JP2005277333A - Ceramic member for semiconductor manufacturing equipment, and processing container and semiconductor manufacturing equipment using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem in a conventional ceramic member for semiconductor manufacturing equipment which has a roughened surface, using a sandblast device, where generation of particles occur due the drop out of grains from the member, and drop off of deposition film components adhered on a surface due to the separation of the grains. <P>SOLUTION: A ceramic member for semiconductor manufacturing equipment has a surface to be exposed to a corrosive gas, wherein at least the surface is formed from a ceramic base 1 and a plurality of granular ceramic bodies 2 deposited on the surface. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a ceramic member used for a film forming apparatus such as CVD or PVD or an etching apparatus in a semiconductor manufacturing apparatus, and particularly used for an inner wall of a processing container having surface irregularities to prevent generation of particles. The present invention relates to a member and a processing container.

  6A and 6B show an example of a conventional processing container for a semiconductor manufacturing apparatus, wherein FIG. 6A is a schematic cross-sectional view, and FIG. 6B is a partial enlarged cross-sectional view.

  Since this processing container 31 is used in a film forming apparatus such as CVD or PVD, an etching apparatus, or the like, it is made of a corrosive gas used in a semiconductor manufacturing apparatus or a ceramic such as alumina having corrosion resistance to the plasma. Thus, the inner surface is roughened to form the uneven portion 32 to improve the durability.

  The reason for roughening the surface is that in the film forming process using the CVD or PVD method of the semiconductor device manufacturing process, the film component to be formed adheres to the inner wall surface of the processing vessel 31 surrounding the apparatus, and this is later peeled off as particles and Therefore, the adhesion area is increased, and the anchor effect with the roughened concavo-convex portion 32 is utilized to make it difficult to peel off.

  Further, as a method of roughening the member used for the inner wall, as shown in FIG. 7, the sintered ceramic member 41 has abrasive grains 42 such as green carbon (hereinafter referred to as GC) made of fused alumina or silicon carbide. A general method is to obtain a roughened surface by hitting the surface of the ceramic member 41 in contact with the corrosive gas with the sandblasting device 43. As another method, in the cold isostatic pressing method, the surface of the molding die is roughened in advance using the sandblasting device 43, and this is transferred to the surface of the molded body at the time of molding. A method, a method of roughening the surface of the ceramic member 41 with an etching solution, and the like have been proposed.

  The surface roughness of the concavo-convex portion 32 is preferably set to 1 μm or more in Ra, and may be processed at the stage of the molded body, or the surface roughness may be set to the burned surface. It has been proposed (see Patent Documents 1 and 2).

In addition, it has also been proposed to roughen the surface by forming the processing vessel 31 from a porous sintered body (see Patent Document 3).
JP 2000-247726 A JP 2000-191370 A JP 2003-234300 A

  However, in the case of a rough surface obtained by using a sandblasting device 43 as in the prior art, a hard surface 42 is made to collide with the surface of the ceramic member 41 after sintering as shown in FIG. In order to obtain, there are an infinite number of cracks 44 at the interface between the crystal particles constituting the ceramic member 41, and the particles are removed from the dotted line portion of FIG. 45 was a cause of particles.

  Furthermore, the abrasive grains 42 used in the sandblasting device 43 bite into the crack 44 portion, and the biting is loosened and dropped by the vibration of the device, or the inner wall of the device is heated and expands, and the opening portion of the crack 44 widens. There is a problem that the biting abrasive grains 42 fall and the dropped abrasive grains 42 become particles.

  Further, in the method of roughening by etching, although the cause of particle generation is less than the method using the sandblasting device 43 as described above, the processing time for obtaining a predetermined roughened surface is long and practical. Absent.

  In addition, it has been proposed to process the molded body and to raise the surface roughness to 1 μm or more by Ra, but the rough surface obtained by cutting is not easily reflected in the sintered body as it is. There was a problem that the obtained rough surface was uneven and reproducibility was poor.

  Further, when the ceramic member is composed of a porous sintered body, the strength of the member is low, the problem that corrosive gas permeates through the porous sintered body, and if the pores are small, The anchor effect is difficult to obtain, and the deposited film peels off, resulting in a problem of becoming particles.

  In view of the above problems, a ceramic member for a semiconductor manufacturing apparatus according to the present invention is a ceramic member for a semiconductor manufacturing apparatus having a surface portion exposed to a corrosive gas, and at least the surface portion is covered with a ceramic base material and the surface thereof. It is characterized by comprising a plurality of attached granular ceramic bodies.

