WO2022270576A1 - Method for manufacturing fused quartz jig and fused quartz jig - Google Patents

Method for manufacturing fused quartz jig and fused quartz jig Download PDF

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Publication number
WO2022270576A1
WO2022270576A1 PCT/JP2022/025076 JP2022025076W WO2022270576A1 WO 2022270576 A1 WO2022270576 A1 WO 2022270576A1 JP 2022025076 W JP2022025076 W JP 2022025076W WO 2022270576 A1 WO2022270576 A1 WO 2022270576A1
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Prior art keywords
quartz glass
glass jig
less
unevenness
uneven
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PCT/JP2022/025076
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French (fr)
Japanese (ja)
Inventor
大輝 藤田
徹 瀬川
洋一郎 丸子
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信越石英株式会社
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Application filed by 信越石英株式会社 filed Critical 信越石英株式会社
Priority to JP2023530114A priority Critical patent/JPWO2022270576A1/ja
Priority to KR1020237044847A priority patent/KR20240036521A/en
Priority to CN202280042598.3A priority patent/CN117529457A/en
Publication of WO2022270576A1 publication Critical patent/WO2022270576A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass

Definitions

  • the present invention relates to a method for manufacturing a quartz glass jig that forms irregularities without microcracks on the quartz glass surface by chemical treatment, and a quartz glass jig having irregularities formed on the surface.
  • quartz glass Due to its high purity and excellent chemical resistance, quartz glass has traditionally been used as a material for semiconductor processing, optics, physics and chemistry equipment, and decoration. Depending on the purpose of use, the surface of these quartz glass products may be roughened by performing various uneven processing. In particular, by providing unevenness on the inner surface of the furnace core tube used in the semiconductor process, it is possible to prevent peeling of the film such as polysilicon film in LPCVD (Low Pressure Chemical Vapor Deposition) processing and prevent particles generated during wafer heat treatment. It is to be.
  • LPCVD Low Pressure Chemical Vapor Deposition
  • Sandblasting and surface treatment with a mixed liquid of HF/CH 3 COOH/NH 4 F are known as methods for processing the surface of the quartz glass to have unevenness.
  • the sandblasting process described above is a processing method that involves mechanical destruction of the surface, so that microcracks exist on the quartz glass surface, and the presence of these microcracks may cause the generation of particles. It was not effective.
  • Patent Documents 1 to 3 disclose examples in which the surface of quartz glass is processed to be uneven with a surface treatment liquid.
  • prevention of film peeling In the semiconductor process, in order to prevent peeling of a polysilicon film or the like from the surface of quartz glass (hereinafter also referred to as "prevention of film peeling"), the rougher the surface, the less likely the peeling of the film will occur. commonly known.
  • the surface treatment method using a quartz glass surface treatment liquid has problems such as variations in surface roughness and difficult control compared to processing methods such as sandblasting that involve mechanical destruction. Furthermore, due to the state of the surface to be treated when immersed in the surface treatment liquid, the resulting cloudy state due to the formation of unevenness on the surface may be uniform, locally uneven, or inconsistent. There is Due to the presence of such non-uniform portions, the film adhering to the quartz becomes locally brittle, causing problems such as film peeling and the failure to achieve the intended function. Conventionally, when non-uniform unevenness (unevenness) was formed, chemical treatment was repeated to erase the unevenness, but unevenness such as large unevenness, streak-like unevenness, and clusters of small unevenness was eliminated. In some cases, it was difficult to erase, and many times of chemical treatment was required.
  • paragraph 0008 mentions the unevenness of the treated surface, and as a countermeasure therefor, a proposal is made focusing on the Reynolds number Re.
  • the unevenness discussed here is a discussion of the shading of the treated surface when viewed from a position about 1 m away from the treated surface. are working as a solution.
  • quartz glass jigs have also increased in size. Due to the increase in the number of Si wafers processed per batch and the fact that 12-inch size Si wafers have become mainstream, quartz glass jigs have become larger, and quartz glass core tubes, round seals, and top plates have become larger. Since the surface area increases due to the size and length of the film, there is a problem that unevenness has become noticeable on the roughened surface of the surface.
  • Uneven surface cloudiness due to irregular finish unevenness More specifically, the existence of transparent and opaque areas is caused by the uneven ridge-and-valley structure of the surface. It is not preferable because a difference occurs in the adhesion effect of the film adhered to the wafer. Another problem is that if there is unevenness in the finish of the quartz glass jig, a difference in the transmission of heat rays from the heater occurs in the film formation process, causing a temperature distribution. unfavorable from
  • a surface having such non-uniform irregularities has a non-uniform white turbid appearance, and there is concern that film peeling at non-uniform locations is likely to occur.
  • the location and content of the dirt on the surface (for example, oil) are specified, it can be wiped off with an organic solvent such as alcohol or acetone. It has been found to be the most effective and effective remedial measure to remove at least the superficial material from the entire workpiece prior to processing.
  • the present invention has been made in view of the above-described problems of the prior art. In forming unevenness by chemical treatment without microcracks, unevenness is conspicuous even in the case of a large-sized quartz glass jig.
  • the method for manufacturing a quartz glass jig according to the present invention is a method for manufacturing a quartz glass jig in which irregularities are formed on the surface by chemical treatment, and includes a deposit removing step for removing deposits on the smooth quartz glass surface. and a finished surface forming chemical treatment step of forming an uneven finished surface by forming unevenness by the chemical treatment on the quartz glass surface from which the deposits have been removed, wherein the surface roughness Ra of the uneven finished surface is set to 10 or more locations.
  • the uneven finished surface has a glossiness of less than 2 with a 60 degree meter. Further, it is preferable that the average value of the visible light transmittance measured by a tintometer on the unevenly finished surface at 10 or more points is 30% or less and the standard deviation is 1% or less. It is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points.
  • the deposit removal step includes an HF cleaning step of removing deposits on the smooth quartz glass surface using a cleaning liquid containing HF, and after the HF cleaning step, the HF component remaining on the quartz glass surface is diluted and removed with water. and a second removing step of removing the attached moisture and/or the attached solvent remaining on the quartz glass surface after the first removing step.
  • the glass surface layer of the quartz glass surface is etched away by 0.10 ⁇ m or more in the HF cleaning step.
  • the second removing step is preferably a drying step of drying the quartz glass surface in a clean environment with a humidity of less than 60%.
  • the chemical treatment is preferably performed using a treatment solution containing HF, NH 4 F and acetic acid.
  • the quartz glass jig of the present invention is a quartz glass jig having a chemical solution-treated portion in which unevenness is formed in an area of at least 20 cm 2 or more on the quartz glass surface, and the chemical solution-treated portion is an uneven finished surface on which unevenness is formed.
  • the quartz glass jig has a standard deviation of 1.00 ⁇ m or less when the surface roughness Ra of the irregularly finished surface is measured at 10 or more locations.
  • the uneven finished surface has a glossiness of less than 2 with a 60 degree meter. Further, it is preferable that the average value of the visible light transmittance measured by a tintometer on the unevenly finished surface at 10 or more points is 30% or less and the standard deviation is 1% or less. It is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points.
  • the quartz glass jig of the present invention can be manufactured by the method of manufacturing a quartz glass jig of the present invention.
  • the present invention in forming unevenness by chemical treatment without microcracks, even with a large-sized quartz glass jig, unevenness is not conspicuous on the surface of the unevenly finished surface, and the unevenly finished surface has excellent uniformity. It is possible to provide a quartz glass jig manufacturing method and a quartz glass jig. That is, according to the present invention, even with a large-sized quartz glass jig, uneven formation of unevenness due to uneven finishing of unevenness due to chemical treatment is reduced, and a method for manufacturing a quartz glass jig with a good appearance is obtained. and a quartz glass jig.
  • FIG. 4 is an electron micrograph of the surface of the quartz glass jig manufactured in Example 1.
  • FIG. 4 is an electron micrograph of a heavily clouded portion on the surface of the quartz glass jig manufactured in Comparative Example 1.
  • FIG. 4 is an electron micrograph of a portion of the surface of the quartz glass jig manufactured in Comparative Example 1, which is lightly opaque and has a sense of transparency.
  • 1 is a schematic explanatory view of a measurement point in a method for measuring surface roughness Ra of a quartz glass jig according to Example 1, viewed from the side of the quartz glass jig; FIG. FIG.
  • FIG. 2 is a schematic explanatory view of a measurement point in the method for measuring the surface roughness Ra of the quartz glass jig of Example 1, viewed from the upper end side of the quartz glass jig; 1 is a photograph of the appearance of a quartz glass jig manufactured according to Example 1.
  • FIG. It is a photograph of the appearance of a quartz glass jig manufactured by performing chemical treatment four times.
  • 4 is a photograph of the appearance of the upper surface of the quartz glass jig obtained in Comparative Example 1.
  • FIG. 1 is a photograph of the appearance of a side surface of a quartz glass jig obtained in Comparative Example 1, where (a) is the entire side surface and (b) is an enlarged photograph of a main part of (a).
  • FIG. 4 is a photograph of the appearance of the lower surface of the quartz glass jig obtained in Comparative Example 1.
  • FIG. It is a photograph of the quartz glass jig obtained in Comparative Example 2, (a) is an enlarged photograph of the main part of the side surface, and (b) is an enlarged photograph of the main part of the lower surface.
  • (a) is an enlarged photograph of the essential part of the upper surface
  • (b) is an enlarged photograph of the essential part of the lower surface.
  • the method for manufacturing a quartz glass jig according to the present invention is a method for manufacturing a quartz glass jig in which irregularities are formed on the surface by chemical treatment, and includes a deposit removing step for removing deposits on the smooth quartz glass surface. and a finished surface forming chemical treatment step of forming an uneven finished surface by forming unevenness by the chemical treatment on the quartz glass surface from which the deposits have been removed, wherein the surface roughness Ra of the uneven finished surface is set to 10 or more locations.
  • a smooth quartz glass surface refers to a quartz glass surface that is not roughened by physical or chemical surface treatment.
  • the quartz glass jig obtained by the method of the present invention has an uneven finished surface with excellent uniformity, and in the present invention, the surface roughness Ra is calculated based on JISB0601:2001. Furthermore, it is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points. It is preferable to measure the surface roughness Ra of the uneven finished surface at 10 or more and 50 or less points.
  • the number of measurement points for the surface roughness Ra should be at least 10, but the number of measurement points may be increased according to the size and surface area of the quartz glass jig so that the surface of the quartz glass jig can be measured evenly. It is preferable to increase or decrease or adjust.
  • the uniformity/non-uniformity of the opacity of the quartz glass jig (that is, the uniformity/non-uniformity of the formation of unevenness) can be determined by measuring the surface roughness Ra of the unevenness-formed surface at 10 or more locations. It is preferable that the deviation is 1.00 ⁇ m or less and the variation coefficient is 0.60 or less when the surface roughness Ra is measured at 10 or more points.
  • the quartz glass jig having a surface that is uniformly opaque and has uniform transparency.
  • the degree of cloudiness or transparency of the uneven surface is not particularly limited, a uniformly cloudy translucent surface is preferable. is preferred.
  • the glossiness can be measured by a known glossmeter based on JIS Z 8741-1997 Specular Glossiness-Measuring Method. It is preferable that the average value of the glossiness measured at 10 or more locations on the uneven finished surface is less than 2, more preferably 1 or less. Furthermore, the maximum value of the glossiness of the irregularly finished surface measured by a 60 degree meter is preferably less than 2, more preferably 1 or less.
  • the average value of the visible light transmittance when measuring the visible light transmittance with a tintometer of the uneven finish surface at 10 or more points is 30% or less.
  • the deviation is 1% or less, more preferably 0.5% or less.
  • the visible light transmittance is measured using a known tintometer (visible light transmittance measuring instrument) on 10 or more samples cut out from the quartz glass jig.
  • the thickness of the measurement sample is preferably 1 mm to 18 mm.
  • the measurement points for the glossiness and visible light transmittance are preferably selected according to the measurement points for the surface roughness Ra.
  • Concavo-convex formation by chemical solution treatment involves chemical components reacting with quartz glass, and part of the reaction product precipitates as (NH 4 ) 2 SiF 4 microcrystals on the quartz glass surface. It is said that unevenness is formed due to non-uniform erosion of the surface due to differences in the progress of etching in areas where there is no etching. In other words, the unevenness is basically caused by erosion of the treated surface by the chemical solution.
  • adherents on the quartz glass surface examples include adhered oil such as oil adhered by touching with a finger, adhered moisture such as adhered water, and dust and debris.
  • the deposit removal step includes an HF cleaning step of removing deposits on the smooth quartz glass surface using a cleaning solution containing HF, and a first removal step of diluting and removing HF components remaining on the quartz glass surface with water. and a second removing step of removing the attached moisture and/or the attached solvent remaining on the quartz glass surface.
  • deposits attached moisture and oil
  • the jig is thoroughly washed with water and dried.
  • a clean dryer or a room where the cleanliness of the atmosphere is controlled is used, and the drying process in a clean environment where the cleanliness is controlled is suitable. After that, surface treatment is quickly performed.
  • the meaning of performing the surface treatment promptly means that the surface treatment is performed promptly without storage such as temporary placement in an atmosphere without cleanliness control. As a result, an uneven surface having excellent uniformity is formed on the surface of the quartz glass jig, and clouding of the surface of the quartz glass jig due to surface roughening is also uniformed.
  • Pure water is also included in the water used in the first removal step. If the HF component remains due to insufficient water washing, it will become a deposit that causes uneven formation of irregularities when the quartz glass is immersed in the surface treatment liquid. .
  • the water used for washing is preferably pure water, preferably pure water with a specific resistance of 15 M ⁇ or more, and more preferably ultrapure water (specific resistance of 17.5 to 18.2 M ⁇ ). .
  • the glass surface layer of the quartz glass surface is removed by etching by 0.10 ⁇ m or more. Further, it is more preferable that the glass surface layer of the quartz glass surface is etched away by 0.10 ⁇ m or more and 30.0 ⁇ m or less.
  • the cleaning liquid containing HF an aqueous solution having a HF concentration of 2 to 25% by mass is suitable.
  • the treatment time for HF cleaning is not particularly limited, but it is preferable to select it appropriately so that the above-described suitable amount of etching removal is performed.
  • the second removing step is a drying step of drying the quartz glass surface in a clean environment with a humidity of less than 60%.
  • the drying process is preferably performed in an atmosphere with a humidity of less than 60%.
  • the clean environment is preferably an environment with a cleanliness level (cleanliness) based on ISO 14644-1 of class 7 (US Federal Standard Class 10,000) or lower, ISO Class 6 (US Federal Standard Class 1,000). The following environment is more preferable.
