KR100614741B1 - Silica glass jig used in process for manufacturing semiconductor and method of manufacturing silica glass jig - Google Patents

Abstract

In the silica glass jig used in the process of manufacturing a semiconductor, irregularities of 0.1 to 20 µm exist as a center line average roughness Ra on a part or all of the surface thereof, and the surface state changes even with a slight surface layer etching treatment. As a silica glass jig characterized by the above-mentioned, there is no generation of particles that contaminate the semiconductor element during use, and furthermore, there is little variation in processing conditions even after repeated use. Moreover, the silica glass jig of this invention can be manufactured easily by repeatedly applying to the surface of silica glass the process by a physical surface removal means and a chemical surface removal means two or more times.

Description

SILICA GLASS JIG USED IN PROCESS FOR MANUFACTURING SEMICONDUCTOR AND METHOD OF MANUFACTURING SILICA GLASS JIG}

The present invention relates to a silica glass jig used in a semiconductor manufacturing process, and more particularly, to a silica glass jig having a fine unevenness on the surface and a small change in the surface state for slight surface layer etching.

Silica glass jigs are used in various processes such as diffusion processes, vapor phase growth processes, etching and ashing processes in the manufacture of semiconductor devices. The surface of this silica glass jig is treated with sandblasting or grinding, which has an uneven finish with irregularities, or a smooth and transparent finish such as flame polishing called mirror polishing or quenching finishing. Although it selects suitably by the etc., the jig | tool which has the transparently finished surface so that washing | cleaning etc. is easy and it is hard to become dirty is used a lot. Among them, in the diffusion process, the gas phase growth process, especially the gas phase growth process, for example, a polysilicon film is grown on a semiconductor device by CVD (Chemical Vapor Deposition) method, but the polysilicon film is also attached to the transparent glass-finished silica glass jig. It accumulates as a product, it peels off, becomes a particle, and contaminates a semiconductor element. Therefore, it was necessary to remove the by-products regularly. For the removal, a solution containing hydrofluoric acid and nitric acid is generally used, but the surface of the smooth jig is also etched simultaneously, resulting in a rough surface, a change in surface state such as surface area, and suddenly a change in the amount of adhesion of the by-products. The consumption amount of the gaseous reaction gas consumed also fluctuates, making it difficult to control the growth amount of the polysilicon film in the semiconductor device. Therefore, it was planned to form fine irregularities on the surface of the jig by sandblasting, and to actively catch the byproducts to prevent the generation of particles. Fine particles of silica glass scattered from the damage portion of the particles during use, and particles were generated to contaminate the semiconductor device. In addition, when the by-products become thick, breakage due to thermal expansion difference between silica glass and polysilicon occurs, and for the prevention, a jig having a transparent surface is cleaned by gas etching or wet etching before use of the jig. As in the case of the by-products need to be removed on a regular basis, there was a problem such that the fine uneven surface is etched at the same time to change the surface state.

This problem was the same in the etching process without remaining in the diffusion into the semiconductor element or the vapor phase growth step. In other words, in the process of etching or ashing using plasma or the like while flowing the processing gas, by-products may be deposited on the silica glass jig and peeled to generate particles. As a result, fine concavities and convexities were formed on the surface to actively capture the by-products and prevent the generation of particles. However, due to damages such as processed fired layers or microcracks generated during the processing of unevenness, there have been problems such as fine particles of silica glass scattering during use, resulting in particles contaminating semiconductor devices. In particular, in dry etching, etching of the surface of the silica glass jig is very similar to that of the hydrogen fluoride-containing solution, so that the surface state changes significantly, making it difficult to control the etching process itself of the semiconductor element.

In order to solve the above problem, a machined jig is etched with a hydrogen fluoride-containing solution to open microcracks, and a silica glass jig (Japanese Patent Laid-Open No. 10-59744) or a silica glass jig with a surface of microcracks. After the surface is roughened by machining, it is treated with a solution containing hydrogen fluoride and ammonium fluoride, and a groove having a width of 0.5 to 50 μm at intervals of 20 to 30 μm with a dimple recess of 20 to 300 μm on the surface. A silica glass jig (Japanese Laid-Open Patent Publication No. 2002-104843) has been proposed in which a small projection having a width of 1 to 50 m and a height of 0.1 to 10 m is uniformly formed between the grooves and in the grooves. However, in actual use, all of the above-mentioned jig has a defect such as a large concave shape by use, suddenly the amount of adhesion of the by-products changes or unevenness decreases, and if the use continues to some extent, peeling particles are generated. .