  The ceramic member for a semiconductor manufacturing apparatus according to the present invention is characterized in that a plurality of layers of the granular ceramic body are applied.

  Furthermore, the ceramic member for a semiconductor manufacturing apparatus according to the present invention is characterized in that the granular ceramic body is composed of at least two kinds of granular ceramic bodies having a small diameter and a large diameter.

  Furthermore, the ceramic member for a semiconductor manufacturing apparatus according to the present invention is characterized in that the granular ceramic body is granular having a maximum diameter of 0.3 to 5.0 mm.

  Moreover, the processing container of the present invention is characterized in that it is a processing container in which the ceramic member for a semiconductor manufacturing apparatus is disposed on an inner wall.

  The semiconductor manufacturing apparatus of the present invention is characterized by using the above-mentioned ceramic member for a semiconductor manufacturing apparatus.

  According to the present invention, the surface of a member is roughened by arranging a plurality of granular ceramic bodies in layers on the surface of a ceramic member for a semiconductor manufacturing apparatus that is exposed to corrosive gases used in semiconductor manufacturing processes and their plasmas. Even if adhesion of a film forming component or the like occurs, peeling hardly occurs due to an anchor effect with a rough surface, and generation of particles can be suppressed.

  Further, by applying a plurality of layers of the granular ceramic body, it is possible to extend the life of the member.

  Further, when the granular ceramic body is composed of at least two kinds of small-diameter and large-diameter granular bodies, it is possible to adjust to a rough surface where better adhesion strength can be obtained.

  Further, by arranging the ceramic member for a semiconductor manufacturing apparatus on the inner wall of the processing container, the generation of particles is reduced and the life of the processing container can be extended.

  Moreover, since the generation of particles is reduced by using the ceramic member for a semiconductor manufacturing apparatus in a semiconductor manufacturing apparatus, it is possible to reduce manufacturing defects caused by the generation of particles.

  Hereinafter, embodiments of a ceramic member for a semiconductor manufacturing apparatus according to the present invention will be described in detail with reference to the drawings.

  1A and 1B show an embodiment of a ceramic member for a semiconductor manufacturing apparatus according to the present invention, wherein FIG. 1A is a partially enlarged view and FIG. 1B is an enlarged schematic view of a surface.

  As shown in FIG. 1A, the ceramic member for a semiconductor manufacturing apparatus according to the present invention is formed by depositing a granular ceramic body 2 on the surface of a ceramic substrate 1 to form an uneven portion 3.

  As a result, the surface of the member can be roughened, and even if deposition of a film forming component or the like occurs, peeling is unlikely to occur due to the anchor effect with the rough surface, and particle generation can be suppressed.

  Here, as the material of the ceramic substrate 1, any ceramic that is generally used can be applied, but alumina ceramic that is used for a semiconductor manufacturing apparatus is particularly preferable.

Any material can be used as the material of the granular ceramic body 2 as long as it is a general ceramic. Among them, alumina, yttria, yttrium aluminum garnet (hereinafter referred to as YAG), aluminum nitride, silicon carbide are applicable. Silicon nitride is good because it is excellent in corrosion resistance against fluorine-based and chlorine-based corrosive gases used in the semiconductor manufacturing process. Furthermore, among the above materials, fluorine-based gases such as SF ₆ , CF ₄ , CHF ₃ , ClF ₃ , NF ₃ , C ₄ F ₈ and HF, chlorine-based gases such as Cl ₂ , HCl, BCl ₃ and CCl ₄ , or It is more preferable to use YAG or yttria ceramics having good corrosion resistance against bromine-based gases such as Br ₂ , HBr, and BBr ₃ . The above YAG and yttria (Y ₂ O ₃ ) are particularly stable because the melting point of the reaction product of fluorine, chlorine and bromine gas is higher than the melting point of the reaction product of other ceramics and corrosive gas. It has corrosion resistance.

  Moreover, as a ceramic material which comprises the ceramic base material 1 and the granular ceramic body 2, it is preferable to use a material having a purity of 95% or more and a primary raw material average particle size of 5 μm or less, and when the purity is lower than 95%, This is because when used as a ceramic member for a semiconductor manufacturing apparatus, the corrosion resistance against corrosive gases and their plasmas is reduced. When the average primary particle size is larger than 5 μm, it is dense if not fired at a higher temperature. This is because it is difficult to achieve the manufacturing cost and the manufacturing cost is greatly increased.