  • the drying process under the clean environment may be performed in a clean room where cleanliness is controlled, or may be performed using a clean dryer. In the specification of the present application, drying in a clean environment where cleanliness is controlled is called clean drying, and drying in an atmosphere without cleanliness control is called normal drying.
  • the form of drying is preferably performed in an environment with a room temperature of 20°C or more and a humidity of less than 60%, and may be a dryer or a room whose atmosphere cleanliness is controlled.
  • a method of directly drying quartz glass using an IR lamp or hot air can also be applied.
  • HF cleaning is performed using an HF cleaning liquid. After washing with water, residual moisture on the surface is removed.
  • a solvent acetone, alcohol, etc.
  • it may be applied by wiping with a dust-free cloth or by spraying.
  • the above-mentioned oil content of the deposit refers to the oil content attached to the glass surface, but it also includes the oil content when the glass surface is touched with fingers. It is preferably washed with water, removed using a solvent (acetone, alcohol, etc.), dried, or irradiated with a UV lamp and then immersed in the surface treatment liquid.
  • a solvent acetone, alcohol, etc.
  • a surface treatment liquid containing hydrogen fluoride (HF) and ammonium fluoride (NH 4 F) (chemical solution ) can be preferably used.
  • a aqueous solution containing 10 to 50% by mass of hydrogen fluoride, 6 to 30% by mass of ammonium fluoride and 30 to 60% by mass of organic acid is preferably used.
  • the organic acid is not particularly limited, for example, acetic acid, formic acid, propionic acid and the like are preferable.
  • the liquid temperature when using the surface treatment liquid is preferably 15 to 25°C.
  • After the chemical solution treatment it is preferable to wash the components of the treatment solution remaining on the quartz glass surface with water or a solvent, and then dry the surface.
  • the chemical solution treatment may be performed once, it is more preferable that the uneven finish surface is formed by performing the unevenness forming step by the chemical solution treatment a plurality of times.
  • the chemical treatment is performed a plurality of times, it is preferable to include, between each chemical treatment step, a step of washing the remaining treatment liquid components on the quartz glass surface with water or a solvent, and then drying the surface. Drying before the chemical solution treatment step is preferably clean drying in a clean environment. Further, it is preferable to immediately perform the next chemical solution treatment after drying.
  • the occurrence of uneven unevenness can be suppressed, the unevenness can be reduced, the number of treatments for eliminating unevenness can be reduced, and uniformity can be achieved even with a small number of chemical treatments, such as one or two times. It is possible to provide a method for manufacturing a quartz glass jig with excellent properties and little unevenness, and the quartz glass jig. By performing the deposit removal step and the chemical solution treatment step on the smooth quartz glass surface, the non-uniform formation of the unevenness caused by the chemical solution treatment is reduced even with a single chemical solution treatment, and the appearance is good.
  • a quartz glass jig can be provided, which makes the second chemical treatment more effective when performing the second chemical treatment.
  • the quartz glass jig of the present invention is a quartz glass jig having a chemical solution-treated portion in which unevenness is formed in an area of at least 20 cm 2 or more on the quartz glass surface, and the chemical solution-treated portion is an uneven finished surface on which unevenness is formed.
  • the quartz glass jig has a standard deviation of 1.00 ⁇ m or less when the surface roughness Ra of the irregularly finished surface is measured at 10 or more locations.
  • the coefficient of variation is 0.60 or less when the surface roughness Ra of the unevenly finished surface is measured at 10 or more points.
  • the uniformity/non-uniformity of the opacity of the quartz glass jig (that is, the uniformity/non-uniformity of the formation of unevenness) can be determined by measuring the surface roughness Ra of the unevenness-formed surface at 10 or more locations. It is preferable that the deviation is 1.00 ⁇ m or less and the variation coefficient is 0.60 or less when the surface roughness Ra is measured at 10 or more points.
  • the uneven finish surface is a uniformly opaque translucent surface.
  • the glossiness of the unevenly finished surface is less than 2 on a 60-degree meter.
  • the average value of the glossiness measured at 10 or more locations on the uneven finished surface is less than 2, more preferably 1 or less.
  • the maximum value of the glossiness of the irregularly finished surface measured by a 60 degree meter is preferably less than 2, more preferably 1 or less.
  • the average value of the visible light transmittance when measuring the visible light transmittance with a tintometer of the uneven finish surface at 10 or more points is 30% or less.
  • the deviation is 1% or less, more preferably 0.5% or less.
  • the method of manufacturing the quartz glass jig of the present invention described above is preferably used.
  • unevenness in finish of unevenness in the range of 200 mm 2 or more does not exist in the portion treated with the chemical solution.
  • uneven finish unevenness include unevenness in various shapes, such as spots, highly transparent (lightly opaque) portions, stripes with a large number of streak patterns, and aggregations of fine spots.
  • directional local unevenness such as brush pattern unevenness and fingerprint traces can be mentioned.
  • Example 1 A quartz glass jig (quartz glass furnace core tube for Si wafer processing for the semiconductor industry, area 6000 cm 2 ) having a smooth and transparent quartz glass surface that has not been subjected to surface treatment (burner-baked surface or mirror-polished surface) is prepared. Then, the quartz glass surface of this quartz glass jig was washed with a 5 mass % HF aqueous solution for 15 minutes to remove the glass surface layer of the quartz glass surface by etching (equivalent to an etching amount of 0.45 ⁇ m), and then washed with pure water. was rinsed for 5 minutes. After that, the quartz glass jig was kept at 30° C. and a humidity of 40 to 50% for 3 hours or longer using a clean dryer (class 1000) for clean drying.
  • a clean dryer class 1000
  • the first chemical treatment process was started within 30 minutes after the clean drying, and the chemical treatment process was performed by immersing the quartz glass surface of the quartz glass jig in the surface treatment liquid for 90 minutes.
  • the surface treatment liquid used for chemical treatment an aqueous solution of HF: 15% by mass, NH 4 F: 15% by mass, and acetic acid: 35% by mass was used.
  • the second chemical treatment process was started within 30 minutes after clean drying. Chemical treatment with the surface treatment liquid, rinsing with pure water, and clean drying were performed in the same manner as in the first chemical treatment step to obtain a quartz glass jig having a chemically treated uneven surface.
  • FIG. 1 shows an electron micrograph of the surface of the quartz glass jig obtained in Example 1. As shown in FIG. The scale at the bottom right of the photograph in FIG. 1 is 100 ⁇ m.
  • FIG. 5 shows a photograph of the quartz glass jig obtained in Example 1. As shown in FIG.
  • the area of the non-uniform white turbidity on the surface of the obtained quartz glass jig was measured.
  • the method of measuring the area of the uneven cloudiness is to use a black plate as the background, visually extract the location where there is a difference in the density of the cloudiness, and roughly calculate the area of that location from the vertical and horizontal dimensions. The percentage of total surface area was measured. If there were a plurality of places with different shades of cloudiness, they were all added up and measured as an area. Table 1 shows the results.
  • the inspection criteria for the area of the non-uniform white turbidity are as follows. case was determined to be defective. As shown in Table 1, the area of non-uniform white turbidity in the quartz glass jig obtained in Example 1 was 10%.
  • FIG. 4a is a side view of the measurement points of the quartz glass jig (silica glass furnace core tube for Si wafer processing), and FIG. ) viewed from the upper end side.
  • reference numeral 10 denotes a quartz glass core tube which is a quartz glass jig
  • reference numeral 12 denotes a body portion of the quartz glass core tube
  • reference numeral 14 denotes a flange portion of the quartz glass core tube.
  • the surface roughness Ra of the upper, middle and lower inner and outer surfaces (arrows O, P, Q, R, S, T) of the body 12 of the quartz glass jig 10 was measured.
  • the circumference of the body portion 12 of the quartz glass jig 10 is divided equally (120°) in three directions, and furthermore, the inner and outer surfaces (arrows O, P, Q, R, S, T) of the upper, middle and lower sides are divided. For each, the surface roughness Ra was measured (18 points).
  • FIG. 4a the surface roughness Ra of the upper, middle and lower inner and outer surfaces (arrows O, P, Q, R, S, T) of the body 12 of the quartz glass jig 10 was measured.
  • the circumference of the body portion 12 of the quartz glass jig 10 is equally divided in three directions (120°), and the measurement points of the inner and outer surfaces (arrows O1, O2, O3 and R1, R2, R3) of the upper portion are determined. is shown.
  • the upper, middle and lower measurement points are the cylindrical portion side planes except for the flange portion 14 in the quartz glass furnace core tube 12, which is a quartz glass jig.
  • Table 1 shows the results such as the average value of the surface roughness Ra and the coefficient of variation.
  • the glossiness of the obtained quartz glass jig was measured at 18 points with a 60 degree meter using a glossmeter (gloss checker IG-330 manufactured by Horiba, Ltd.). Measurement points conform to the surface roughness measurement points. Table 2 shows the average value of glossiness and the like. Further, 10 samples were cut out from the obtained quartz glass jig, and the visible light transmittance was measured (10 points) using a tintometer (MJ-TM110 manufactured by Sato Shoji Co., Ltd.). The ten locations where the sample was cut are, as shown in FIG.
  • Table 2 shows the average value and standard deviation of the visible light transmittance measured by a tintometer.
  • Example 2 As in Example 1, a quartz glass jig having a smooth and transparent surface that has not undergone surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, and then washed with pure water. I rinsed with After that, the quartz glass jig was wiped with a dust-free cloth impregnated with ethanol, and then clean-dried in the same manner as in the first embodiment. Subsequently, within 30 minutes after the clean drying, the first chemical treatment process was started. Using the same treatment liquid and treatment conditions as in Example 1, the surface of the quartz glass jig was treated with the chemical solution. After chemical treatment, rinsing was performed with pure water.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. Moreover, the area of the non-uniform part of cloudiness at this time was 5%.
  • Example 3 In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, Rinsing was performed with pure water. Clean drying was performed for 2 hours or more using an IR lamp and a hot air dryer (blowing temperature 80° C.) in a space (class 10,000 clean room) where the degree of cleanliness was controlled. Subsequently, within 30 minutes after the clean drying, the first chemical treatment process was started. Using the same treatment liquid and treatment conditions as in Example 1, chemical treatment was performed.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 20%.
  • Example 4 In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, Rinsing was performed with pure water. Clean drying was performed for 2 hours or more using an IR lamp and a hot air dryer (blowing temperature 80° C.) in a space (class 10,000 clean room) where the degree of cleanliness was controlled. Subsequently, the chemical treatment process was started within 30 minutes after clean drying. Using the same treatment liquid as in Example 1, the same chemical treatment was performed. After the chemical treatment, rinsing with pure water and clean drying similar to the clean drying after the HF cleaning were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 20%.
  • the surface of the quartz glass jig was a uniform translucent surface that was uniformly clouded, and a uniform uneven finish surface in which unevenness was continuously formed.
  • the quartz glass jigs of Examples 1 to 4 are non-defective products in which the ratio of the area of the non-uniform white turbidity to the entire surface area of the quartz glass jig is 25% or less, the standard deviation is 1 or less, and the coefficient of variation is 1 or less. has achieved a surface roughness of 0.6 or less.
  • Example 1 the step of forming unevenness by chemical treatment was repeated twice to form an uneven finished surface, but the step of forming unevenness by chemical treatment was further repeated, and the unevenness forming step by chemical treatment was performed four times in total.
  • a photograph of the quartz glass jig in this case is shown in FIG. As shown in FIG. 6, the surface is cloudy and translucent, and even more visually than the quartz glass jig of FIG. A quartz glass jig with a face was obtained.
  • Example 1 In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface that was not surface-treated was prepared, and the quartz glass surface of this quartz glass jig was subjected to a deposit removal step (5 wt% HF).
  • a deposit removal step 5 wt% HF
  • the same chemical treatment as in Example 1 was performed without performing the washing, pure water washing, and drying steps.
  • the substrate was rinsed with pure water in the same manner as in Example 1, and then dried normally. Subsequently, the chemical solution treatment process was started again, and the chemical solution treatment was performed under the same concentration conditions. After the chemical treatment, rinsing with pure water and clean drying in the same manner as in Example 1 were performed to obtain a quartz glass jig having an uneven surface.
  • FIG. 2 shows an electron micrograph of a heavily clouded portion on the surface of the quartz glass jig obtained in Comparative Example 1. As shown in FIG. The scale at the bottom right of the photograph in FIG. 2 is 100 ⁇ m. Observation of the portion where the white turbidity was light and had a sense of transparency revealed a portion where unevenness was not formed.
  • FIG. 3 shows an electron micrograph of a portion of the quartz glass jig obtained in Comparative Example 1 where the surface unevenness is not formed.
  • the scale at the bottom right of the photograph in FIG. 3 is 100 ⁇ m.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 30%.
  • Photographs of the quartz glass jig obtained in Comparative Example 1 are shown in FIGS.
  • FIG. 7 shows a portion corresponding to the upper surface of the quartz glass jig (quartz glass furnace core tube for Si wafer processing) laid down and immersed in the treatment liquid for chemical treatment, and FIG.
  • FIG. 9 shows a portion corresponding to the bottom surface of the quartz glass jig. 7 to 9, it can be seen that irregularities 16, 18 and 20 are present, respectively.
  • the unevenness 18 is streak-like unevenness and localized unevenness with directionality.
  • Example 2 In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was treated in the same manner as in Example 1 except for the washing time. Then, it was washed with 5% by mass HF for 1 minute (equivalent to an etching amount of 0.03 ⁇ m) and rinsed with pure water. It was clean-dried in a clean dryer (class 1000) at 30° C. and humidity of 50 to 60% for 3 hours or longer. The quartz glass jig after drying was insufficiently removed by HF cleaning, and the adherents remained on the surface of the quartz glass.
  • a clean dryer class 1000
  • Example 1 the first chemical treatment was performed in the same manner as in Example 1. After the chemical treatment, rinsing with pure water and clean drying were performed in the same manner as in Example 1, and chemical treatment, rinsing with pure water and clean drying were performed again in the same manner as in Example 1. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
  • Example 1 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2.
  • the surface of the quartz glass jig obtained in Comparative Example 1 was cloudy and translucent, but uneven, and there were portions with deep cloudiness and portions with light cloudiness and a sense of transparency.
  • unevenness in finish which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface. Observation of the portion where the white turbidity was light and had a sense of transparency revealed a portion where unevenness was not formed.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like.
  • FIG. 10A shows streaky unevenness 22, which is local unevenness with directionality
  • FIG. 10B shows unevenness 24, which is an aggregate of small unevennesses.
