped protrusions is seen as a nucleus, and the center of the sprayed powder is sprayed without being melted. I understood.

Comparative Example 6
A surface layer was formed under the same conditions as in Example 15 except that the thermal spraying power was 30 kW and the preheating temperature was 200 ° C. As a result of observing the surface with a microscope, flat island-like protrusions were observed on the surface layer, the size per protrusion was 50 to 150 μm, the height was 5 to 15 μm, and the average value of the ratio of height to width Was 0.1, and the number of protrusions was 1200 / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 3 μm. When the cross-section of the island-shaped protrusions was polished and observed with a polarizing microscope, most of the island-shaped protrusions showed no nuclei, and it was found that the sprayed powder was melted and sprayed to the center.

Comparative Example 7
A continuous sprayed film having a film thickness of 160 μm was formed by spraying under the same conditions as in Example 15 except that the amount of molybdenum powder supplied was 30 g / min and sprayed twice at a power of 20 kW.

Example 16
Using a plasma spraying apparatus as shown in FIG. 8, argon is flowed at 50 SLM as the plasma gas 82, the spraying distance 84 is set to 80 mm without supplying the powder 83, and the spraying gun is sprayed at a speed of 400 mm / second and a pitch of 4 mm. While moving the gun, a thermal plasma was generated at a power of 25 kW, and the stainless steel substrate surface 85 previously smoothed by polishing (surface roughness 0.1 μm) was preheated twice. The preheating temperature immediately after plasma heating was 200 ° C.

Next, a powder coated with 20 wt% Co around tungsten carbide spherical sintered particles having an average particle size of 30 μm was used, the powder supply rate was 10 g / min, the speed was 400 mm / sec, and the spray gun was applied at a pitch of 4 mm. While being moved, thermal spraying was performed once at a power of 22 kW to form a surface layer having island-shaped protrusions. After spraying, the substrate was placed in a heat treatment furnace and heated at 600 ° C. for 1 hour. The finished sample was ultrasonically cleaned with pure water, dried, and observed on the surface with a microscope. As a result, bell-shaped island-shaped protrusions were observed on the surface layer, and the size per protrusion was 30 to 90 μm in width. The height was 15 to 90 μm, the average value of the ratio of height to width was 0.8, and the number of protrusions was 600 pieces / mm ² . The surface roughness Ra measured with a stylus type surface roughness meter was 7 μm. When the cross-section of the island-shaped protrusions was polished and observed with a polarizing microscope, the core of most of the island-shaped protrusions was seen as a nucleus, and the tungsten carbide particles in the center of the sprayed powder were sprayed without melting. I found out.

Example 17
Next, in order to evaluate the retention of the obtained sample against the deposit, a silicon nitride film was directly formed on the samples of Examples 12 to 16 and Comparative Examples 4 and 6 using a sputtering method, and the adhesion was tested. 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 Examples 12-16. However, peeling was observed in the samples of Comparative Examples 4 and 6.

Example 18
Under the conditions of Examples 12 to 13 and Comparative Examples 4 to 5, a quartz bell jar for a plasma cleaning apparatus to which a deposited film adheres was prototyped and used for plasma processing. When the evacuation time was compared in Example 12 and Comparative Example 5, in Example 12, the ultimate vacuum was reached in 2/3 time of Comparative Example 5. On the other hand, compared with Comparative Example 5, in Examples 12 to 13, the time until the deposited film began to peel after the start of use of the bell jar with the apparatus was more than doubled.

Example 19
Under the conditions of Examples 14 to 16 and Comparative Examples 6 to 7, an upper shield of a PVD apparatus to which a deposited film of TiN adhered was prototyped and used for film formation on a wafer. When the evacuation time was compared between Example 15 and Comparative Example 7, the ultimate vacuum was reached in Example 15 in half the time of Comparative Example 7. On the other hand, in Examples 14 to 16 compared to Comparative Example 6, the time until the deposited film began to peel after the start of using the upper shield in the apparatus was more than twice as long.