  Furthermore, as the shape of the granular ceramic body 2, any shape can be applied as long as it can be formed, such as a spherical shape, a flat shape, a prismatic shape, a cylindrical shape, and the like. Considering the ease of handling and manufacturing costs, it is more preferable to use a spherical shape.

  Moreover, the granular ceramic body 2 exhibits good corrosion resistance if it is applied as a layer of one or more layers to the ceramic substrate 1, and is preferably applied so that there is no gap.

  A method for depositing the granular ceramic body 2 on the surface of the ceramic substrate 1 will be described later.

  The granular ceramic body 2 is preferably deposited in a plurality of layers as shown in FIGS.

  For example, FIG. 2 shows a case where two layers are deposited, (a) is a partially enlarged view, and (b) is an enlarged schematic view of the surface. By making the granular ceramic body 2 into two layers, since the thickness of the corrosion-resistant layer is thick against the corrosive gas and its plasma, the durability time is doubled. In order to further enhance the corrosion resistance, the number of layers may be increased to deposit a plurality of layers.

  If an attempt is made to increase the durability by simply increasing the thickness of the ceramic substrate 1, it is difficult to uniformly sinter the ceramic substrate 1 by the increased thickness, and the firing time must also be extended. . In addition to this, after producing the ceramic substrate 1 having an increased thickness, a sand blasting process or the like for roughening the surface is required, which significantly increases time and manufacturing cost. By using the present invention, it is possible to extend the durability time and roughen the surface at the same time, and the merit for cost is very large.

  Moreover, although it leads to the extension of endurance time by making it into multiple layers, since it will lead to a cost increase when manufacturing too many layers, it depends on the particle size of the granular ceramic body 2, Is preferably 5 layers or less.

  In addition, as shown in FIGS. 3A and 3B, the granular ceramic body 2 is preferably composed of at least two kinds of granular bodies having a small diameter and a large diameter.

  For example, FIG. 3 shows a case where the granular ceramic body 2 is composed of a small-diameter granular ceramic body 5 and a large-diameter granular ceramic body 4, wherein (a) is a partially enlarged view and (b) is an enlarged schematic view of the surface. Thus, the small-diameter granular ceramic body 5 and the large-diameter granular ceramic body 4, that is, the so-called granular ceramic body 2 mixed with the particle size, are deposited on the surface of the ceramic substrate 1, so that the small-diameter granular ceramic body 4 is spaced in the gap between the large-diameter granular ceramic bodies 4. Since the ceramic body 5 is filled in such a manner as to fill the gap, it is possible to increase the density of the deposition layer as compared with the case where a granular ceramic body having the same diameter is deposited on the surface of the substrate. This makes it possible to further improve the corrosion resistance to corrosive gases.

  The small diameter and large diameter of the granular ceramic body 2 indicate that there is a difference of at least 10 μm or more. More preferably, the small-diameter particles should have a particle size not more than half that of the large-diameter particles. With such a particle size, particularly when the particle shape is spherical, one particle is provided in the gap between the four large-diameter particles. Since the above small-diameter particles are filled, the density of the adherend layer can be further improved.

  Furthermore, each of the above-mentioned granular ceramic bodies 2 is preferably composed of one or more kinds of small-diameter and large-diameter particles from the viewpoint of increasing the density of the deposited layer. Therefore, it is difficult to satisfactorily adhere to the ceramic substrate 1 for reasons such as the arrangement when the ceramic substrate 1 is adhered. Therefore, it is more preferable to fill the gap between one type of large-diameter particles with one or more types of small-diameter particles.

  Further, the granular ceramic body 2 preferably has a maximum diameter in the range of 0.3 to 5.0 mm.

  When the maximum diameter is less than 0.3 mm, the interval between the concavo-convex portions 3 to be formed to prevent peeling of the deposited film forming component becomes narrow, and a good anchoring effect cannot be obtained. Peeling easily occurs. On the other hand, if it is larger than 5 mm, the interval between the concavo-convex portions 3 is too wide and it is difficult to obtain the anchor effect, and the attached film forming component is peeled off.

  Although it depends on the amount of particles generated in the semiconductor manufacturing apparatus using the ceramic member for semiconductor manufacturing apparatus of the present invention, it is possible to obtain a better delamination preventing effect and to make the maximum of the granular ceramic body 2 from the viewpoint of easy production. The diameter range is more preferably 1 to 3 mm.