  • Example 3 (Comparative Example 3) In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared. After washing with HF, rinsing with pure water and general drying were performed. After being stored in an environment where the degree of cleanliness is not controlled for 24 hours, chemical treatment was performed in the same manner as in Example 1. After the chemical treatment, rinsing with pure water and normal drying were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
  • Example 2 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2.
  • the surface of the quartz glass jig was cloudy and translucent, but it was uneven, and there were a part with deep cloudiness and a part with light cloudiness and a sense of transparency.
  • unevenness in finish which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface.
  • FIG. 11(a) shows streaky unevenness 26, which is local unevenness with directionality
  • FIG. 11(b) shows unevenness 28 with a relatively large area.
  • Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 30%.
  • Example 4 A quartz jig used in the film forming process was immersed in a pure water bath, and immediately after that, chemical treatment was performed in the same manner as in Example 1 without drying. After the chemical treatment, rinsing with pure water and normal drying were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
  • Comparative Examples 1 to 4 the surfaces of the quartz glass jigs were not uniformly clouded, and the uneven surfaces were not uniformly finished with unevenness formed continuously.
  • the quartz glass jigs of Comparative Examples 1 to 4 are defective products in which the ratio of the area of the non-uniform white turbidity to the entire surface area of the quartz glass jig is 30% or more, and the standard deviation is 1 or less. A surface roughness with a coefficient of 0.6 or less has not been achieved.
  • the quartz glass jig of the present invention obtained as described above can be used as a material for semiconductor processing, optics, physics and chemistry equipment, decoration, and the like.
  • it is suitable as a quartz glass jig used in a semiconductor process for manufacturing semiconductors.
  • 10 quartz glass furnace core tube
  • 12 body
  • 14 flange
  • 16, 18, 20, 22, 24, 26 unevenness
  • O, P, Q, R, S, T, O1, O2, O3, R1 , R2, R3 arrows indicating measurement points of surface roughness Ra
  • U arrows indicating measurement points of visible light transmittance.

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Abstract

Provided are a method for manufacturing a fused quartz jig, and the fused quartz jig, which has, in a raised and recessed formation formed by chemical treatment where no micro-cracks are present, a front-surface raised and recessed finished surface having excellent uniformity without any conspicuous irregularity even if the fused quartz jig is large in size. The method for manufacturing the fused quartz jig having raises and recesses formed on the surface by chemical treatment includes an adhered matter removal step for removing adhered matter on a smooth fused quartz surface, and a finished surface-forming chemical treatment step for forming a raised and recessed finished surface by forming raises and recesses by using said chemical treatment on the fused quartz surface from which the adhered matter has been removed. The standard deviation when the surface roughness Ra of the raised and recessed finished surface has been measured in 10 or more places is 1.00 μm or less.

Description

石英ガラス治具の製造方法及び石英ガラス治具Quartz glass jig manufacturing method and quartz glass jig
　本発明は、薬液処理により石英ガラス表面にマイクロクラックの存在しない凹凸を形成する石英ガラス治具の製造方法及び表面に凹凸が形成された石英ガラス治具に関する。 The present invention relates to a method for manufacturing a quartz glass jig that forms irregularities without microcracks on the quartz glass surface by chemical treatment, and a quartz glass jig having irregularities formed on the surface.
　石英ガラスは、高純度で、耐化学薬品性に優れているところから、従来から、半導体処理用、光学用、理化学機器用、装飾用等の材料として使用されている。これらの石英ガラス加工品は使用目的によりその表面に各種の凹凸加工を施して粗面化することがある。特に、半導体プロセスで使用する炉心管の内面に凹凸を設けることにより、ＬＰＣＶＤ（Low Pressure Chemical Vapor Deposition）処理におけるポリシリコン膜等の成膜の剥離を防止し、ウェーハの熱処理時に発生するパーティクルを防止することである。 Due to its high purity and excellent chemical resistance, quartz glass has traditionally been used as a material for semiconductor processing, optics, physics and chemistry equipment, and decoration. Depending on the purpose of use, the surface of these quartz glass products may be roughened by performing various uneven processing. In particular, by providing unevenness on the inner surface of the furnace core tube used in the semiconductor process, it is possible to prevent peeling of the film such as polysilicon film in LPCVD (Low Pressure Chemical Vapor Deposition) processing and prevent particles generated during wafer heat treatment. It is to be.
　上記の石英ガラス表面に凹凸加工を施す方法としては、サンドブラスト処理やＨＦ／ＣＨ３ＣＯＯＨ／ＮＨ４Ｆの混合液（表面処理液）による表面処理が知られている。上記のサンドブラスト処理は、表面に機械的破壊を伴う加工方法であり、このため石英ガラス表面にはマイクロクラックが存在し、そのマイクロクラックの存在がパーティクルなどの発生の要因となることもあり、必ずしも有効とはいえなかった。また、表面処理液による表面処理による表面凹凸加工では、上記のようなマイクロクラックは存在しないので半導体プロセスでの使用に適しているということで長く採用されてきた。表面処理液によって石英ガラス表面に凹凸加工を施した例として例えば特許文献１～３がある。また、半導体プロセスにおいて、石英ガラス表面からポリシリコン膜等の剥離を防止（以下、「膜剥がれ防止」ともいう。）するためには、表面粗さの粗い方が、膜剥がれが起き難いことが一般的に知られている。 Sandblasting and surface treatment with a mixed liquid of HF/CH 3 COOH/NH 4 F (surface treatment liquid) are known as methods for processing the surface of the quartz glass to have unevenness. The sandblasting process described above is a processing method that involves mechanical destruction of the surface, so that microcracks exist on the quartz glass surface, and the presence of these microcracks may cause the generation of particles. It was not effective. In addition, since the above-mentioned microcracks do not exist in surface unevenness processing by surface treatment with a surface treatment liquid, it has been adopted for a long time because it is suitable for use in semiconductor processes. Patent Documents 1 to 3, for example, disclose examples in which the surface of quartz glass is processed to be uneven with a surface treatment liquid. In the semiconductor process, in order to prevent peeling of a polysilicon film or the like from the surface of quartz glass (hereinafter also referred to as "prevention of film peeling"), the rougher the surface, the less likely the peeling of the film will occur. commonly known.
　しかしながら、石英ガラスの表面処理液による表面処理方法では、サンドブラスト処理といった機械的破壊を伴う加工方法に比べて、表面粗さのバラツキやコントロールが難しいといった問題がある。更に、表面処理液に浸漬させる際の被処理面の状態に起因して、出来上がった、表面の凹凸の形成による白濁状態が、均一であったり、局所的に不均一であったり、一定しない事がある。その不均一な箇所が存在することで、石英に付着した膜が、局所的に脆くなり、膜剥がれを起こす等、目的の機能が達成されない等、問題となる。また、従来、不均一な凹凸（ムラ）が形成された場合、ムラを消すために薬液処理を繰り返すことも行われたが、大きなムラや筋状のムラ、小さいムラの集合体等のムラは消し難く、多数回の薬液処理を必要とする場合もあった。 However, the surface treatment method using a quartz glass surface treatment liquid has problems such as variations in surface roughness and difficult control compared to processing methods such as sandblasting that involve mechanical destruction. Furthermore, due to the state of the surface to be treated when immersed in the surface treatment liquid, the resulting cloudy state due to the formation of unevenness on the surface may be uniform, locally uneven, or inconsistent. There is Due to the presence of such non-uniform portions, the film adhering to the quartz becomes locally brittle, causing problems such as film peeling and the failure to achieve the intended function. Conventionally, when non-uniform unevenness (unevenness) was formed, chemical treatment was repeated to erase the unevenness, but unevenness such as large unevenness, streak-like unevenness, and clusters of small unevenness was eliminated. In some cases, it was difficult to erase, and many times of chemical treatment was required.
　特許文献４では、段落０００８に処理面のムラについての言及が有り、その対策として、レイノルズ数Ｒｅに着目した提案がなされている。ここで議論されているムラとは、処理面を１ｍ程度離れた位置から見た場合の前記処理面の濃淡についての議論で有る為、大きな処理面を同条件で処理する為のレイノルズ数の規定等が解決策として機能している。 In Patent Document 4, paragraph 0008 mentions the unevenness of the treated surface, and as a countermeasure therefor, a proposal is made focusing on the Reynolds number Re. The unevenness discussed here is a discussion of the shading of the treated surface when viewed from a position about 1 m away from the treated surface. are working as a solution.
　一方、近年の半導体製造プロセスの中の成膜プロセスでは、より局所的な「凹凸仕上げ面」のムラが重要視されるようになってきた。このような局所的なムラは、表面の凹凸の形成によって白濁して不透明となっている凹凸仕上げ面の中に出来た、やや透明がかった（つまり表面粗さＲａが極端に小さい箇所又は極端に大きい箇所）１ｃｍ角程度の領域であったり、或いは１ｃｍ角程度のサイズの刷毛模様や指紋のような方向性を持った局所的なムラである。方向性を持った局所的なムラは、周囲の凹凸仕上げ面と、同程度の表面粗さレベルの場合と、異なった表面粗さレベルの場合がある。成膜プロセスに用いる石英ガラス冶具には、成膜回数に応じて積層された膜が付着するが、生産性向上の為の洗浄サイクル延長により石英ガラス冶具上の膜厚が厚くなってくると、成膜プロセス前後の昇温・降温過程で、上述した局所的なムラを起点に微細な剥がれが生じ、プロセス中のパーティクル汚染の原因になる事がある為である。 On the other hand, in recent years, in the film formation process of semiconductor manufacturing processes, more local unevenness in the "unevenness finish surface" has come to be emphasized. Such local unevenness is caused by the formation of unevenness on the surface, which is cloudy and opaque. Large part) It is a region of about 1 cm square, or a local unevenness with directionality such as a brush pattern of about 1 cm square or a fingerprint. The directional local unevenness may have a surface roughness level similar to that of the surrounding uneven finished surface, or may have a different surface roughness level. Depending on the number of times the film is formed, a layer of film adheres to the quartz glass jig used in the film forming process. This is because fine peeling occurs starting from the above-described local unevenness during the process of temperature rise and temperature drop before and after the film formation process, which may cause particle contamination during the process.
　特許文献１～４に記載されたような従来の表面処理では、比較的小さな領域を対象としていたため、表面積が小さいと凹凸形成にムラはあっても目立たない為、ムラが無いように（ムラが少なく）見えていた。 Conventional surface treatments, such as those described in Patent Documents 1 to 4, target relatively small areas. less) was visible.
　しかしながら、近年、半導体ウェーハの大型化に伴い、石英ガラス治具も大型化しており、従来のＳｉウェーハ直径６インチ～８インチサイズ用途では、表面の凹凸仕上げ面にムラが目立たなかったものが、１バッチあたりのＳｉウェーハ処理枚数の増加と、Ｓｉウェーハの１２インチサイズが主流となってきたことにより、石英ガラス治具の大型化が進み、石英ガラスの炉心管や丸封、天板の大型化、長尺化によって表面積が大きくなるので、表面の凹凸仕上げ面にムラが目立つようになってきたという問題がある。 However, in recent years, as the size of semiconductor wafers has increased, quartz glass jigs have also increased in size. Due to the increase in the number of Si wafers processed per batch and the fact that 12-inch size Si wafers have become mainstream, quartz glass jigs have become larger, and quartz glass core tubes, round seals, and top plates have become larger. Since the surface area increases due to the size and length of the film, there is a problem that unevenness has become noticeable on the roughened surface of the surface.
　凹凸仕上げムラによる表面白濁の不均一詳しくは透明部と不透明部の存在は、表面の山谷構造不均一に起因するため、凹凸仕上げムラが石英ガラス治具に存在すると、結果的に、成膜プロセスでウェーハに付着した膜の接着効果に差異が生じ好ましくない。また、別の問題として、凹凸仕上げムラが石英ガラス治具に存在すると、成膜プロセスにおいて、ヒーターから熱線透過差異が生じて温度分布の原因となり、これもまた、ウェーハ処理の膜均一性の観点から好ましくない。 Uneven surface cloudiness due to irregular finish unevenness More specifically, the existence of transparent and opaque areas is caused by the uneven ridge-and-valley structure of the surface. It is not preferable because a difference occurs in the adhesion effect of the film adhered to the wafer. Another problem is that if there is unevenness in the finish of the quartz glass jig, a difference in the transmission of heat rays from the heater occurs in the film formation process, causing a temperature distribution. unfavorable from
特開平１０－２７３３３９Japanese Patent Laid-Open No. 10-273339 ＷＯ２００４／０５１７２４WO2004/051724 特開２００１－３３５３４２JP 2001-335342 特開２００５－１４５７２１JP 2005-145721
　従来は、薬液処理の前処理としては、長期間放置されていた処理用ワークについては、アルコール拭き等を行う事はあったが、通常の製品製造工程で表面火炎研磨を行ったワーク等については、清浄な表面を持っていることから、クリーンな環境で冷却した後に、そのまま薬液に依る凹凸処理面の形成工程に進む事があった。 In the past, as a pretreatment for chemical treatment, alcohol wipes, etc. were performed for processing workpieces that had been left for a long period of time, but for workpieces that had undergone surface flame polishing in the normal product manufacturing process, Since the substrate has a clean surface, there are cases in which, after cooling in a clean environment, the step of forming an uneven surface using a chemical liquid is performed as it is.
　本発明者らは、局所的なムラの解決について鋭意取り組んだ結果、短い工程間の移動等の際においても、指紋や手袋由来の油脂や、付着した水などの付着水分、ほこりやゴミ、ほこり避けのプラスティック・カバーについた汚れがワーク表面に付着し、薬液工程での反応を妨げる事で、上述した局所的なムラが生じる事を発見した。
　このため被処理面に付着物（付着水分、油分）がある箇所は薬液処理による反応が不安定になり、部分的に形成される凹凸の大きさが異なる、もしくは形成されず、石英ガラス治具全体で見ると、不均一な凹凸面が形成されてしまう。成膜工程で使用した時に、部分的に充分な効果が得られない箇所ができてしまう。このような不均一な凹凸を持つ面は、その外観も不均一に白濁した面になり、不均一箇所における膜剥がれが、発生しやすいことが、懸念される。 As a result of diligent efforts to solve local unevenness, the present inventors have found that even during a short transfer between processes, fingerprints, oils and fats derived from gloves, attached moisture such as attached water, dust, dirt, dust, etc. It was found that the above-mentioned local unevenness was caused by dirt attached to the plastic cover of the avoidance sticking to the surface of the work and interfering with the reaction in the chemical solution process.