In view of this phenomenon, the inventors have intensively studied, and as a result, the surface roughness of the silica glass jig is set to 0.1-20 µm in terms of the centerline average roughness Ra, and the surface state changes even with a slight surface layer etching treatment. By doing this, it was found that there was no peeling of the by-products and scattering of fine debris of the silica glass, and there was little change in the consumption of the processing gas and the control of the treatment in each step was easy. The silica glass jig has been found to be easily manufactured by alternately repeating a specific physical surface removal means and a specific chemical surface removal means several times, thereby completing the present invention. In other words

An object of the present invention is to provide a silica glass jig that does not generate particles that contaminate a semiconductor element during use and that does not vary processing conditions even after repeated use.

Moreover, an object of this invention is to provide the manufacturing method of the said silica glass jig.

1 is a 500 times photograph of the jig surface for dry etching of Example 1 observed with a microscope.

FIG. 2 is a 500-fold photograph of the jig surface for dry etching of Example 1, observed under a microscope after immersion in 3.5 mass% hydrofluoric acid for 16 hours.

Figure 3 is a photograph 500 times the observation of the jig surface for dry etching of Example 1 with a scanning electron microscope

4 is a 200-fold photograph of the wafer boat of Example 2 observed with a scanning electron microscope;

5 is a photograph of 1,000 times the wafer boat of Example 2 observed with a scanning electron microscope;

Fig. 6 is a 200-fold photograph of the wafer boat of Example 2 observed with SEM after 16 hours of etching test with 20 ° C. and 3.5% hydrofluoric acid solution.

FIG. 7 is a 1000-fold photograph of the wafer boat of Example 2 observed with SEM after 16 hours of etching test with 20 ° C. and 3.5% hydrofluoric acid solution.

8 is a 200-fold photograph observing the wafer boat of Comparative Example 2 with SEM.

9 is a 1000-fold photograph of the wafer boat of Comparative Example 2 observed with SEM.

FIG. 10 is a 200-fold photograph of a wafer boat of Comparative Example 2 observed with SEM after 16 hours of etching test with 20% and 3.5% hydrofluoric acid solution.

FIG. 11 is a 1,000-fold photograph of a wafer boat of Comparative Example 2 observed with a SEM boat of a wafer boat after etching test for 16 hours with 20 ° C. and 3.5% hydrofluoric acid solution. FIG.

In the silica glass jig to be used in the process of manufacturing a semiconductor, the present invention has unevenness of 0.1 to 20 µm in the center line average roughness Ra on a part or all of the surface thereof, The present invention relates to a silica glass jig and a method of manufacturing the same, wherein the change is small.

The silica glass jig of the present invention is a jig used in a process for manufacturing a semiconductor device, such as a core tube, a wafer mounting boat, an etching and ashing chamber, and the center line average roughness Ra on a part or all of its surface. This is a jig having a small unevenness of 0.1 to 20 µm and a small change in the surface state with respect to a slight surface layer etching treatment. The small change in the surface state is etched with a hydrofluoric acid solution having a concentration of 3.0 to 4.0% and a liquid temperature of 17 to 23 DEG C for 15 to 17 hours, and a center line average roughness based on JISB0601 on the surface before etching. It is good to measure by the surface roughness measuring device of the stylus type which R of needle tip is 2-10 micrometers, and the change rate of the center line average roughness shall be 50% or less. That is, the surface of the silica glass jig changes due to the actual etching, for example, etching with plasma gas, but specifically Ra increases in the initial stage, but the magnitude of the change indicates that the change of the surface state is small. Regarding the rate of change of the center line average roughness, if the rate of change is 50% or less, the change in Ra is small even in actual use. If the concentration of the hydrofluoric acid solution is less than the above range, the change takes too long to be efficient, and if it exceeds the above range, the initial change rate is faster and the determination time is shorter, but the measurement object is removed from the solution, and the surface is replaced with water. An error occurs until the etching is stopped. In addition, the temperature of 17-23 degreeC of a hydrofluoric acid solution is employ | adopted because the temperature is the most common.