  The granular ceramic body 2 is not limited to a curved surface with a smooth surface, but can be rough or uneven, as long as it is granular. If the surface is rough and has unevenness, the film forming component is more difficult to peel off, which is favorable.

  Next, the manufacturing method of the ceramic member for semiconductor manufacturing apparatuses of this invention is demonstrated.

  First, a molded body to be the ceramic substrate 1 is prepared. The ceramic base material 1 is prepared by adding a predetermined amount of a molding aid or the like to the ceramic primary raw material powder used for the base material to produce a secondary raw material powder, which is formed by a press molding method or a cold isostatic press molding method (cold).・ I shape it to a required shape and size by a general forming method such as isostatic pressing.

  However, at this time, the molding pressure is molded at a molding pressure of about 50 to 80% of the molding pressure at which a dense body is obtained after firing. This is because the granular ceramic body 2 is later deposited on the surface and molded again by a normal molding pressure to increase the adhesion between the ceramic substrate 1 and the granular ceramic body 2.

  Next, a granular ceramic molded body to be the plurality of granular ceramic bodies 2 is produced. As a forming method to be used, it can be formed by the same method as the manufacturing method of the ceramic substrate 1, and can be formed by an extrusion method as another forming method. However, considering the efficiency of molding and the adjustment of the size of the molded body, it is more preferable to mold by the press molding method. At this time, the molding pressure may be molded at a normal pressure at which a dense body is obtained after firing, but is later arranged in a layer on the surface of the ceramic substrate 1, and is again pressed by cold isostatic pressing at a normal pressure. More preferably, the molding pressure is 50 to 80% of the normal pressure. Moreover, about the particle size and shape of the said granular ceramic molded object, when manufacturing with a press molding method, it performs by adjusting the shaping | molding die to be used. When manufacturing by extrusion molding, the particle diameter is adjusted by adjusting the diameter of the die of the molding machine. As for the shape, since the variation is more severe than that of press molding, it is necessary to align the shape using a rolling granulator after molding.

  Then, the above-mentioned granular ceramic molded body is arranged in layers on the surface of the molded body to be the ceramic substrate 1 obtained as described above, and this is pressed again by a cold isostatic press molding method, and the ceramic substrate is formed. A granular ceramic molded body is pressed and adhered to the surface of the molded body to be the material 1 to obtain an integrated ceramic member molded body for a semiconductor manufacturing apparatus.

  At this time, as a method of disposing the granular ceramic molded body on the surface of the molded body to be the ceramic base material 1 without a gap, for example, as a method using a mold, the surface of the molded body to be the ceramic base material 1 and the mold A rubber mold prepared so as to provide a gap corresponding to the maximum diameter of the granular ceramic molded body is prepared, and this mold is fitted into the molded body to be the ceramic substrate 1 and installed in a part of the mold. In this method, the granular ceramic molded body is introduced from the inlet and filled in the gap between the mold and the surface of the molded body to be the ceramic substrate 1. As another example, the granular ceramic molded body, in which a slurry-like binder having adhesiveness is previously applied to the surface of the molded body to be the ceramic base material 1 and placed in a predetermined container. Is dropped while keeping the distance between the container and the surface of the molded body constant, and is arranged on the surface by the adhesive force of the applied binder. In this method, a plurality of layers can be formed by applying a binder once and arranging the above-mentioned granular ceramic molded bodies, then applying a binder from the top and repeating the arrangement of the granular ceramic molded bodies.

  There are various other methods, but after passing through the above steps, a ceramic base material is re-pressurized by a cold isostatic press molding method using a rubber mold that matches the shape of the molded body of the present invention. By pressing and adhering the granular ceramic body 2 to 1, the molded body of the ceramic member for a semiconductor manufacturing apparatus of the present invention can be obtained.

  Here, general binders such as polyvinyl alcohol and polyethylene glycol are applicable as the binder, and water and organic solvents are applicable as the solvent. As the method for applying the slurry binder, various coating methods such as brushing and spray coating can be applied. However, in consideration of application efficiency and uniformity, spray coating is preferably used. In this way, by arranging the granular ceramic molded body through the binder on the surface of the ceramic substrate molded body, and pressurizing again, it is simply filled in the mold, arranged, and compared with the manufacturing method of repressurizing, The granular ceramic molded body can be more firmly bonded to the surface of the substrate molded body, and the handleability of the molded body is improved.