It is a schematic diagram which shows the structure of the island-shaped protrusion modification component of this invention. 2 is a top surface observation result of a scanning microscope of the sample obtained in Example 1. FIG. It is a cross-sectional observation result of the scanning microscope of the sample obtained in Example 1. It is a schematic diagram which shows the structure of the island-shaped protrusion modification component of this invention. It is the upper surface observation result of the scanning microscope of the sample obtained in Example 3. FIG. It is a cross-sectional observation result of the scanning microscope of the sample obtained in Example 3. It is a schematic diagram which shows the structure of the glass modification component of this invention. It is a figure which shows an example of a general plasma spraying apparatus. It is a figure which shows an example of a double torch type plasma spraying apparatus. It is a schematic diagram which shows the structure of the bell-shaped island-shaped protrusion modification component of this invention. It is a schematic diagram which shows the structure of a disk-shaped island-shaped protrusion modification component. It is a schematic diagram which shows the structure of the island-shaped protrusion modification component of this invention which formed the bell-shaped island-shaped protrusion in the base material with a negative skewness. It is a schematic diagram which shows the structure of the island-shaped protrusion modification component of this invention which formed the bell-shaped island-shaped protrusion in the base material with a positive skewness. It is a schematic diagram showing the structure of the island-shaped protrusion modified part of the present invention in which the island-shaped protrusion is shaped like a bell so that a material having a low melting point wraps a material having a high melting point. It is a schematic diagram which shows the manufacturing method of the bell-shaped island-shaped projection modified component of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10: Base material 11: Surface modification layer 12: Spherical protrusion 40: Base material 41: Surface modification layer 42: Bell-shaped protrusion 70: Base material 71: Glass spraying base layer 72: Surface modification layer 80: Cathode 81: Anode 82: Plasma gas 83: Thermal spray powder (supply port)
84: Spraying distance 85: Base material 86: Glass sprayed film 87: Power supply 90: Cathode 91: Anode 92: Plasma gas (supply port)
93: Thermal spray powder (supply port)
94: Spraying distance 95: Base material 96: Glass sprayed film 97: Plasma gas (supply port)
98: Main power supply 99: Auxiliary power supply 100: Substrate 101: Bell-shaped island-shaped protrusion with hemispherical upper part 102: Bell-shaped island-shaped protrusion with rounded upper part 103: Width of bell-shaped island-shaped protrusion 104: Height of bell-shaped island-shaped protrusion 110: Base material 111: Disc-shaped island-shaped protrusion 112: Width of disk-shaped island-shaped protrusion 113: Height of disk-shaped island-shaped protrusion 120: Substrate with negative roughness skewness 121 : Bell-shaped island-shaped protrusions 130: Base material with positive skewness of roughness 131: Bell-shaped island-shaped protrusions 132: Portions where some of the bell-shaped island-shaped protrusions bounced 133: Pore 140: Base material 141: High melting point Material 142: Material having a low melting point 143: Bell-shaped island-shaped protrusion 150: Thermal spray gun 151: Thermal spray frame 152: Thermal spray powder 153: Unmelted portion of flying spray particles 154: Melted portion of flying spray particles 155: Flight Morphism bell island projections nucleus 156 consisting of unmelted portion of the particle: the flight consisting of fused portion of the spray particles bell island projections skin 157: substrate 158: spray distance

Claims (19)

A component used for a film forming apparatus or a plasma processing apparatus, having an island-shaped protrusion having a width of 5 to 300 μm and a height of 2 to 200 μm on a base material of the component, and the island-shaped protrusion is formed of glass. , their shape, spherical shape, the shape of a sphere is missing, hemispherical, be those bell shape or chevron-shaped, or two or more of these is mixed, rounded overall shape, each projection An island-shaped protrusion-modified part that is isolated on a base material and has no film formed as a whole by connecting the protrusions to each other , and the number of island-shaped protrusions is 20 to 5000 / mm ² . Island projections, island-shaped protrusions modified component according to claim 1 Symbol mounting is formed on a glass sprayed film formed on the substrate. The island-shaped projection modified component according to claim 2, wherein the glass sprayed film does not have a cavity of 100 µm or more, and the surface roughness Ra of the glass sprayed film is 1 to 5 µm. Island projection-modified part as claimed in claim 1, wherein the glass forming the island-shaped projections is quartz glass. 4. The island-shaped projection modified component according to claim 2 , wherein the sprayed film is quartz glass. Plasma spraying is performed on the surface of the base material or the glass sprayed film formed on the base material so that the protrusion forming raw material supply amount is 1 to 20 mg / cm ² with respect to the surface area of the surface to provide island-like protrusions. The method for producing a protrusion-modified part according to claim 1, wherein: A film forming apparatus using the island-shaped protrusion-modifying component according to claim 1. 6. A plasma etching apparatus using the island-shaped projection modified component according to claim 1 in a portion where a film is deposited or etched by plasma etching. 6. A plasma cleaning apparatus using the island-shaped projection modified component according to claim 1 in a portion where a film is deposited or etched by reverse sputtering. A component used for a film forming apparatus or a plasma processing apparatus, having an island-shaped protrusion having a width of 5 to 300 μm and a height of 2 to 200 μm on a base material of the component, wherein the island-shaped protrusion is ceramic and / or It is made of metal and has a mountain shape and / or bell shape, rounded as a whole shape, each protrusion is isolated on the base material, and the protrusion is connected to each other to form a film as a whole And the number of island-shaped protrusions is 20 to 5000 / mm ² Is an island-shaped projection modified part. The island-shaped projection modified part according to claim 1, wherein an average value of a ratio of height to width (height / width) of the island-shaped projection is 0.3 to 1.5. The island-shaped protrusion-modified component according to claim 10 or 11, wherein the surface of the substrate on which the island-shaped protrusions are formed has a surface roughness Ra of 5 µm or less. The island-shaped protrusion-modified component according to any one of claims 10 to 12, wherein the island-shaped protrusion is made of a material having a different melting point, and a material having a low melting point wraps the material having a high melting point. Protrusions are provided by colliding on a substrate with a supply amount of 1 to ²⁰ mg / cm ² with respect to the surface area of the surface in a semi-molten state with the protrusion-forming raw material powder on the substrate surface, The manufacturing method of the protrusion modification component in any one of Claims 10-13. Prepare a powder containing a material with a low melting point and a material with a high melting point as the thermal spraying powder. During spraying, the material with a low melting point is completely melted. The method for producing an island-shaped protrusion-modified part according to claim 10, wherein the island-shaped protrusion-modified component is caused to collide with the island. 16. The method for manufacturing an island-shaped protrusion-modified part according to claim 14 or 15, wherein the island-shaped protrusion is formed on the substrate by a thermal spraying method, and further heat-treated. The film-forming apparatus using the components in any one of Claims 10-13 in the part in which a film | membrane is deposited by PVD or CVD. A plasma etching apparatus using the component according to claim 10 at a portion where a film is deposited or etched by plasma etching. A plasma cleaning apparatus using the component according to claim 10 at a portion where a film is deposited or etched by plasma etching.

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