For this reason, the reaction of chemical treatment becomes unstable where there is adhesion (adhered moisture, oil) on the surface to be treated, and the size of irregularities formed partially varies or is not formed, resulting in quartz glass jigs. When viewed as a whole, a non-uniform uneven surface is formed. When used in the film-forming process, there will be places where a sufficient effect cannot be obtained. A surface having such non-uniform irregularities has a non-uniform white turbid appearance, and there is concern that film peeling at non-uniform locations is likely to occur.
　表面の汚れの箇所と内容（例えば、油）が特定されている場合においては、アルコールやアセトンといった有機溶剤でのふき取りでも対応可能であるが、薄い油汚れ等の検出、特定は難しい為、薬液処理前に、ワーク全体の少なくとも極表面の物質を除去することが最も有効で、効果的な改善策である事が判った。 If the location and content of the dirt on the surface (for example, oil) are specified, it can be wiped off with an organic solvent such as alcohol or acetone. It has been found to be the most effective and effective remedial measure to remove at least the superficial material from the entire workpiece prior to processing.
　本発明は、上記した従来技術の問題点に鑑みてなされたもので、マイクロクラックの存在しない薬液処理による凹凸形成において、大型の石英ガラス治具であっても表面の凹凸仕上げ面にムラが目立たず、優れた均一性を有する凹凸仕上げ面を備えた石英ガラス治具の製造方法及び石英ガラス治具を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art. In forming unevenness by chemical treatment without microcracks, unevenness is conspicuous even in the case of a large-sized quartz glass jig. First, it is an object of the present invention to provide a method for manufacturing a quartz glass jig having an uneven finished surface with excellent uniformity, and the quartz glass jig.
　本発明の石英ガラス治具の製造方法は、薬液処理により、凹凸が表面に形成されてなる石英ガラス治具の製造方法であり、平滑な石英ガラス表面の付着物を除去する付着物除去工程と、前記付着物が除去された前記石英ガラス表面に前記薬液処理による凹凸形成により凹凸仕上げ面を形成する仕上げ面形成薬液処理工程と、を含み、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス治具の製造方法である。 The method for manufacturing a quartz glass jig according to the present invention is a method for manufacturing a quartz glass jig in which irregularities are formed on the surface by chemical treatment, and includes a deposit removing step for removing deposits on the smooth quartz glass surface. and a finished surface forming chemical treatment step of forming an uneven finished surface by forming unevenness by the chemical treatment on the quartz glass surface from which the deposits have been removed, wherein the surface roughness Ra of the uneven finished surface is set to 10 or more locations. A method for manufacturing a quartz glass jig, wherein the standard deviation when measured is 1.00 μm or less.
　前記凹凸仕上げ面の６０度計での光沢度が２未満であるのが好適である。また、前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の平均値が３０％以下で標準偏差が１％以下であるのが好適である。
　前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下であるのが好適である。 It is preferable that the uneven finished surface has a glossiness of less than 2 with a 60 degree meter. Further, it is preferable that the average value of the visible light transmittance measured by a tintometer on the unevenly finished surface at 10 or more points is 30% or less and the standard deviation is 1% or less.
It is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points.
　前記付着物除去工程が、ＨＦを含む洗浄液を用いて前記平滑な石英ガラス表面の付着物を除去するＨＦ洗浄工程と、前記ＨＦ洗浄工程後、石英ガラス表面に残留するＨＦ成分を水により希釈除去する第一除去工程と、前記第一除去工程後、石英ガラス表面に残留する付着水分及び／又は付着溶剤を除去する第二除去工程と、を含むのが好適である。 The deposit removal step includes an HF cleaning step of removing deposits on the smooth quartz glass surface using a cleaning liquid containing HF, and after the HF cleaning step, the HF component remaining on the quartz glass surface is diluted and removed with water. and a second removing step of removing the attached moisture and/or the attached solvent remaining on the quartz glass surface after the first removing step.
　前記ＨＦ洗浄工程において、前記石英ガラス表面のガラス表層が０．１０μｍ以上エッチング除去されるのが好適である。 It is preferable that the glass surface layer of the quartz glass surface is etched away by 0.10 μm or more in the HF cleaning step.
　前記第二除去工程が、湿度６０％未満雰囲気且つクリーンな環境下で前記石英ガラス表面を乾燥する乾燥工程であるのが好適である。 The second removing step is preferably a drying step of drying the quartz glass surface in a clean environment with a humidity of less than 60%.
　前記薬液処理が、ＨＦ、ＮＨ４Ｆ及び酢酸を含む処理液を用いて行われるのが好ましい。 The chemical treatment is preferably performed using a treatment solution containing HF, NH 4 F and acetic acid.
　本発明の石英ガラス冶具は、石英ガラス表面の少なくとも２０ｃｍ２以上の面積に凹凸が形成されてなる薬液処理部分を有する石英ガラス冶具であり、前記薬液処理部分が、凹凸が形成された凹凸仕上げ面とされてなり、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス冶具である。 The quartz glass jig of the present invention is a quartz glass jig having a chemical solution-treated portion in which unevenness is formed in an area of at least 20 cm 2 or more on the quartz glass surface, and the chemical solution-treated portion is an uneven finished surface on which unevenness is formed. The quartz glass jig has a standard deviation of 1.00 μm or less when the surface roughness Ra of the irregularly finished surface is measured at 10 or more locations.
　前記凹凸仕上げ面の６０度計での光沢度が２未満であるのが好適である。また、前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の平均値が３０％以下で標準偏差が１％以下であるのが好適である。
　前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下であるのが好適である。 It is preferable that the uneven finished surface has a glossiness of less than 2 with a 60 degree meter. Further, it is preferable that the average value of the visible light transmittance measured by a tintometer on the unevenly finished surface at 10 or more points is 30% or less and the standard deviation is 1% or less.
It is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points.
　本発明の石英ガラス治具は、本発明の石英ガラス治具の製造方法により製造することができる。 The quartz glass jig of the present invention can be manufactured by the method of manufacturing a quartz glass jig of the present invention.
　本発明によれば、マイクロクラックの存在しない薬液処理による凹凸形成において、大型の石英ガラス治具であっても表面の凹凸仕上げ面にムラが目立たず、優れた均一性を有する凹凸仕上げ面を備えた石英ガラス治具の製造方法及び石英ガラス治具を提供することができるという著大な効果を奏する。即ち、本発明によれば、大型の石英ガラス治具であっても、薬液処理による凹凸仕上げのムラとなる凹凸形成の不均一さが低減され、外観の見栄えの良い石英ガラス治具の製造方法及び石英ガラス治具を提供することができる。
　また、石英ガラス治具の表面粗さのバラツキ低減を行う事で、大型の石英ガラス治具であっても、表面状態の白濁の均一化が図られ、白濁の不均一な箇所の膜剥がれが、防止できるという効果もある。
　さらに、白濁の不均一解消は、石英ガラス治具を半導体製造装置に用いた場合に、半導体製造プロセスにおいて、ヒーターから熱線透過の差異軽減に伴う温度分布抑制効果があり、ウェーハ処理の均一性に寄与するという効果もある。 According to the present invention, in forming unevenness by chemical treatment without microcracks, even with a large-sized quartz glass jig, unevenness is not conspicuous on the surface of the unevenly finished surface, and the unevenly finished surface has excellent uniformity. It is possible to provide a quartz glass jig manufacturing method and a quartz glass jig. That is, according to the present invention, even with a large-sized quartz glass jig, uneven formation of unevenness due to uneven finishing of unevenness due to chemical treatment is reduced, and a method for manufacturing a quartz glass jig with a good appearance is obtained. and a quartz glass jig.
In addition, by reducing the variation in the surface roughness of the quartz glass jig, even with a large-sized quartz glass jig, the whiteness of the surface condition is made uniform, and film peeling at places where the whiteness is uneven is prevented. There is also the effect of being able to prevent .
Furthermore, when quartz glass jigs are used in semiconductor manufacturing equipment, elimination of uneven white turbidity has the effect of suppressing the temperature distribution associated with the reduction of differences in heat ray transmission from heaters in the semiconductor manufacturing process, which improves the uniformity of wafer processing. There is also the effect of contributing
実施例１で製造された石英ガラス治具の表面の電子顕微鏡写真である。4 is an electron micrograph of the surface of the quartz glass jig manufactured in Example 1. FIG. 比較例１で製造された石英ガラス治具の表面の白濁が濃い部分の電子顕微鏡写真である。4 is an electron micrograph of a heavily clouded portion on the surface of the quartz glass jig manufactured in Comparative Example 1. FIG. 比較例１で製造された石英ガラス治具の表面の白濁が薄く透明感がある部分の電子顕微鏡写真である。4 is an electron micrograph of a portion of the surface of the quartz glass jig manufactured in Comparative Example 1, which is lightly opaque and has a sense of transparency. 実施例１の石英ガラス治具の表面粗さＲａの測定方法における測定ポイントを石英ガラス治具の側面から見た概略説明図である。1 is a schematic explanatory view of a measurement point in a method for measuring surface roughness Ra of a quartz glass jig according to Example 1, viewed from the side of the quartz glass jig; FIG. 実施例１の石英ガラス治具の表面粗さＲａの測定方法における測定ポイントを石英ガラス治具の上端側から見た概略説明図である。FIG. 2 is a schematic explanatory view of a measurement point in the method for measuring the surface roughness Ra of the quartz glass jig of Example 1, viewed from the upper end side of the quartz glass jig; 実施例１によって製造された石英ガラス治具の外観の写真である。1 is a photograph of the appearance of a quartz glass jig manufactured according to Example 1. FIG. 薬液処理を４回行うことによって製造された石英ガラス治具の外観の写真である。It is a photograph of the appearance of a quartz glass jig manufactured by performing chemical treatment four times. 比較例１で得られた石英ガラス治具の上面の外観の写真である。4 is a photograph of the appearance of the upper surface of the quartz glass jig obtained in Comparative Example 1. FIG. 比較例１で得られた石英ガラス治具の側面の外観の写真であり、（ａ）が側面全体、（ｂ）が（ａ）の要部拡大写真である。1 is a photograph of the appearance of a side surface of a quartz glass jig obtained in Comparative Example 1, where (a) is the entire side surface and (b) is an enlarged photograph of a main part of (a). 比較例１で得られた石英ガラス治具の下面の外観の写真である。4 is a photograph of the appearance of the lower surface of the quartz glass jig obtained in Comparative Example 1. FIG. 比較例２で得られた石英ガラス治具の写真であり、（ａ）が側面の要部拡大写真、（ｂ）が下面の要部拡大写真である。It is a photograph of the quartz glass jig obtained in Comparative Example 2, (a) is an enlarged photograph of the main part of the side surface, and (b) is an enlarged photograph of the main part of the lower surface. 比較例３で得られた石英ガラス治具の写真であり、（ａ）が上面の要部拡大写真、（ｂ）が下面の要部拡大写真である。It is a photograph of the quartz glass jig obtained in Comparative Example 3, (a) is an enlarged photograph of the essential part of the upper surface, and (b) is an enlarged photograph of the essential part of the lower surface.
　以下に本発明の実施の形態を説明するが、これら実施の形態は例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 Embodiments of the present invention will be described below, but these embodiments are shown by way of example, and it goes without saying that various modifications are possible without departing from the technical concept of the present invention.
　本発明の石英ガラス治具の製造方法は、薬液処理により、凹凸が表面に形成されてなる石英ガラス治具の製造方法であり、平滑な石英ガラス表面の付着物を除去する付着物除去工程と、前記付着物が除去された前記石英ガラス表面に前記薬液処理による凹凸形成により凹凸仕上げ面を形成する仕上げ面形成薬液処理工程と、を含み、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス治具の製造方法である。 The method for manufacturing a quartz glass jig according to the present invention is a method for manufacturing a quartz glass jig in which irregularities are formed on the surface by chemical treatment, and includes a deposit removing step for removing deposits on the smooth quartz glass surface. and a finished surface forming chemical treatment step of forming an uneven finished surface by forming unevenness by the chemical treatment on the quartz glass surface from which the deposits have been removed, wherein the surface roughness Ra of the uneven finished surface is set to 10 or more locations. A method for manufacturing a quartz glass jig, wherein the standard deviation when measured is 1.00 μm or less.
　平滑な石英ガラス表面とは、物理的又は化学的な表面処理による凹凸形成がされていない石英ガラス表面をいう。 A smooth quartz glass surface refers to a quartz glass surface that is not roughened by physical or chemical surface treatment.
　本発明方法により得られる石英ガラス冶具は、優れた均一性を有する凹凸仕上げ面を備えるものであり、本発明において、前記表面粗さＲａはＪＩＳＢ０６０１：２００１に基づき算出される。さらに、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下であるのが好適である。前記凹凸仕上げ面の表面粗さＲａの測定は、１０箇所以上５０箇所以下が好適である。表面粗さＲａの測定箇所の数は、少なくとも１０箇所は必要であるが、石英ガラス治具の表面を偏りなく測定できるように、石英ガラス治具のサイズや表面積に応じて、測定箇所を増やしたり又は減らしたり、調整することが好適である。
　このように、石英ガラス治具の白濁の均一／不均一（即ち凹凸形成の均一／不均一）の判定については、凹凸が形成された表面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下で、且つ、表面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下である事が好ましい。 The quartz glass jig obtained by the method of the present invention has an uneven finished surface with excellent uniformity, and in the present invention, the surface roughness Ra is calculated based on JISB0601:2001. Furthermore, it is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points. It is preferable to measure the surface roughness Ra of the uneven finished surface at 10 or more and 50 or less points. The number of measurement points for the surface roughness Ra should be at least 10, but the number of measurement points may be increased according to the size and surface area of the quartz glass jig so that the surface of the quartz glass jig can be measured evenly. It is preferable to increase or decrease or adjust.
As described above, the uniformity/non-uniformity of the opacity of the quartz glass jig (that is, the uniformity/non-uniformity of the formation of unevenness) can be determined by measuring the surface roughness Ra of the unevenness-formed surface at 10 or more locations. It is preferable that the deviation is 1.00 μm or less and the variation coefficient is 0.60 or less when the surface roughness Ra is measured at 10 or more points.