  Thereafter, the molded body is fired in a predetermined firing furnace at the densification temperature of the ceramic powder used for the ceramic base material 1 and the granular ceramic body 2, and the two are joined and integrated to form the semiconductor manufacturing apparatus of the present invention. A ceramic member is obtained.

  The above-described method is a method in which the ceramic base material and the granular ceramic body are pressed and adhered to each other between the molded bodies, and then fired to be integrated, but the sintered bodies can also be adhered. In this case, an adhesive slurry containing an inorganic binder is applied to the substrate surface in advance, and a granular ceramic sintered body is adhered and arranged on the slurry, and then fired at a predetermined temperature. As a result, the sintered bodies are joined together by the action of the inorganic binder. Thereby, the ceramic member for semiconductor manufacturing apparatuses can be manufactured.

  The ceramic member for a semiconductor manufacturing apparatus thus obtained exhibits good corrosion resistance against a corrosive gas such as fluorine, chlorine or bromine used in the semiconductor manufacturing process. In addition, it is possible to prevent the deposits of film forming components from dropping during film formation on the semiconductor substrate by the anchor effect with the unevenness of the surface, and the generation of particles can be reduced.

  Next, an example of a processing container using the ceramic member for a semiconductor manufacturing apparatus according to the present invention is shown in FIGS. 4A and 4B. FIG. 4A is a schematic cross-sectional view of the processing container, and FIG. The enlarged view of the A section of (a) is shown.

  As shown in FIG. 4, the processing container 6 has a structure in which a granular ceramic body layer 7 in which the granular ceramic body 2 is layered is deposited on the surface of the inner wall exposed to corrosive gas or plasma. Corrosion resistance. Further, the inner wall of the container is roughened by this, and even when the film forming component adheres to the inner wall surface when the film is formed on the semiconductor using the CVD method or the like in the container, The film-forming component does not fall because it forms an anchor effect with the rough wall surface, and the generation of particles in the semiconductor manufacturing apparatus processing container can be reduced.

FIG. 4B shows an example in which the granular ceramic body layer 7 is one layer. However, depending on the required corrosion resistance, it can be divided into two layers, three layers, and a plurality of layers. is there. Furthermore, in the present invention, even if the cross section has a curved shape as shown in FIG. 4A, it is possible to cope with it. Next, an example in which the processing container 6 of the present invention is used in a semiconductor manufacturing apparatus is shown in FIG. Will be described.

FIG. 5 is a schematic sectional view showing an inductively coupled plasma etching apparatus. Reference numeral 10 in the figure is the processing container of the present invention. The processing vessel 10 has a dome shape, and has a rough surface portion 11 on the inner wall surface. A lower chamber 12 made of metal is provided so as to be in close contact with the processing vessel 10, thereby forming the chamber 12. Has been. A support table 13 is disposed in the upper part of the lower chamber 12, and an electrostatic chuck 14 is provided thereon, and a semiconductor wafer 15 is placed on the electrostatic chuck 14. A DC power supply is connected to the electrode of the electrostatic chuck 14, and thereby the semiconductor wafer 15 is electrostatically adsorbed. Further, an RF power source is connected to the support table 13. On the other hand, a vacuum pump 18 is connected to the bottom of the lower chamber 12 so that the inside of the lower chamber 12 can be evacuated. In addition, a gas supply nozzle 16 for supplying an etching gas, for example, CF ₄ gas, is provided above the semiconductor wafer 15 above the lower chamber 12. An induction coil 17 is provided around the processing container 10, and a high frequency of 400 kHz, for example, is applied to the induction coil 17 from an RF power source.

In such an etching apparatus, the inside of the chamber 12 is evacuated to a predetermined degree of vacuum by the vacuum pump 18, the semiconductor wafer 15 is electrostatically adsorbed by the electrostatic chuck 14, and then, for example, CF _{4 is used} as an etching gas from the gas supply nozzle 16. By supplying power to the induction coil 18 from the RF power supply while supplying the gas, an etching gas plasma is formed in the upper portion of the semiconductor wafer 15, and the semiconductor wafer 15 is etched into a predetermined pattern. Note that the anisotropy of etching can be increased by supplying power to the support table 13 from a high-frequency power source.