The etching process time of 15 to 17 hours is a time for obtaining a highly accurate rate of change for determination. In measuring the change rate, it is important to use a stylus type surface measuring apparatus having a R of 2 to 10 탆 at the tip of the stylus part based on J1SB0601. The reason for using the stylus type surface measuring apparatus having a R of 2 to 10 µm at the tip of the stylus portion is that microcracks whose surface state changes in the initial state of the silica glass jig during actual use are etched. Is enlarged or the jagged irregularities on its surface cause a change in shape by the etching treatment and are greatly changed. In the non-contact type measuring device, for example, the measuring device using the reflected light of the laser, the center line average roughness calculated from the measured shape is correct, but the narrow valley part which is immediately filled by the by-product during use is also detected. It is hard to know big state change that process condition changes. By using the measuring method using this stylus type surface measuring apparatus, it becomes easy to capture not only the change of a convex part, but also the change of the valley part which is especially sensitive to the adhesion situation of a by-product. The R of the tip of the contact portion is 2 to 10 µm, from 2 µm, which is a range not detecting fine valleys, to 10 µm in which substantial irregularities can be determined, thereby making it easy to change the surface state based on actual use. Can be measured.

In actual use of the silica glass jig, there is an appropriate capture amount of by-products according to the use process. For example, in the case of the CVD process, the excess gas of the film growth on the wafer is a dry etching process by plasma or the like. The etched reaction gas makes the surface of the silica glass jig rough, thereby trapping and depositing it on the jig as more by-products. If the deposition of by-products is too large, the gas forming the film on the wafer is reduced more than necessary to inhibit film growth or etching. On the other hand, when there is little trapping, a particle will generate | occur | produce by peeling etc., and the roughness and state of the silica glass jig by etching at the time of use change from an initial state, and raise the same problem as the above. The surface irregularities of the silica glass jig may have a jagged or trapezoidal convex portion in which jagged irregularities and irregular, acute valleys are continuous, but all have sharp edges due to etching at the time of actual use. It becomes uneven | corrugated shape of big rice bowl which became large, and changes with a big change from an initial state, such as the ability of capturing by-products. In addition, when the rice-shaped irregularities are formed from the initial state, since the surface area is small, the capturing ability of the by-products cannot be tolerated in practical use, and the sharpened portions of the rice-shaped edges fall further to generate particles. do. Therefore, in the silica glass jig of this invention, the unevenness | corrugation of 0.1-20 micrometers exists in part or all of the surface by center line average roughness Ra. The presence of this unevenness ensures the capture of by-products, and can suppress the peeling of the film. Preferably, the concave-convex is made into a multi-layer structure in which a large concave-convex concave and a fine shallow rice-shaped concave portion are formed on the surface thereof. By having this multiple structure, the unevenness | corrugation which can capture the by-product of thickness required by large wavy unevenness | corrugation which is hard to change by slight etching can be ensured.

By presenting the fine shallow rice-shaped irregularities in the larger wavy irregularities, the captured by-products can be fixed without peeling off, thereby obtaining a jig having a stable surface. Particularly preferably, the shallow rice-shaped recesses are not convex in which the depth of the bottom is smaller than the edge diameter of the recesses and the edges of the boundary between adjacent recesses are acute. Thereby, even if the recess is etched at the time of use, the vicinity of the edge portion is equally deteriorated, and it is possible to prevent the projection-shaped trimmer from being easily dropped off at an acute angle between the adjacent recesses.

The silica glass jig of the present invention can be produced by repeatedly applying two or more times alternately the physical surface removal means and the chemical surface removal means. Preferably, it is preferable to select treatment conditions such that the surface roughness formed by the physical surface removal means is sequentially reduced.