　前記凹凸仕上げ面の均一性を高めることにより、均一に白濁し且つ透明性も均一な表面を有する石英ガラス治具を提供することができる。
　前記凹凸仕上げ面の白濁や透明性の程度は特に制限はないが、均一に白濁した半透明な表面が好適であり、特に、前記凹凸仕上げ面の６０度計での光沢度が２未満であるのが好適である。本発明において、前記光沢度の測定は、ＪＩＳ　Ｚ　８７４１－１９９７　鏡面光沢度－測定方法に基づき、６０度鏡面光沢を公知の光沢計により測定することができる。前記凹凸仕上げ面を１０箇所以上測定した時の光沢度の平均値が２未満であることが好適であり、１以下がより好適である。さらに、前記凹凸仕上げ面の６０度計での光沢度の最大値が２未満であることが好ましく、１以下がより好ましい。
　また、前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の可視光透過率の平均値が３０％以下であるのが好適であり、また、前記可視光透過率の標準偏差が１％以下であるのが好適であり、０．５％以下がより好適である。本発明において、前記可視光透過率の測定は、前記石英ガラス治具から切出した１０箇所以上のサンプルに対し、公知のティントメーター（可視光線透過率測定器）を用いて可視光線透過率を測定するものであり、測定サンプルの厚みは１ｍｍ～１８ｍｍが好適である。
　前記光沢度及び可視光線透過率の測定ポイントは、表面粗さＲａの測定ポイントに準じて選択することが好適である。 By improving the uniformity of the uneven finished surface, it is possible to provide a quartz glass jig having a surface that is uniformly opaque and has uniform transparency.
Although the degree of cloudiness or transparency of the uneven surface is not particularly limited, a uniformly cloudy translucent surface is preferable. is preferred. In the present invention, the glossiness can be measured by a known glossmeter based on JIS Z 8741-1997 Specular Glossiness-Measuring Method. It is preferable that the average value of the glossiness measured at 10 or more locations on the uneven finished surface is less than 2, more preferably 1 or less. Furthermore, the maximum value of the glossiness of the irregularly finished surface measured by a 60 degree meter is preferably less than 2, more preferably 1 or less.
In addition, it is preferable that the average value of the visible light transmittance when measuring the visible light transmittance with a tintometer of the uneven finish surface at 10 or more points is 30% or less. Preferably the deviation is 1% or less, more preferably 0.5% or less. In the present invention, the visible light transmittance is measured using a known tintometer (visible light transmittance measuring instrument) on 10 or more samples cut out from the quartz glass jig. The thickness of the measurement sample is preferably 1 mm to 18 mm.
The measurement points for the glossiness and visible light transmittance are preferably selected according to the measurement points for the surface roughness Ra.
　薬液処理による凹凸形成は、薬液成分と石英ガラスが反応し、反応生成物の一部が石英ガラス表面に（ＮＨ４）２ＳｉＦ４微結晶として析出し微結晶の析出した部分と、析出していない部分のエッチング進行に差が生じる事によって、不均一に表面が浸食されて凹凸が形成されると言われている。つまり、基本的に薬液に処理面が浸食される事で凹凸が生じている。 Concavo-convex formation by chemical solution treatment involves chemical components reacting with quartz glass, and part of the reaction product precipitates as (NH 4 ) 2 SiF 4 microcrystals on the quartz glass surface. It is said that unevenness is formed due to non-uniform erosion of the surface due to differences in the progress of etching in areas where there is no etching. In other words, the unevenness is basically caused by erosion of the treated surface by the chemical solution.
　上記石英ガラス表面の付着物としては、指で触ったりすることにより付着した油脂などの付着油分、付着した水などの付着水分、埃やゴミ、など、が挙げられる。 Examples of the adherents on the quartz glass surface include adhered oil such as oil adhered by touching with a finger, adhered moisture such as adhered water, and dust and debris.
　前記付着物除去工程としては、ＨＦを含む洗浄液を用いて前記平滑な石英ガラス表面の付着物を除去するＨＦ洗浄工程と、前記石英ガラス表面に残留するＨＦ成分を水により希釈除去する第一除去工程と、前記石英ガラス表面に残留する付着水分及び／又は付着溶剤を除去する第二除去工程と、を含む工程が好ましい。このように、石英ガラス治具の表面の付着物（付着水分、油分）を、ＨＦを含む洗浄液により除去し、ＨＦ洗浄による除去後は、水により十分に水洗し、乾燥させる。乾燥には、クリーン乾燥機もしくは雰囲気クリーン度が管理された部屋等を使用し、クリーン度が管理されたクリーンな環境下での乾燥工程が好適である。その後、速やかに表面処理を行う。速やかに表面処理を行うという意味は、クリーン度管理無し雰囲気で仮置きするなどの保管をすることなしに速やかに表面処理を行うという意味である。これにより、石英ガラス治具表面に優れた均一性を有する凹凸仕上げ面が形成され、粗面化による石英ガラス治具表面の白濁も均一化する。 The deposit removal step includes an HF cleaning step of removing deposits on the smooth quartz glass surface using a cleaning solution containing HF, and a first removal step of diluting and removing HF components remaining on the quartz glass surface with water. and a second removing step of removing the attached moisture and/or the attached solvent remaining on the quartz glass surface. In this way, deposits (attached moisture and oil) on the surface of the quartz glass jig are removed with a cleaning solution containing HF, and after removal by HF cleaning, the jig is thoroughly washed with water and dried. For drying, a clean dryer or a room where the cleanliness of the atmosphere is controlled is used, and the drying process in a clean environment where the cleanliness is controlled is suitable. After that, surface treatment is quickly performed. The meaning of performing the surface treatment promptly means that the surface treatment is performed promptly without storage such as temporary placement in an atmosphere without cleanliness control. As a result, an uneven surface having excellent uniformity is formed on the surface of the quartz glass jig, and clouding of the surface of the quartz glass jig due to surface roughening is also uniformed.
　前記第一除去工程に用いられる水には純水も含まれる。水洗不足により、ＨＦ成分が残留すると、表面処理液に石英ガラスを浸漬させた際に、凹凸形成の不均一を招く付着物となってしまうために、水洗による洗浄は、十分に行う事が好ましい。水洗に使用される水としては、純水が好ましく、比抵抗値で、１５ＭΩ以上の純水が好ましく、更には、超純水（比抵抗値１７．５～１８．２ＭΩ）であると尚良い。 Pure water is also included in the water used in the first removal step. If the HF component remains due to insufficient water washing, it will become a deposit that causes uneven formation of irregularities when the quartz glass is immersed in the surface treatment liquid. . The water used for washing is preferably pure water, preferably pure water with a specific resistance of 15 MΩ or more, and more preferably ultrapure water (specific resistance of 17.5 to 18.2 MΩ). .
　前記ＨＦ洗浄工程において、前記石英ガラス表面のガラス表層が０．１０μｍ以上エッチング除去されるのが好適である。また、前記石英ガラス表面のガラス表層が０．１０μｍ以上３０．０μｍ以下エッチング除去されるのがさらに好適である。
　前記ＨＦを含む洗浄液としては、ＨＦの濃度が、２～２５質量％である水溶液が好適である。ＨＦ洗浄の処理時間としては特に制限はないが、前述した好適な量のエッチング除去が行われるように、適宜選択することが好適である。 Preferably, in the HF cleaning step, the glass surface layer of the quartz glass surface is removed by etching by 0.10 μm or more. Further, it is more preferable that the glass surface layer of the quartz glass surface is etched away by 0.10 μm or more and 30.0 μm or less.
As the cleaning liquid containing HF, an aqueous solution having a HF concentration of 2 to 25% by mass is suitable. The treatment time for HF cleaning is not particularly limited, but it is preferable to select it appropriately so that the above-described suitable amount of etching removal is performed.
　前記第二除去工程が、湿度６０％未満雰囲気且つクリーンな環境下で前記石英ガラス表面を乾燥する乾燥工程であるのが好適である。このように、乾燥工程は、湿度６０％未満の雰囲気下で行うのが好ましい。
　前記クリーンな環境下としては、ＩＳＯ　１４６４４－１に基づくクリーン度（清浄度）がクラス７（米国連邦規格　クラス１０，０００）以下の環境が好ましく、ＩＳＯ　クラス６（米国連邦規格　クラス１，０００）以下の環境がより好ましい。前記クリーンな環境下での乾燥工程は、クリーン度が管理されたクリーンルームで行ってもよく、クリーン乾燥機を用いて行ってもよい。本願明細書において、クリーン度が管理されたクリーンな環境下での乾燥をクリーン乾燥と称し、クリーン度管理無し雰囲気での乾燥を通常乾燥と称する。 Preferably, the second removing step is a drying step of drying the quartz glass surface in a clean environment with a humidity of less than 60%. Thus, the drying process is preferably performed in an atmosphere with a humidity of less than 60%.
The clean environment is preferably an environment with a cleanliness level (cleanliness) based on ISO 14644-1 of class 7 (US Federal Standard Class 10,000) or lower, ISO Class 6 (US Federal Standard Class 1,000). The following environment is more preferable. The drying process under the clean environment may be performed in a clean room where cleanliness is controlled, or may be performed using a clean dryer. In the specification of the present application, drying in a clean environment where cleanliness is controlled is called clean drying, and drying in an atmosphere without cleanliness control is called normal drying.
　乾燥を行う際の形態は、室温２０℃以上湿度６０％未満の環境で行うことが好適であり、乾燥機や、雰囲気クリーン度が管理された部屋であってよい。乾燥時間を短縮するために、ＩＲランプや、熱風を用い、石英ガラスを直接乾燥させる方法も適用できる。 The form of drying is preferably performed in an environment with a room temperature of 20°C or more and a humidity of less than 60%, and may be a dryer or a room whose atmosphere cleanliness is controlled. In order to shorten the drying time, a method of directly drying quartz glass using an IR lamp or hot air can also be applied.
　このように、本発明の石英ガラス治具の製造方法では、石英ガラス表面の水分を完全に除去するために、ＨＦによる洗浄液を用いてＨＦ洗浄を行い、水洗した後に、表面の残留水分を除去、乾燥させるために溶剤（アセトンやアルコール等）を用いて、乾燥させ、その後表面処理液に浸漬させてもよい。溶剤（アセトンやアルコール等）を使用する際は、無塵布による布による拭き取りや、スプレーにより、塗布する方法であってよい。 As described above, in the method for manufacturing a quartz glass jig according to the present invention, in order to completely remove moisture from the surface of the quartz glass, HF cleaning is performed using an HF cleaning liquid. After washing with water, residual moisture on the surface is removed. Alternatively, a solvent (acetone, alcohol, etc.) may be used for drying, followed by immersion in the surface treatment liquid. When using a solvent (acetone, alcohol, etc.), it may be applied by wiping with a dust-free cloth or by spraying.
　上述した付着物の油分とは、ガラス表面に付着した、油分を指すが、ガラス表面を手指で、触れた際の油分も含み、油分の除去は、ＨＦによる洗浄液を用いた後に、水で十分に水洗し、溶剤（アセトンやアルコール等）を使用して除去し、乾燥させ、あるいは、ＵＶランプを照射した後に、表面処理液に浸漬させることが好ましい。 The above-mentioned oil content of the deposit refers to the oil content attached to the glass surface, but it also includes the oil content when the glass surface is touched with fingers. It is preferably washed with water, removed using a solvent (acetone, alcohol, etc.), dried, or irradiated with a UV lamp and then immersed in the surface treatment liquid.
　付着物としての、水分や油分については、前述しているが、有機物（例えば、炭素水素化合物等）も付着物として挙げられる。このような有機物であっても、前述した工程により、同時に除去されることとなる。 Although the moisture and oil content as deposits have been described above, organic substances (eg, hydrocarbon compounds, etc.) can also be cited as deposits. Even such an organic matter is removed at the same time by the steps described above.
　前記薬液処理に用いる処理液としては、従来から使用されているものと用いることができ、具体的には、フッ化水素（ＨＦ）とフッ化アンモニウム（ＮＨ４Ｆ）を含む表面処理液（薬液）が好適に使用できる。特に、フッ化水素１０～５０質量％、フッ化アンモニウム６～３０質量％及び有機酸３０～６０質量％を含有する水溶液が好適に用いられる。有機酸としては、特に限定されないが、例えば、酢酸、ギ酸、プロピオン酸等が好ましい。また、上記表面処理液を使用する際の液温は１５～２５℃であることが好適である。特に、ＨＦ、ＮＨ４Ｆ及び酢酸を含む処理液を用いて表面処理を行うのが好適である。
　薬液処理後は、石英ガラス表面に残留する処理液の成分を水や溶剤を用いて洗浄した後、乾燥することが好適である。 As the treatment liquid used for the chemical treatment, conventionally used treatment liquids can be used. Specifically, a surface treatment liquid containing hydrogen fluoride (HF) and ammonium fluoride (NH 4 F) (chemical solution ) can be preferably used. In particular, an aqueous solution containing 10 to 50% by mass of hydrogen fluoride, 6 to 30% by mass of ammonium fluoride and 30 to 60% by mass of organic acid is preferably used. Although the organic acid is not particularly limited, for example, acetic acid, formic acid, propionic acid and the like are preferable. Further, the liquid temperature when using the surface treatment liquid is preferably 15 to 25°C. In particular, it is preferable to perform the surface treatment using a treatment liquid containing HF, NH4F and acetic acid.
After the chemical solution treatment, it is preferable to wash the components of the treatment solution remaining on the quartz glass surface with water or a solvent, and then dry the surface.
　前記薬液処理は１回でも良いが、前記薬液処理による凹凸形成工程が複数回行われることで前記凹凸仕上げ面が形成されてなることがより好適である。薬液処理を複数回行う場合は、各薬液処理工程の間に、石英ガラス表面に残留する処理液の成分を水や溶剤を用いて洗浄した後、乾燥する工程を含むことが好適である。薬液処理工程前の乾燥は、クリーンな環境下でのクリーン乾燥が好ましい。また、乾燥後、速やかに次の薬液処理を行うことが好適である。
　本発明によれば、不均一な凹凸（ムラ）の発生を抑え、ムラの低減が図れ、ムラを消すための処理回数を少なくすることができ、１～２回の少数回の薬液処理でも均一性に優れたムラの少ない石英ガラス治具の製造方法及び石英ガラス治具を提供することができる。平滑な石英ガラス表面に前記付着物除去工程及び薬液処理工程を行うことにより、１回の薬液処理でも薬液処理による凹凸仕上げのムラとなる凹凸形成の不均一さが低減され、外観の見栄えの良い石英ガラス治具を提供することができ、それにより、２回目の薬液処理を行う場合も２回目の薬液処理がより効果的になる。 Although the chemical solution treatment may be performed once, it is more preferable that the uneven finish surface is formed by performing the unevenness forming step by the chemical solution treatment a plurality of times. When the chemical treatment is performed a plurality of times, it is preferable to include, between each chemical treatment step, a step of washing the remaining treatment liquid components on the quartz glass surface with water or a solvent, and then drying the surface. Drying before the chemical solution treatment step is preferably clean drying in a clean environment. Further, it is preferable to immediately perform the next chemical solution treatment after drying.