During such an etching process, the inner surface of the processing vessel 10 is corroded by CF ₄ gas or plasma thereof, and a fluoride film or the like adheres thereto. However, since the processing container 10 is composed of the above-described ceramic member for a semiconductor manufacturing apparatus according to the present invention, the corrosion resistance against plasma is high and deposits are difficult to fall.

  The ceramic member for a semiconductor manufacturing apparatus of the present invention is not limited to the processing container of the semiconductor manufacturing apparatus as shown in FIG. 5, but is applied to all parts as a processing member using a corrosive gas such as an etching apparatus or a CVD film formation. Is possible.

  Examples of the present invention will be described below.

  As an example of the present invention, a ceramic member for a semiconductor manufacturing apparatus as shown in FIGS.

  First, several ceramic substrates made of alumina are prepared. As alumina, a primary raw material powder having a purity of 95% or more and having an average particle diameter of around 1 μm is mixed with a predetermined binder and solvent using a mixing mill, and then mixed with a spray granulator such as a spray dryer. After granulating with an apparatus to make a secondary raw material powder, it is put into a rubber mold to be molded with a cold isostatic press (cold isostatic press) molding apparatus, and then the normal pressure is applied with the molding apparatus. Was molded into a predetermined shape with a molding pressure of 70%. Then, the said molded object was processed into the shape of outer diameter 60mm x thickness 10mm by cutting, and it was set as the ceramic base material.

As a granular ceramic body, a primary material made of alumina, YAG, Y ₂ O ₃ was prepared. The purity is 95% or more, and the average particle size is about 1 μm. Next, the primary raw material is made into a secondary raw material powder through the same steps as the above-mentioned base material, and as shown in Table 1, this is the average particle size (when the number of particle types is two or more, the maximum). Using a press molding machine for each material so as to obtain a spherical shape having a small diameter and a maximum diameter), molding was performed at a molding pressure similar to that of the base material, thereby obtaining a granular ceramic molded body made of three kinds of materials.

  Next, a slurry containing an adhesive binder is applied to the surface of the ceramic base material in advance, and the granular ceramic green body is placed on the ceramic base material until the ceramic base material is covered. Sift out the ceramic body. By repeating this several times, the granular ceramic molded bodies were arranged on the surface of the ceramic substrate molded body in the number of layers as shown in Table 1. In addition, as said slurry, what mixed this using water as a solvent and PVA (polyvinyl alcohol) as a binder was used.

  Thereafter, the above-mentioned granular ceramic body and ceramic base body are put into the prepared rubber mold in such a direction that pressure is applied in the thickness direction, and formed at normal pressure by cold isostatic pressing. A molded body is obtained.

  Thereafter, this compact was fired at 1600 to 1800 ° C. in an atmospheric furnace to obtain a sample of the ceramic member 19 for a semiconductor manufacturing apparatus as shown in FIG. In the figure, 20 indicates a ceramic substrate, and 21 indicates a granular ceramic body.

  As a comparative example, a sample was also prepared in which the surface of a ceramic substrate made of alumina of the same size as the ceramic member 19 for a semiconductor manufacturing apparatus was roughened to a surface roughness (Ra) of 10 μm by a commercially available sandblast apparatus.

  The porosity of the sample of the obtained ceramic member 19 for a semiconductor manufacturing apparatus was measured by the Archimedes method, and a sample having a porosity of 0.1% or less was used as an evaluation sample.

And the corrosion resistance of each sample was evaluated with the RIE (Reactive Ion Etching) apparatus. In the evaluation, plasma is generated with the inside of the apparatus as a Cl ₂ gas atmosphere, and the plasma is exposed to this plasma for 3 hours, and the etching rate per minute is calculated from the weight loss before and after the test. Further, when the etching rate of the alumina sintered body (alumina content 99.5% by mass, sample surface mirror-finished product Ra 0.1 μm) is set to 1, the etching rate of the relative comparison value obtained with this etching rate is etched. The rate ratio.

  In addition, each sample is placed in a predetermined position in the CVD film forming apparatus for 3 days, and after depositing film forming components on its surface, it is taken out from the apparatus and put in a container containing pure water, and the entire container is commercially available. After washing in an ultrasonic cleaner, the sample was taken out and the amount of particles in pure water remaining in the container was measured with a commercially available particle counter.

Table 1 shows the results.

From Table 1, it can be seen that all of the samples (Nos. 1 to 14) of the present invention have an etching rate ratio of 1.15 or less and a particle amount of 220 cm ³ / piece or less, and there is little peeling of the deposited film forming components. It was.