The physical surface removal means means a grinding treatment with a fixed abrasive grain grinding wheel, a polishing treatment with glass grinding particles, a blast treatment with glass grinding particles, a treatment with liquid honing or a combination thereof. Specific examples of the fixed abrasive grinding wheel include resin bonded diamond grinding wheels, and the like. The glass grinding particles include silica and SiC. As the treatment by liquid honing, the glass grinding particles are dispersed in a liquid. Flushing treatment; and the like. In this physical surface removal means, a damage layer such as a worked calcined layer or microcracks is formed on the surface of the silica glass, and fine particles of the silica glass are scattered when the jig is used to generate particles. In addition, heterogeneous erosion occurs at the time of the etching treatment, deep grooves are generated due to the incomplete opening of the microcracks, and the surface state is greatly changed, and it is necessary to change the processing conditions such as the CVD process or the etching process. However, by applying the chemical surface removal means following the physical surface removal means, removal of the processed plastic layer or opening of microcracks results in less generation of particles, and less fluctuations in the surface state. When the removal amount of the surface layer is small, the removal of the processed fired layer and opening of the microcracks are not sufficiently performed. Therefore, when a sufficient amount of the work hardening layer formed by the physical surface removal means or the damage layer having microcracks is to be sufficiently removed, the edges of the outer circumference sharpened at the large grooves, the rice-air-shaped or the mortar-shaped recesses There is a lot. Particularly, fine glass fragments are likely to scatter from the edges of the outer circumference. Although there is a treatment method described in Japanese Patent Laid-Open No. 2002-104843 as a treatment method in which the edges of the outer edges are not sharpened, this method does damage such as processed plastic layers or microcracks formed by physical surface removal means. Insufficient removal of the layer results in a large change in the surface state during the etching process. In addition, when etching in actual use proceeds, many concave portions having sharp edges on the outer circumference appear and particles are likely to be generated.

In the manufacturing method of the present invention, after the first physical surface removing means forms a surface on which microcracks on the surface are opened by chemical surface removing means, for example, a surface having a large number of mortars and rice irregularities, Again, by applying the physical surface removal means to equalize the acute angles of the irregularities in the shape of a wave, and by applying the chemical surface removal means to open the processed plastic layer or the remaining microcracks remaining on a relatively flat surface. The physical surface removal means and the chemical surface removal means are preferably applied repeatedly two or more times. Thereby, the jig | tool with a small change of the surface state of the silica glass jig in use can be obtained. The physical surface removing means is more preferably selected from the following physical surface removing means such that the surface roughness becomes smaller than the first. By this, only the damage and micro cracks of the next physical surface removal means can be easily opened to the next chemical surface removal means within the range that the shape of the large wavy concave-convex unevenness is not greatly changed. It can be set as the multiple structure which has many rice ball-shaped recessed parts on the surface of the uneven | corrugated shape. For example, grinding particles having a relatively large particle size are first used, and grinding particles having a relatively small particle size are used in the following removal means. In that case, a combination of physical surface removal means which combines the grinding treatment with the fixed abrasive grinding wheel, followed by the polishing treatment with the glass grinding particles, or the like can also be employed. For example, sandblasting treatment with SiC glass grinding particles of # 600 may be applied after using the fixed abrasive grinding wheel including diamond grinding particles of # 120 first.

Examples of the chemical surface removal means used in the present invention include a treatment with a solution containing hydrogen fluoride. Preferably, the chemical surface removal means after the last physical surface removal means further contains ammonium fluoride in the solution. It is good. As a result, the structure is not clear, but, for example, sharp protrusions or other acute angle protrusions formed on the outer periphery of the rice-shaped or mortar-shaped recess formed by the chemical surface removal means are removed and smoothed. Uneven surface can be made. This is because crystals formed by the reaction between hydrogen fluoride, ammonium and silica glass frequently occur at the bottom of a rice ball shape, for example, and do not occur at the protrusions or immediately lose the crystals absorbing the protrusions. It is thought that it becomes the round shape which does not have an acute angle part by etching-removing. More preferably, it is preferable to disperse the fine particles of any one or combination of resins, silicas, or ceramics having a particle diameter of 10 to 200 µm in the solution containing hydrogen fluoride. By disperse | distributing these microparticles | fine-particles, the damage layer of a jig surface is easy to remove, the ability to form fine unevenness | corrugation becomes high, and a manufacturing procedure can be simplified. In addition, the efficiency of further processing can be improved by adding ultrasonic vibration and stirring means.

The silica glass jig of the present invention has the effect of being able to process a stable and high quality semiconductor element with little generation of particles at the time of use, and almost no change in processing conditions even after repeated use. In addition, the silica glass jig can be easily manufactured by repeatedly applying a specific physical surface removing means and a chemical surface removing means two or more times, and its industrial value is high.

Best Mode for Carrying Out the Invention

Next, although the Example of this invention is described, this invention is not limited at all by this. In addition, the centerline average roughness Ra of the following Example 1 and the comparative example 1 was measured by the surface roughness measuring instrument (surfcom300B by Tokyo Precision Co., Ltd.). In Examples other than that, the surface roughness measuring instrument (SJ-400) of Mitutoyo Co., Ltd. was used.