According to the present invention, the occurrence of uneven unevenness (unevenness) can be suppressed, the unevenness can be reduced, the number of treatments for eliminating unevenness can be reduced, and uniformity can be achieved even with a small number of chemical treatments, such as one or two times. It is possible to provide a method for manufacturing a quartz glass jig with excellent properties and little unevenness, and the quartz glass jig. By performing the deposit removal step and the chemical solution treatment step on the smooth quartz glass surface, the non-uniform formation of the unevenness caused by the chemical solution treatment is reduced even with a single chemical solution treatment, and the appearance is good. A quartz glass jig can be provided, which makes the second chemical treatment more effective when performing the second chemical treatment.
　本発明の石英ガラス冶具は、石英ガラス表面の少なくとも２０ｃｍ２以上の面積に凹凸が形成されてなる薬液処理部分を有する石英ガラス冶具であり、前記薬液処理部分が、凹凸が形成された凹凸仕上げ面とされてなり、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス冶具である。 The quartz glass jig of the present invention is a quartz glass jig having a chemical solution-treated portion in which unevenness is formed in an area of at least 20 cm 2 or more on the quartz glass surface, and the chemical solution-treated portion is an uneven finished surface on which unevenness is formed. The quartz glass jig has a standard deviation of 1.00 μm or less when the surface roughness Ra of the irregularly finished surface is measured at 10 or more locations.
　さらに、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下であるのが好適である。このように、石英ガラス治具の白濁の均一／不均一（即ち凹凸形成の均一／不均一）の判定については、凹凸が形成された表面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下で、且つ、表面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下である事が好ましい。 Furthermore, it is preferable that the coefficient of variation is 0.60 or less when the surface roughness Ra of the unevenly finished surface is measured at 10 or more points. As described above, the uniformity/non-uniformity of the opacity of the quartz glass jig (that is, the uniformity/non-uniformity of the formation of unevenness) can be determined by measuring the surface roughness Ra of the unevenness-formed surface at 10 or more locations. It is preferable that the deviation is 1.00 μm or less and the variation coefficient is 0.60 or less when the surface roughness Ra is measured at 10 or more points.
　また、前記凹凸仕上げ面を均一に白濁した半透明な表面とすることが好適である。
　前記凹凸仕上げ面の白濁や透明性の程度は特に制限はないが、前記凹凸仕上げ面の６０度計での光沢度が２未満であるのが好適である。特に、前記凹凸仕上げ面を１０箇所以上測定した時の光沢度の平均値が２未満であることがより好適であり、１以下がさらに好適である。さらに、前記凹凸仕上げ面の６０度計での光沢度の最大値が２未満であることが好ましく、１以下がより好ましい。
　また、前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の可視光透過率の平均値が３０％以下であるのが好適であり、また、前記可視光透過率の標準偏差が１％以下であるのが好適であり、０．５％以下がより好適である。 Further, it is preferable that the uneven finish surface is a uniformly opaque translucent surface.
Although there is no particular limitation on the degree of opacity or transparency of the unevenly finished surface, it is preferable that the glossiness of the unevenly finished surface is less than 2 on a 60-degree meter. In particular, it is more preferable that the average value of the glossiness measured at 10 or more locations on the uneven finished surface is less than 2, more preferably 1 or less. Furthermore, the maximum value of the glossiness of the irregularly finished surface measured by a 60 degree meter is preferably less than 2, more preferably 1 or less.
In addition, it is preferable that the average value of the visible light transmittance when measuring the visible light transmittance with a tintometer of the uneven finish surface at 10 or more points is 30% or less. Preferably the deviation is 1% or less, more preferably 0.5% or less.
　本発明の石英ガラス冶具を製造するには、上記した本発明の石英ガラス冶具の製造方法が好適に用いられる。 In order to manufacture the quartz glass jig of the present invention, the method of manufacturing the quartz glass jig of the present invention described above is preferably used.
　また、前記薬液処理部分に、２００ｍｍ２以上の範囲の凹凸仕上げムラが存在しないのが好適である。前記凹凸仕上げムラとしては、斑状のもの、透明感の強い（白濁の薄い）部分、多数のスジ模様によるストライプ状、微細斑点の集合など、様々な形状のムラが挙げられる。特に、刷毛模様のようなムラや指紋跡のような、方向性をもった局所ムラが挙げられる。 Further, it is preferable that unevenness in finish of unevenness in the range of 200 mm 2 or more does not exist in the portion treated with the chemical solution. Examples of uneven finish unevenness include unevenness in various shapes, such as spots, highly transparent (lightly opaque) portions, stripes with a large number of streak patterns, and aggregations of fine spots. In particular, directional local unevenness such as brush pattern unevenness and fingerprint traces can be mentioned.
　以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 Although the present invention will be described in more detail with reference to examples below, it goes without saying that these examples are illustrative and should not be construed as limiting.
（実施例１）
　表面処理のされていない平滑で透明な石英ガラス表面（バーナーによる焼仕上げ面や鏡面研磨面）を持つ石英ガラス治具（半導体工業用のＳｉウェーハ処理用石英ガラス炉心管、面積６０００ｃｍ２）を準備し、この石英ガラス治具の石英ガラス表面を５質量％ＨＦ水溶液で１５分間ＨＦ洗浄し、石英ガラス表面のガラス表層のエッチング除去（エッチング量０．４５μｍに相当）を行った後、純水でのリンスを５分間行った。その後、石英ガラス治具を、クリーン乾燥機（クラス１０００）を用いて３０℃で湿度４０～５０％で３時間以上保持し、クリーン乾燥した。 (Example 1)
A quartz glass jig (quartz glass furnace core tube for Si wafer processing for the semiconductor industry, area 6000 cm 2 ) having a smooth and transparent quartz glass surface that has not been subjected to surface treatment (burner-baked surface or mirror-polished surface) is prepared. Then, the quartz glass surface of this quartz glass jig was washed with a 5 mass % HF aqueous solution for 15 minutes to remove the glass surface layer of the quartz glass surface by etching (equivalent to an etching amount of 0.45 μm), and then washed with pure water. was rinsed for 5 minutes. After that, the quartz glass jig was kept at 30° C. and a humidity of 40 to 50% for 3 hours or longer using a clean dryer (class 1000) for clean drying.
　続いて、クリーン乾燥後３０分以内に１回目の薬液処理工程を開始し、表面処理液に石英ガラス治具の石英ガラス表面を９０分間浸漬させる薬液処理工程を行った。薬液処理に用いる表面処理液は、ＨＦ：１５質量％、ＮＨ４Ｆ：１５質量％、酢酸：３５質量％の水溶液を使用した。薬液処理後に純水でリンスした後、前記クリーン乾燥機で同様のクリーン乾燥を行った。
　続いて、クリーン乾燥後３０分以内に２回目の薬液処理工程を開始した。１回目の薬液処理工程と同様の方法で、前記表面処理液での薬液処理、純水でのリンス及びクリーン乾燥を行い、薬液処理された凹凸表面を持つ石英ガラス治具を得た。 Subsequently, the first chemical treatment process was started within 30 minutes after the clean drying, and the chemical treatment process was performed by immersing the quartz glass surface of the quartz glass jig in the surface treatment liquid for 90 minutes. As the surface treatment liquid used for chemical treatment, an aqueous solution of HF: 15% by mass, NH 4 F: 15% by mass, and acetic acid: 35% by mass was used. After rinsing with pure water after chemical treatment, similar clean drying was performed with the clean dryer.
Subsequently, the second chemical treatment process was started within 30 minutes after clean drying. Chemical treatment with the surface treatment liquid, rinsing with pure water, and clean drying were performed in the same manner as in the first chemical treatment step to obtain a quartz glass jig having a chemically treated uneven surface.
　得られた石英ガラス治具は、表面が白濁し半透明であり、目視で白濁の濃さに大きな分布は見られなかった。また、表面には２００ｍｍ２以上の範囲の凹凸仕上げムラは存在しなかった。図１に実施例１で得られた石英ガラス治具の表面の電子顕微鏡写真を示す。図１の写真の右下のスケールは１００μｍである。図５に実施例１によって得られた石英ガラス治具の写真を示す。 The resulting quartz glass jig had a cloudy and translucent surface, and no large distribution of cloudiness was visually observed. In addition, there was no irregularity in finishing of 200 mm 2 or more on the surface. FIG. 1 shows an electron micrograph of the surface of the quartz glass jig obtained in Example 1. As shown in FIG. The scale at the bottom right of the photograph in FIG. 1 is 100 μm. FIG. 5 shows a photograph of the quartz glass jig obtained in Example 1. As shown in FIG.
　また、前記得られた石英ガラス治具の表面の白濁の不均一箇所の面積を測定した。白濁の不均一箇所の面積の測定方法は、背景に黒色の板を用い、目視において、白濁の濃淡の違いがある箇所を抽出し、その箇所の面積を概算で縦、横の寸法から求め、全体の表面積に対する割合を測定した。白濁の濃淡のある個所が複数あれば全て合算し、面積として測定した。結果を表１に示す。表１において、白濁の不均一箇所の面積の検査基準は、石英ガラス治具の全体の表面積に対する白濁の不均一箇所の面積の割合が２５％以下の場合を良品と判定し、２５％超の場合を不良品と判定した。表１に示した如く、実施例１で得られた石英ガラス治具の白濁の不均一箇所の面積は、１０％であった。 In addition, the area of the non-uniform white turbidity on the surface of the obtained quartz glass jig was measured. The method of measuring the area of the uneven cloudiness is to use a black plate as the background, visually extract the location where there is a difference in the density of the cloudiness, and roughly calculate the area of that location from the vertical and horizontal dimensions. The percentage of total surface area was measured. If there were a plurality of places with different shades of cloudiness, they were all added up and measured as an area. Table 1 shows the results. In Table 1, the inspection criteria for the area of the non-uniform white turbidity are as follows. case was determined to be defective. As shown in Table 1, the area of non-uniform white turbidity in the quartz glass jig obtained in Example 1 was 10%.
　また、前記得られた石英ガラス治具の表面粗さＲａを、表面粗さ計（ミツトヨ社製小型表面粗さ測定機『サーフテストＳＪ－３１０』）を用いて１８箇所のＲａ測定箇所（測定ポイント）にて測定した。図４ａ及び図４ｂは、実施例１の石英ガラス治具の表面粗さＲａの測定方法におけるＲａ測定箇所（測定ポイント）を矢印で示した概略説明図である。図４ａは、測定ポイントを石英ガラス治具（Ｓｉウェーハ処理用石英ガラス炉心管）の側面から見た図であり、図４ｂは、測定ポイントを石英ガラス治具（Ｓｉウェーハ処理用石英ガラス炉心管）の上端側から見た図である。図４ａ及び図４ｂにおいて、符号１０は、石英ガラス治具である石英ガラス炉心管、符号１２は石英ガラス炉心管の胴部、符号１４は石英ガラス炉心管のフランジ部、をそれぞれ示す。 The surface roughness Ra of the quartz glass jig thus obtained was measured at 18 Ra measurement points (measurement point). 4a and 4b are schematic explanatory diagrams showing Ra measurement points (measurement points) in the method of measuring the surface roughness Ra of the quartz glass jig of Example 1 with arrows. FIG. 4a is a side view of the measurement points of the quartz glass jig (silica glass furnace core tube for Si wafer processing), and FIG. ) viewed from the upper end side. 4a and 4b, reference numeral 10 denotes a quartz glass core tube which is a quartz glass jig, reference numeral 12 denotes a body portion of the quartz glass core tube, and reference numeral 14 denotes a flange portion of the quartz glass core tube.
　図４ａに示したように、石英ガラス治具１０の胴部１２の上中下の内外面（矢印Ｏ，Ｐ，Ｑ，Ｒ，Ｓ，Ｔ）の表面粗さＲａを測定し、図４ｂに示した如く、石英ガラス治具１０の胴部１２の周３方向を均等割り（１２０°）し、更に、その上中下の内外面（矢印Ｏ，Ｐ，Ｑ，Ｒ，Ｓ，Ｔ）のそれぞれについて、表面粗さＲａを測定（１８ポイント）した。図４ｂでは、石英ガラス治具１０の胴部１２の周３方向を均等割り（１２０°）し、上の部分の内外面（矢印Ｏ１，Ｏ２，Ｏ３及びＲ１，Ｒ２，Ｒ３）の測定ポイントを示してある。 As shown in FIG. 4a, the surface roughness Ra of the upper, middle and lower inner and outer surfaces (arrows O, P, Q, R, S, T) of the body 12 of the quartz glass jig 10 was measured. As shown, the circumference of the body portion 12 of the quartz glass jig 10 is divided equally (120°) in three directions, and furthermore, the inner and outer surfaces (arrows O, P, Q, R, S, T) of the upper, middle and lower sides are divided. For each, the surface roughness Ra was measured (18 points). In FIG. 4b, the circumference of the body portion 12 of the quartz glass jig 10 is equally divided in three directions (120°), and the measurement points of the inner and outer surfaces (arrows O1, O2, O3 and R1, R2, R3) of the upper portion are determined. is shown.
　前記上中下の測定ポイントは、表面粗さの測定ポイントを簡略的に示した図４ａ及び図４ｂより、石英ガラス治具である石英ガラス炉心管１２におけるフランジ部１４を除き、円筒部分側面平面の上端から下端までを全高としたとき、上端から全高の２０％（１０～３０％）中央寄りの上測定点、全高中央の中央測定点（中央～±１５％以内）、下端から全高の２０％（１０～３０％）中央寄りの下測定点、とした。表面粗さＲａの平均値や変動係数などの結果を表１に示す。 4a and 4b, which show the surface roughness measurement points in a simplified manner, the upper, middle and lower measurement points are the cylindrical portion side planes except for the flange portion 14 in the quartz glass furnace core tube 12, which is a quartz glass jig. When the total height is from the top end to the bottom end, the upper measurement point near the center of 20% (10 to 30%) of the total height from the top end, the center measurement point at the center of the total height (within ± 15% from the center), 20% of the total height from the bottom end % (10 to 30%) at the lower measurement point near the center. Table 1 shows the results such as the average value of the surface roughness Ra and the coefficient of variation.