In particular, the samples (Nos. 13 and 14) in which the granular ceramic body is composed of YAG and Y ₂ O ₃ reflect the corrosion resistance of the used material itself, the etching rate ratio is 0.65 or less, and the particle amount is 10 cm. It was found to have excellent corrosion resistance at ³ / piece or less.

In addition, the sample (No. 2 to 4) in which the granular ceramic body was deposited in two layers and three layers had an etching rate ratio of 1.15 or less and a particle amount of 220 cm ³ / piece or less. It was found that there was little peeling.

  Further, it can be seen that the samples (No. 3, 11, 12) in which the granular ceramic body is mixed with two kinds of small diameter and large diameter show particularly good corrosion resistance because the density of the granular ceramic body layer on the surface is improved. . Among them, the sample (No. 3) in which the granular ceramic bodies having two kinds of particle sizes were deposited in two layers showed good values for both the etching rate ratio and the amount of particles.

  Moreover, the sample (No. 6-9) in the range whose maximum diameter of a granular ceramic body is 0.3-5 micrometers is a range with the favorable space | interval of a granular ceramic body, and there are especially few particle amounts.

On the other hand, the sample (No. 15) not coated with the granular ceramic body as a comparative example is roughened by sandblasting the surface, so that the contact area with the corrosive gas is increased and etching is performed. It was found that the rate ratio was as large as 1.22, inferior in corrosion resistance, and the amount of particles was as large as 500 cm ³ / piece.

It is the schematic which shows one Embodiment of the ceramic member for semiconductor manufacturing apparatuses of this invention, (a) is a partial enlarged view, (b) is the enlarged schematic view of the surface. It is the schematic which shows other embodiment of the ceramic member for semiconductor manufacturing apparatuses of this invention, (a) is a partial enlarged view, (b) is the enlarged schematic view of the surface. It is the schematic which shows other embodiment of the ceramic member for semiconductor manufacturing apparatuses of this invention, (a) is a partial enlarged view, (b) is the enlarged schematic view of the surface. It is the schematic which shows an example of the processing container using the ceramic member for semiconductor manufacturing apparatuses of this invention, (a) is a processing container cross-sectional schematic, (b) is an enlarged view which shows the A section of the same figure (a). is there. It is a schematic sectional drawing of the inductively coupled plasma etching apparatus using the processing container which consists of a ceramic member for semiconductor manufacturing apparatuses of this invention. It is the schematic of the processing container for conventional semiconductor manufacturing apparatuses, (a) is sectional drawing, (b) is the elements on larger scale of the figure (a). It is a conceptual diagram which shows a mode that the inner wall surface of the conventional ceramic member for semiconductor manufacturing apparatuses is processed by a sandblast process. It is an expanded sectional view of the inner wall surface of the conventional ceramic member for semiconductor manufacturing apparatuses.

Explanation of symbols

1: Ceramic base material 2: Granular ceramic body 3: Uneven portion 4: Large diameter granular ceramic body 5: Small diameter granular ceramic body 6, 10: Processing vessel 7: Granular ceramic body layer 11: Rough surface portion 12: Chamber 13: Support table 14: Electrostatic chuck 15: Semiconductor wafer 16: Gas supply nozzle 17: Inductive coil 18: Vacuum pump 31: Processing container 41, 51: Ceramic member 32: Concavity and convexity part 42: Abrasive grain 43: Sand blasting device 44: Crack 45: Particle

Claims (6)

A ceramic member for a semiconductor manufacturing apparatus having a surface portion exposed to a corrosive gas, wherein at least the surface portion is composed of a ceramic base material and a plurality of granular ceramic bodies deposited on the surface. Ceramic member for semiconductor manufacturing equipment. The ceramic member for a semiconductor manufacturing apparatus according to claim 1, wherein the granular ceramic body is deposited in a plurality of layers. 3. The ceramic member for a semiconductor manufacturing apparatus according to claim 1, wherein the granular ceramic body is composed of at least two kinds of small-diameter and large-diameter granular bodies. The ceramic member for a semiconductor manufacturing apparatus according to any one of claims 1 to 3, wherein the granular ceramic body is granular having a maximum diameter of 0.3 to 5.0 mm. A processing container comprising the ceramic member for a semiconductor manufacturing apparatus according to claim 1 disposed on an inner wall. A semiconductor manufacturing apparatus using the ceramic member for a semiconductor manufacturing apparatus according to claim 1.

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