WO2022270576A1 - Method for manufacturing fused quartz jig and fused quartz jig - Google Patents
Method for manufacturing fused quartz jig and fused quartz jig Download PDFInfo
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- 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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- quartz glass
- glass jig
- less
- unevenness
- uneven
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000005350 fused silica glass Substances 0.000 title abstract 8
- 239000000126 substance Substances 0.000 claims abstract description 98
- 238000011282 treatment Methods 0.000 claims abstract description 91
- 230000003746 surface roughness Effects 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 28
- 238000002834 transmittance Methods 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 33
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 238000004381 surface treatment Methods 0.000 description 28
- 238000005259 measurement Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 19
- 230000003749 cleanliness Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- 235000012431 wafers Nutrition 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 238000000691 measurement method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
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- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000004439 roughness measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 dirt Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000007524 flame polishing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
-
- 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
Description
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.
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.
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
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.
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.
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.
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.
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.
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.
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
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.
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.
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.
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.
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
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.
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
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.
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
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%.
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.
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%.
Claims (11)
- 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. - 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. - 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.
- 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: - 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.
- 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%.
- 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.
- 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.
- 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. - 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.
- 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.
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JP2023530114A JPWO2022270576A1 (en) | 2021-06-25 | 2022-06-23 | |
KR1020237044847A KR20240036521A (en) | 2021-06-25 | 2022-06-23 | Manufacturing method of quartz glass jig and quartz glass jig |
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Citations (5)
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 |
-
2022
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- 2022-06-23 WO PCT/JP2022/025076 patent/WO2022270576A1/en active Application Filing
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Patent Citations (5)
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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