　また、前記得られた石英ガラス治具の光沢度を、光沢計（堀場製作所社製グロスチェッカ　ＩＧ－３３０）を用いて６０度計での測定を１８箇所行った。測定ポイントは表面粗さの測定ポイントに準ずる。光沢度の平均値などを表２に示す。
　また、前記得られた石英ガラス治具から１０箇所サンプルを切出し、ティントメーター（佐藤商事社製ＭＪ－ＴＭ１１０）を用いて可視光線透過率を測定（１０ポイント）した。サンプルを切出した１０箇所は、図４ａに示したように、石英ガラス治具１０の胴部１２の上中下（矢印Ｏ，Ｐ，Ｑ）とし、図４ｂに示した如く、石英ガラス治具１０の胴部１２の周３方向を均等割り（１２０°）し、更に、その上中下（矢印Ｏ，Ｐ，Ｑ）のそれぞれについてと、石英ガラス治具の頭頂部（矢印Ｕ、符号１４フランジ部と反対の位置）とした。ティントメーターによる可視光透過率の平均値や標準偏差などを表２に示す。 Further, the glossiness of the obtained quartz glass jig was measured at 18 points with a 60 degree meter using a glossmeter (gloss checker IG-330 manufactured by Horiba, Ltd.). Measurement points conform to the surface roughness measurement points. Table 2 shows the average value of glossiness and the like.
Further, 10 samples were cut out from the obtained quartz glass jig, and the visible light transmittance was measured (10 points) using a tintometer (MJ-TM110 manufactured by Sato Shoji Co., Ltd.). The ten locations where the sample was cut are, as shown in FIG. 10 is equally divided (120°) in three directions around the circumference of the body 12, and furthermore, each of the upper, middle and lower (arrows O, P, Q) and the top of the quartz glass jig (arrow U, reference 14 position opposite to the flange). Table 2 shows the average value and standard deviation of the visible light transmittance measured by a tintometer.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（実施例２）
　実施例１と同様に、表面処理のされていない平滑で透明な面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を実施例１と同様にＨＦ洗浄し、純水でリンスを行った。その後石英ガラス治具を無塵布にエタノールを浸み込ませ、拭き取りを行い、実施例１と同様にクリーン乾燥を行った。
　続いて、クリーン乾燥後３０分以内に１回目の薬液処理工程を開始した。実施例１と同様の処理液及び処理条件により、石英ガラス治具の表面の薬液処理を行った。薬液処理後に純水でリンスを行った。そして、クリーン乾燥機（クラス１０００）を用いて３０℃で湿度５０～６０％でクリーン乾燥を３時間以上行った。
　続いて、クリーン乾燥後３０分以内に２回目の薬液処理工程を開始した。１回目の薬液処理工程と同様の方法で、薬液処理、純水によるリンス及びクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Example 2)
As in Example 1, a quartz glass jig having a smooth and transparent surface that has not undergone surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, and then washed with pure water. I rinsed with After that, the quartz glass jig was wiped with a dust-free cloth impregnated with ethanol, and then clean-dried in the same manner as in the first embodiment.
Subsequently, within 30 minutes after the clean drying, the first chemical treatment process was started. Using the same treatment liquid and treatment conditions as in Example 1, the surface of the quartz glass jig was treated with the chemical solution. After chemical treatment, rinsing was performed with pure water. Then, using a clean dryer (class 1000), clean drying was performed at 30° C. and a humidity of 50 to 60% for 3 hours or longer.
Subsequently, the second chemical treatment process was started within 30 minutes after clean drying. Chemical treatment, rinsing with pure water, and clean drying were performed in the same manner as in the first chemical treatment process. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は、表面が白濁し半透明であり、目視で白濁の濃さに大きな分布は見られなかった。また、表面には２００ｍｍ２以上の範囲の凹凸仕上げムラは存在しなかった。表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、５％であった。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig was cloudy and translucent, and no large distribution of cloudiness was observed visually. In addition, there was no irregularity in finishing of 200 mm 2 or more on the surface. Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. Moreover, the area of the non-uniform part of cloudiness at this time was 5%.
（実施例３）
　実施例１と同様に、表面処理のされていない平滑で透明な石英ガラス表面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を実施例１と同様にＨＦ洗浄し、純水でリンスを行った。クリーン度が制御された空間（クラス１０，０００のクリーンルーム）内で、ＩＲランプと熱風乾燥機（吹き出し温度８０℃）を用いて２時間以上クリーン乾燥した。
　続いて、クリーン乾燥後３０分以内に１回目の薬液処理工程を開始した。実施例１と同様の処理液及び処理条件により、薬液処理を行った。薬液処理後に純水でリンスした後、前記ＨＦ洗浄後のクリーン乾燥と同様の方法で、クリーン度が制御された空間（クラス１０，０００のクリーンルーム）内でクリーン乾燥を行った。
　続いて、クリーン乾燥後３０分以内に、２回目の薬液処理工程を開始した。１回目の薬液処理工程と同様の方法で、薬液処理、純水でのリンス及びクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Example 3)
In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, Rinsing was performed with pure water. Clean drying was performed for 2 hours or more using an IR lamp and a hot air dryer (blowing temperature 80° C.) in a space (class 10,000 clean room) where the degree of cleanliness was controlled.
Subsequently, within 30 minutes after the clean drying, the first chemical treatment process was started. Using the same treatment liquid and treatment conditions as in Example 1, chemical treatment was performed. After rinsing with pure water after the chemical treatment, clean drying was performed in a space (class 10,000 clean room) where the degree of cleanliness was controlled in the same manner as the clean drying after the HF cleaning.
Subsequently, within 30 minutes after the clean drying, the second chemical treatment process was started. Chemical treatment, rinsing with pure water, and clean drying were performed in the same manner as in the first chemical treatment process. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は、表面が白濁し半透明であり、目視で白濁の濃さに大きな分布は見られなかった。また、表面には２００ｍｍ２以上の範囲の凹凸仕上げムラは存在しなかった。表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、２０％であった。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig was cloudy and translucent, and no large distribution of cloudiness was observed visually. In addition, there was no irregularity in finishing of 200 mm 2 or more on the surface. Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 20%.
（実施例４）
　実施例１と同様に、表面処理のされていない平滑で透明な石英ガラス表面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を実施例１と同様にＨＦ洗浄し、純水でリンスを行った。クリーン度が制御された空間（クラス１０，０００のクリーンルーム）内で、ＩＲランプと熱風乾燥機（吹き出し温度８０℃）を用いて２時間以上クリーン乾燥した。
　続いて、クリーン乾燥後３０分以内に薬液処理工程を開始した。実施例１と同様の処理液を用いて同様の薬液処理を行った。薬液処理後に純水によるリンス、前記ＨＦ洗浄後のクリーン乾燥と同様のクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Example 4)
In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was washed with HF in the same manner as in Example 1, Rinsing was performed with pure water. Clean drying was performed for 2 hours or more using an IR lamp and a hot air dryer (blowing temperature 80° C.) in a space (class 10,000 clean room) where the degree of cleanliness was controlled.
Subsequently, the chemical treatment process was started within 30 minutes after clean drying. Using the same treatment liquid as in Example 1, the same chemical treatment was performed. After the chemical treatment, rinsing with pure water and clean drying similar to the clean drying after the HF cleaning were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は、表面が白濁し半透明であり、目視で白濁の濃さに大きな分布は見られなかった。また、表面には２００ｍｍ２以上の範囲の凹凸仕上げムラは存在しなかった。表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、２０％であった。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig was cloudy and translucent, and no large distribution of cloudiness was observed visually. In addition, there was no irregularity in finishing of 200 mm 2 or more on the surface. Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 20%.
　表１及び２からわかるように、実施例１～４では石英ガラス治具の表面が均一に白濁した均一な半透明面となっており、凹凸が連続的に形成された均一な凹凸仕上げ面となっており、大型の石英ガラス治具であっても表面の凹凸仕上げ面にムラが目立たず、優れた均一性を有する凹凸仕上げ面を備えた石英ガラス治具となった。そして、実施例１～４の石英ガラス治具は、石英ガラス治具の全体の表面積に対する白濁の不均一箇所の面積の割合が２５％以下の良品であり、さらに標準偏差が１以下、変動係数が０．６以下の表面粗さを実現できている。 As can be seen from Tables 1 and 2, in Examples 1 to 4, the surface of the quartz glass jig was a uniform translucent surface that was uniformly clouded, and a uniform uneven finish surface in which unevenness was continuously formed. Thus, even with a large-sized quartz glass jig, unevenness is not conspicuous on the unevenly finished surface, and the quartz glass jig has an unevenly finished surface with excellent uniformity. The quartz glass jigs of Examples 1 to 4 are non-defective products in which the ratio of the area of the non-uniform white turbidity to the entire surface area of the quartz glass jig is 25% or less, the standard deviation is 1 or less, and the coefficient of variation is 1 or less. has achieved a surface roughness of 0.6 or less.
　さらに、実施例１では、薬液処理による凹凸形成工程を２回繰り返して凹凸仕上げ面を形成したが、さらに薬液処理による凹凸形成工程を繰り返して、合計４回の薬液処理による凹凸形成工程を行った場合の石英ガラス治具の写真を図６に示す。図６に示されるように、表面が白濁し半透明であり、図５の石英ガラス治具よりもさらに、目視で、表面の凹凸仕上げ面にムラが目立たず、優れた均一性を有する凹凸仕上げ面を備えた石英ガラス治具となった。 Furthermore, in Example 1, the step of forming unevenness by chemical treatment was repeated twice to form an uneven finished surface, but the step of forming unevenness by chemical treatment was further repeated, and the unevenness forming step by chemical treatment was performed four times in total. A photograph of the quartz glass jig in this case is shown in FIG. As shown in FIG. 6, the surface is cloudy and translucent, and even more visually than the quartz glass jig of FIG. A quartz glass jig with a face was obtained.
（比較例１）
　実施例１と同様に、表面処理のされていない平滑で透明な石英ガラス表面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を、付着物除去工程（５質量％ＨＦ洗浄、純水洗浄及び乾燥工程）を行わずに、実施例１と同様の薬液処理を行った。薬液処理後に実施例１と同様に純水でリンスした後、通常乾燥を行った。
　続いて、再度、薬液処理工程を開始し、同様な濃度条件で、薬液処理を行った。薬液処理後に純水によるリンス、実施例１と同様のクリーン乾燥を行い、凹凸表面を持つ石英ガラス治具を得た。 (Comparative example 1)
In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface that was not surface-treated was prepared, and the quartz glass surface of this quartz glass jig was subjected to a deposit removal step (5 wt% HF The same chemical treatment as in Example 1 was performed without performing the washing, pure water washing, and drying steps. After the chemical treatment, the substrate was rinsed with pure water in the same manner as in Example 1, and then dried normally.
Subsequently, the chemical solution treatment process was started again, and the chemical solution treatment was performed under the same concentration conditions. After the chemical treatment, rinsing with pure water and clean drying in the same manner as in Example 1 were performed to obtain a quartz glass jig having an uneven surface.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は白濁し半透明であるが不均一で、白濁の濃い部分と白濁が薄く透明感のある部分が見られた。また、表面には２００ｍｍ２以上の範囲の方向性をもった局所ムラである凹凸仕上げムラが存在した。図２に比較例１で得られた石英ガラス治具の表面の白濁の濃い部分の電子顕微鏡写真を示す。図２の写真の右下のスケールは１００μｍである。
　白濁が薄く透明感がある部分を観察すると、凹凸が形成されていない部分が見られた。図３に比較例１で得られた石英ガラス治具の表面の凹凸が形成されていない部分の電子顕微鏡写真を示す。図３の写真の右下のスケールは１００μｍである。
　表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、３０％であった。
　比較例１で得られた石英ガラス治具の写真を図７～９に示す。図７は、石英ガラス治具（Ｓｉウェーハ処理用石英ガラス炉心管）を横に倒して処理液に浸漬して薬液処理した際の石英ガラス治具の上面に該当する部分、図８は該石英ガラス治具の側面に該当する部分、図９は該石英ガラス治具の下面に該当する部分をそれぞれ示す。そして、図７～図９において、それぞれムラ１６，１８，２０が存在するのがわかる。特に、図８（ｂ）には、ムラ１８は筋状のムラとなっており、方向性を持った局所ムラとなっているのがわかる。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The quartz glass jig was cloudy and translucent, but uneven, and there were dark cloudy parts and light cloudy transparent parts. In addition, unevenness in finish, which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface. FIG. 2 shows an electron micrograph of a heavily clouded portion on the surface of the quartz glass jig obtained in Comparative Example 1. As shown in FIG. The scale at the bottom right of the photograph in FIG. 2 is 100 μm.
Observation of the portion where the white turbidity was light and had a sense of transparency revealed a portion where unevenness was not formed. FIG. 3 shows an electron micrograph of a portion of the quartz glass jig obtained in Comparative Example 1 where the surface unevenness is not formed. The scale at the bottom right of the photograph in FIG. 3 is 100 μm.
Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 30%.
Photographs of the quartz glass jig obtained in Comparative Example 1 are shown in FIGS. FIG. 7 shows a portion corresponding to the upper surface of the quartz glass jig (quartz glass furnace core tube for Si wafer processing) laid down and immersed in the treatment liquid for chemical treatment, and FIG. A portion corresponding to the side surface of the glass jig, and FIG. 9 shows a portion corresponding to the bottom surface of the quartz glass jig. 7 to 9, it can be seen that irregularities 16, 18 and 20 are present, respectively. In particular, in FIG. 8B, it can be seen that the unevenness 18 is streak-like unevenness and localized unevenness with directionality.
（比較例２）
　実施例１と同様に、表面処理のされていない平滑で透明な石英ガラス表面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を、洗浄時間以外は実施例１と同様に、５質量％ＨＦで１分洗浄（エッチング量０．０３μｍに相当）を行い、純水でリンスを行った。クリーン乾燥機（クラス１０００）で３０℃で湿度５０～６０％で３時間以上保持しクリーン乾燥した。前記乾燥後の石英ガラス治具は、ＨＦ洗浄による付着物除去が不十分であり、石英ガラス表面に付着物が残存していた。
　続いて、クリーン乾燥後３０分以内に実施例１と同様に、１回目の薬液処理を行った。薬液処理後に実施例１と同様に、純水によるリンス、クリーン乾燥を行い、更にもう一度、実施例１と同様に、薬液処理、純水によるリンス及びクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Comparative example 2)
In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared, and the quartz glass surface of this quartz glass jig was treated in the same manner as in Example 1 except for the washing time. Then, it was washed with 5% by mass HF for 1 minute (equivalent to an etching amount of 0.03 μm) and rinsed with pure water. It was clean-dried in a clean dryer (class 1000) at 30° C. and humidity of 50 to 60% for 3 hours or longer. The quartz glass jig after drying was insufficiently removed by HF cleaning, and the adherents remained on the surface of the quartz glass.