Example 1

A 300 mm diameter quartz glass surface was ground with a resin bond grinding wheel containing diamond grinding particles of # 300 to prepare a disc-shaped dry etching jig. The centerline average roughness Ra of the obtained jig was 1.2 µm. This jig was immersed in 50% hydrofluoric acid solution for 10 minutes. The centerline average roughness Ra of the obtained jig was 2.8 micrometers. Subsequently, the jig was subjected to surface removal with a resin-bonded grinding wheel of SiC grinding particles of # 1000, with a center line average roughness Ra of 0.5 µm, 15 mass% hydrogen fluoride, 15 mass% ammonium fluoride, and 50 mass% acetic acid. And the treatment liquid made of water for 1 hour. The centerline average roughness Ra at that time was 1.4 µm. The jig was immersed in a 3.5% by mass hydrofluoric acid solution at 20 ° C. and the change of Ra was examined. The surface photograph observed with the microscope of the said 0 hour time is shown in FIG. 1, and the surface photograph observed with the microscope after the etching process for 16 hours is shown in FIG. In addition, the photograph observed with the scanning electron microscope at 0 hours is shown in FIG.

Comparative Example 1

The quartz glass jig similar to Example 1 was ground with a resin bond grinding wheel containing diamond grinding particles of # 300 to prepare a disc for dry etching. The centerline average roughness Ra of the obtained jig was 1.2 µm. This jig was subsequently immersed in 10% hydrofluoric acid solution for 10 minutes. Ra at that time was 1.3 micrometers. This jig was examined as in Example 1, and the change in surface roughness caused by 3.5% by mass of hydrofluoric acid was examined.

0 hours 4 hours 8 hours 16 hours Example 1 Ra 1.4 μm 1.8㎛ 1.9 μm 1.9 μm Rate of change 0% 29% 36% 36% Comparative Example 1 Ra 1.3 μm 1.9 μm 2.8 μm 3.3㎛ Rate of change 0% 46% 115% 130%

As shown in Table 1, in the silica glass jig of the present invention of Example 1, the change in the surface state such as Ra was very small in the etching test of the 3.5 mass% hydrofluoric acid solution. Therefore, the jig according to Example 1 and Comparative Example 1 was actually put into a plasma dry etching apparatus of CF ₄ / Ar gas and 2 kw, and 5 batches were processed in the jig of Example 1, whereby the number of particles generated was Neither batch was less than ten. On the other hand, in the jig of the comparative example 1, 50 or more large particles generate | occur | produced in the 3rd arrangement | positioning, and the use was stopped. In addition, Ra after each use was 2 micrometers in the jig of Example 1, and 5.2 micrometers of the jig of the comparative example 1, and there existed a big gap similarly to the etching test by 3.5 mass% hydrofluoric acid solution. Moreover, when the etching rate of the process wafer of the 5th batch of Example 1 and the 3rd batch of Comparative Example 1 was compared, the jig of Comparative Example 1 was small with respect to the jig of Example 1.

Example 2

A vertical vapor phase wafer boat corresponding to a 150 mm diameter silicon wafer was prepared. The wafer boat was sandblasted with # 150 silicon carbide abrasive particles, and then 20 minutes with 15% hydrofluoric acid solution, followed by sandblasting with # 600 silicon carbide grinding particles. Then, it processed for 1 hour with the process liquid which consists of 14 mass% hydrogen fluoride, 12 mass% ammonium fluoride, and water. The surface of the obtained wafer boat was image | photographed with the scanning electron microscope (SEM). The results are shown in FIGS. 4 and 5. The roughness of the wafer boat surface was 2.1 占 퐉 with a centerline average roughness Ra. As shown in FIG.4,5, it was a multiple structure in which the shallow recessed part was formed in the surface of a large wavy concavo-convex. The wafer boat was subjected to an etching test for 16 hours with 20 ° C. and 3.5% hydrofluoric acid solution. 6 and 7 show photographs taken by SEM of the surface of the wafer boat after the test. The larger wavy recess was slightly wider than before, reducing the number, but was multi-structured. Ra at this time was 2.1 micrometers. Further, the wafer boat was used in the actual vapor phase growth process of silicon nitride to deposit a 2 탆 film. For each cumulative growth in the growth step, one hour of washing with 4% hydrofluoric acid solution was repeated five times. Ra of the surface after use was 2.5 micrometers.