Then, within 30 minutes after clean drying, the first chemical treatment was performed in the same manner as in Example 1. After the chemical treatment, rinsing with pure water and clean drying were performed in the same manner as in Example 1, and chemical treatment, rinsing with pure water and clean drying were performed again in the same manner as in Example 1. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。比較例１で得られた石英ガラス治具は、その表面が白濁し半透明であるが不均一で、白濁の濃い部分と白濁が薄く透明感のある部分が見られた。また、表面には２００ｍｍ２以上の範囲の方向性をもった局所ムラである凹凸仕上げムラが存在した。白濁が薄く透明感がある部分を観察すると、凹凸が形成されていない部分が見られた。
　表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、３５％であった。比較例２で得られた石英ガラス治具の写真を図１０に示す。図１０（ａ）には方向性をもった局所ムラである筋状のムラ２２が存在し、図１０（ｂ）には小さいムラの集合体であるムラ２４が存在するのがわかる。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig obtained in Comparative Example 1 was cloudy and translucent, but uneven, and there were portions with deep cloudiness and portions with light cloudiness and a sense of transparency. In addition, unevenness in finish, which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface. Observation of the portion where the white turbidity was light and had a sense of transparency revealed a portion where unevenness was not formed.
Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 35%. A photograph of the quartz glass jig obtained in Comparative Example 2 is shown in FIG. FIG. 10A shows streaky unevenness 22, which is local unevenness with directionality, and FIG. 10B shows unevenness 24, which is an aggregate of small unevennesses.
（比較例３）
　実施例１と同様に、表面処理のされていない平滑で透明な石英ガラス表面を持つ石英ガラス治具を準備し、この石英ガラス治具の石英ガラス表面を、実施例１と同様に５質量％ＨＦで洗浄した後、純水によるリンス、通常乾燥を行った。
　２４時間クリーン度の管理されていない環境で保管した後、実施例１と同様に、薬液処理を行った。薬液処理後に純水によるリンス、通常乾燥を行い、更にもう一度薬液処理及び純水によるリンス、実施例１と同様のクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Comparative Example 3)
In the same manner as in Example 1, a quartz glass jig having a smooth and transparent quartz glass surface without surface treatment was prepared. After washing with HF, rinsing with pure water and general drying were performed.
After being stored in an environment where the degree of cleanliness is not controlled for 24 hours, chemical treatment was performed in the same manner as in Example 1. After the chemical treatment, rinsing with pure water and normal drying were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は、表面が白濁し半透明であるが不均一で、白濁の濃い部分と白濁が薄く透明感のある部分が見られた。また、表面には２００ｍｍ２以上の範囲の方向性をもった局所ムラである凹凸仕上げムラが存在した。比較例３で得られた石英ガラス治具の写真を図１１に示す。図１１（ａ）には方向性をもった局所ムラである筋状のムラ２６が存在し、また、図１１（ｂ）には比較的大きな面積のムラ２８が存在するのがわかる。
　表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、３０％であった。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig was cloudy and translucent, but it was uneven, and there were a part with deep cloudiness and a part with light cloudiness and a sense of transparency. In addition, unevenness in finish, which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface. A photograph of the quartz glass jig obtained in Comparative Example 3 is shown in FIG. FIG. 11(a) shows streaky unevenness 26, which is local unevenness with directionality, and FIG. 11(b) shows unevenness 28 with a relatively large area.
Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 30%.
（比較例４）
　成膜プロセスに使用する石英治具を、純水槽に浸漬し、その直後に、乾燥は行わず、実施例１と同様に、薬液処理を行った。
　薬液処理後に純水によるリンス、通常乾燥を行い、更にもう一度薬液処理、純水によるリンス、実施例１と同様のクリーン乾燥を行った。薬液処理された凹凸表面を持つ石英ガラス治具を得た。 (Comparative Example 4)
A quartz jig used in the film forming process was immersed in a pure water bath, and immediately after that, chemical treatment was performed in the same manner as in Example 1 without drying.
After the chemical treatment, rinsing with pure water and normal drying were performed. A quartz glass jig having an uneven surface treated with a chemical solution was obtained.
　前記得られた石英ガラス治具に対し、実施例１と同様の測定方法により各測定を行った。結果を表１及び２に示す。石英ガラス治具は、表面が白濁し、半透明であるが、不均一で、白濁の濃い部分と薄く透明感のある部分が見られた。また、表面には２００ｍｍ２以上の範囲の方向性をもった局所ムラである凹凸仕上げムラが存在した。
　表面粗さＲａや光沢度、ティントメーターによる可視光透過率の平均値や変動係数などは表１及び２のようになった。また、この時の白濁の不均一箇所の面積は、３０％であった。 Each measurement was performed by the same measurement method as in Example 1 for the obtained quartz glass jig. Results are shown in Tables 1 and 2. The surface of the quartz glass jig was cloudy and translucent, but it was uneven, and a part with a deep cloudiness and a part with a thin transparent feeling were observed. In addition, unevenness in finish, which is local unevenness with directionality in the range of 200 mm 2 or more, was present on the surface.
Tables 1 and 2 show the surface roughness Ra, the glossiness, the average value of the visible light transmittance measured by the tintometer, the coefficient of variation, and the like. In addition, the area of the non-uniform white turbidity at this time was 30%.
　表１及び２からわかるように、比較例１～４では石英ガラス治具の表面が均一に白濁しておらず、凹凸が連続的に形成された均一な凹凸仕上げ面となっていない。そして、比較例１～４の石英ガラス治具は、石英ガラス治具の全体の表面積に対する白濁の不均一箇所の面積の割合が３０％以上の不良品であり、さらに標準偏差が１以下、変動係数が０．６以下の表面粗さを実現できていない。 As can be seen from Tables 1 and 2, in Comparative Examples 1 to 4, the surfaces of the quartz glass jigs were not uniformly clouded, and the uneven surfaces were not uniformly finished with unevenness formed continuously. The quartz glass jigs of Comparative Examples 1 to 4 are defective products in which the ratio of the area of the non-uniform white turbidity to the entire surface area of the quartz glass jig is 30% or more, and the standard deviation is 1 or less. A surface roughness with a coefficient of 0.6 or less has not been achieved.
　上述のようにして得られた本発明の石英ガラス治具は、半導体処理用、光学用、理化学機器用、装飾用等の材料として使用することができる。特に、半導体を製造するための半導体プロセスで使用する石英ガラス治具として好適である。 The quartz glass jig of the present invention obtained as described above can be used as a material for semiconductor processing, optics, physics and chemistry equipment, decoration, and the like. In particular, it is suitable as a quartz glass jig used in a semiconductor process for manufacturing semiconductors.
　１０：石英ガラス炉心管、１２：胴部、１４：フランジ部、１６，１８，２０，２２，２４，２６：ムラ、Ｏ，Ｐ，Ｑ，Ｒ，Ｓ，Ｔ，Ｏ１，Ｏ２，Ｏ３，Ｒ１，Ｒ２，Ｒ３：表面粗さＲａの測定ポイントを示す矢印、Ｕ：可視光線透過率の測定ポイントを示す矢印。 10: quartz glass furnace core tube, 12: body, 14: flange, 16, 18, 20, 22, 24, 26: unevenness, O, P, Q, R, S, T, O1, O2, O3, R1 , R2, R3: arrows indicating measurement points of surface roughness Ra, U: arrows indicating measurement points of visible light transmittance.

Claims (11)

  1. 　薬液処理により、凹凸が表面に形成されてなる石英ガラス治具の製造方法であり、
    　平滑な石英ガラス表面の付着物を除去する付着物除去工程と、
    　前記付着物が除去された前記石英ガラス表面に前記薬液処理による凹凸形成により凹凸仕上げ面を形成する仕上げ面形成薬液処理工程と、
    を含み、
    　前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス治具の製造方法。     A method for manufacturing a quartz glass jig having irregularities formed on its surface by chemical treatment,
    a deposit removing step of removing deposits on the smooth quartz glass surface;
    a finished surface forming chemical solution treatment step of forming an uneven finished surface by forming unevenness by the chemical solution treatment on the quartz glass surface from which the deposits have been removed;
    including
    A method for manufacturing a quartz glass jig, wherein the standard deviation is 1.00 μm or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more points.
  2. 　前記凹凸仕上げ面の６０度計での光沢度が２未満であり、
    　前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の平均値が３０％以下で標準偏差が１％以下である、請求項１記載の石英ガラス治具の製造方法。     The uneven finish surface has a glossiness of less than 2 with a 60 degree meter,
    2. The method of manufacturing a quartz glass jig according to claim 1, wherein the average value of the visible light transmittance measured by a tintometer at 10 or more locations on the unevenly finished surface is 30% or less and the standard deviation is 1% or less.
  3. 　前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下である、請求項１記載の石英ガラス治具の製造方法。 The method for manufacturing a quartz glass jig according to claim 1, wherein the variation coefficient is 0.60 or less when the surface roughness Ra of the uneven finished surface is measured at 10 or more locations.
  4. 　前記付着物除去工程が、
    　ＨＦを含む洗浄液を用いて前記平滑な石英ガラス表面の付着物を除去するＨＦ洗浄工程と、
    　前記ＨＦ洗浄工程後、石英ガラス表面に残留するＨＦ成分を水により希釈除去する第一除去工程と、
    　前記第一除去工程後、石英ガラス表面に残留する付着水分及び／又は付着溶剤を除去する第二除去工程と、
    を含む、請求項１記載の石英ガラス治具の製造方法。     The deposit removal step includes
    an HF cleaning step of removing deposits on the smooth quartz glass surface using a cleaning liquid containing HF;
    a first removal step of diluting and removing the HF component remaining on the quartz glass surface after the HF cleaning step with water;
    a second removing step of removing the attached moisture and/or the attached solvent remaining on the surface of the quartz glass after the first removing step;
    The method for manufacturing a quartz glass jig according to claim 1, comprising:
  5. 　前記ＨＦ洗浄工程において、前記石英ガラス表面のガラス表層が０．１０μｍ以上エッチング除去される、請求項４記載の石英ガラス治具の製造方法。 The method for manufacturing a quartz glass jig according to claim 4, wherein the glass surface layer of the quartz glass surface is etched away by 0.10 µm or more in the HF cleaning step.
  6. 　前記第二除去工程が、湿度６０％未満雰囲気且つクリーンな環境下で前記石英ガラス表面を乾燥する乾燥工程である、請求項４記載の石英ガラス治具の製造方法。 The method for manufacturing a quartz glass jig according to claim 4, wherein the second removal step is a drying step of drying the quartz glass surface in a clean environment with a humidity of less than 60%.
  7. 　前記薬液処理が、ＨＦ、ＮＨ４Ｆ及び酢酸を含む処理液を用いて行われる、請求項１記載の石英ガラス治具の製造方法。 2. The method of manufacturing a quartz glass jig according to claim 1, wherein said chemical solution treatment is performed using a treatment solution containing HF, NH4F and acetic acid.
  8. 　石英ガラス表面の少なくとも２０ｃｍ２以上の面積に凹凸が形成されてなる薬液処理部分を有する石英ガラス冶具であり、前記薬液処理部分が、凹凸が形成された凹凸仕上げ面とされてなり、前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の標準偏差が１．００μｍ以下である、石英ガラス冶具。 A quartz glass jig having a chemical solution-treated portion in which unevenness is formed on a quartz glass surface having an area of at least 20 cm 2 , wherein the chemical solution-treated portion has an uneven finished surface on which unevenness is formed, and the uneven finish is provided. A quartz glass jig having a standard deviation of 1.00 μm or less when surface roughness Ra is measured at 10 or more locations.
  9. 　前記凹凸仕上げ面の６０度計での光沢度が２未満であり、
    　前記凹凸仕上げ面のティントメーターによる可視光透過率を１０箇所以上測定した時の平均値が３０％以下で標準偏差が１％以下である、請求項８記載の石英ガラス治具。     The uneven finish surface has a glossiness of less than 2 with a 60 degree meter,
    9. The quartz glass jig according to claim 8, wherein the average value of the visible light transmittance measured by a tintometer at 10 or more points on the uneven finished surface is 30% or less and the standard deviation is 1% or less.
  10. 　前記凹凸仕上げ面の表面粗さＲａを１０箇所以上測定した時の変動係数が０．６０以下である、請求項８記載の石英ガラス治具。 The quartz glass jig according to claim 8, wherein the variation coefficient is 0.60 or less when the surface roughness Ra of the irregularly finished surface is measured at 10 or more points.
  11. 　請求項１～７のいずれか１項記載の石英ガラス治具の製造方法により製造されてなる、請求項８～１０のいずれか１項記載の石英ガラス治具。 The quartz glass jig according to any one of claims 8 to 10, which is produced by the method for producing a quartz glass jig according to any one of claims 1 to 7.
PCT/JP2022/025076 2021-06-25 2022-06-23 Method for manufacturing fused quartz jig and fused quartz jig WO2022270576A1 (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH07267679A (en) * 1994-03-31 1995-10-17 Shinetsu Quartz Prod Co Ltd Surface treating solution for quartz glass and method for using the same solution
JP2001335342A (en) * 2000-05-19 2001-12-04 Shinetsu Quartz Prod Co Ltd Glass surface treatment liquid and treatment method
JP2005053730A (en) * 2003-08-01 2005-03-03 Shinetsu Quartz Prod Co Ltd Surface treating method of quartz glass and quartz glass tool
JP2008528432A (en) * 2005-02-03 2008-07-31 ヘラオイス．クヴァールツグラース．ゲゼルシャフト．ミット．ベシュレンクテル．ハフツング．ウント．コンパニー．コマンディットゲゼルシャフト Method of forming a component of quartz glass for use in semiconductor manufacturing and component obtained according to the method
WO2021112113A1 (en) * 2019-12-04 2021-06-10 信越石英株式会社 Method for producing quartz glass

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07267679A (en) * 1994-03-31 1995-10-17 Shinetsu Quartz Prod Co Ltd Surface treating solution for quartz glass and method for using the same solution
JP2001335342A (en) * 2000-05-19 2001-12-04 Shinetsu Quartz Prod Co Ltd Glass surface treatment liquid and treatment method
JP2005053730A (en) * 2003-08-01 2005-03-03 Shinetsu Quartz Prod Co Ltd Surface treating method of quartz glass and quartz glass tool
JP2008528432A (en) * 2005-02-03 2008-07-31 ヘラオイス．クヴァールツグラース．ゲゼルシャフト．ミット．ベシュレンクテル．ハフツング．ウント．コンパニー．コマンディットゲゼルシャフト Method of forming a component of quartz glass for use in semiconductor manufacturing and component obtained according to the method
WO2021112113A1 (en) * 2019-12-04 2021-06-10 信越石英株式会社 Method for producing quartz glass

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