Comparative Example 2

The wafer boat similar to Example 2 was sandblasted with silicon carbide abrasive grains of # 150, and sandblasted with silicon carbide abrasive grains of # 600. Next, the hydrofluoric acid solution at 10% was treated for 1 hour. The surface of the obtained wafer boat was image | photographed with the scanning electron microscope (SEM). The results are shown in FIGS. 8 and 9. The roughness of the wafer boat was 2.2 탆 with a centerline average roughness Ra. This wafer boat was subjected to an etching test for 16 hours with 20 ° C and 3.5% hydrofluoric acid solution in the same manner as in Example 2. 10 and 11 show photographs taken by SEM of the surface of the wafer boat after the test. However, the surface of the wafer boat was significantly different from the surface of FIG. 6 in which a large concave shape was formed with acute angled edges, and Ra was 4.8 µm. In addition, the wafer boat was used in the actual gas phase growth process of silicon nitride, and washing was repeated 5 times for 1 hour with 4% hydrofluoric acid solution for each cumulative growth of the film of 2 µm. Ra of the surface after use was 5.1 micrometers. Also, from the third time, the growth film thickness decreased on the sudden wafer, and an increase in particles on the processed wafer was observed.

The silica glass jig of the present invention does not generate particles that contaminate the semiconductor element during use, and the processing conditions do not change even after repeated use, so that the core tube, wafer mounting boat, etching and ashing chamber, and ring are used. It can be usefully used as a plate.

Claims (11)

In the silica glass jig used in the process of manufacturing a semiconductor, a large wavy irregularities of 0.1 to 20 µm exist on the surface with a centerline average roughness Ra, and a plurality of fine shallow rice-shaped recesses are formed on the surface. Silica glass jig made of a multi-layer structure, characterized by a small change in the surface state for a light surface etching treatment. The method of claim 1, A silica glass jig, wherein the fine shallow rice-shaped recesses are shallower with a smaller depth of the bottom than the edge diameter of the recesses, and the edges of the boundary between adjacent recesses are acute. The method according to claim 1 or 2, The slight surface layer etch treatment showed a slight change in the surface state, the surface of the jig was etched for 15 to 17 hours with a hydrogen fluoride solution having a concentration of 3.0 to 4.0% and a liquid temperature of 17 to 23 ° C, and JISB0601 of the surface of the jig before etching. The silica glass jig characterized by measuring the center line average roughness Ra according to the above by a stylus type surface roughness measuring device in which the tip of the tip of the tip is in the range of 2 to 10 µm, and the change rate of the center line average roughness is 50% or less. . After the unevenness is formed on the surface of the silica glass jig by physical surface removal means, the step of applying the chemical surface removal means of the solution containing hydrogen fluoride is repeated two or more times, so that the large wavy irregularities on the surface of the silica glass jig are performed. And a plurality of fine rice ball-shaped recesses formed on the surface thereof. The method of claim 4, wherein Silica glass jig manufacturing method characterized in that the irregularities formed by the physical surface layer removal means are sequentially reduced in the later step. The method of claim 4, wherein A method for producing a silica glass jig, characterized in that the unevenness formed by the first physical surface removal means is in the range of 0.1-20 탆 or more with the center line roughness Ra. The method according to any one of claims 4 to 6, Manufacture of silica glass jig, characterized in that the physical surface removal means is any one of a grinding treatment with a fixed abrasive grinding stone, a polishing treatment with glass grinding particles, a blast treatment with glass grinding particles, a liquid honing treatment or a combination thereof. Way. The method of claim 4, wherein A method for producing a silica glass jig, wherein the chemical surface removal means performed after the final physical surface removal means is a treatment with a solution containing hydrogen fluoride and ammonium fluoride. The method of claim 4, wherein At least one of the chemical surface removal means is a process for producing a silica glass jig, characterized in that the treatment by a solution containing hydrogen fluoride in which any one of the fine particles of resin, silica or ceramic having a particle diameter of 10 ~ 200㎛. . The method of claim 4, wherein A method for producing a silica glass jig, further comprising ultrasonic vibration or stirring means after the last chemical surface removal means is applied. delete