WO2019017489A1 - Dispositif de fabrication d'élément à semi-conducteurs et procédé de fabrication d'éléments à semi-conducteurs - Google Patents

Dispositif de fabrication d'élément à semi-conducteurs et procédé de fabrication d'éléments à semi-conducteurs Download PDF

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Publication number
WO2019017489A1
WO2019017489A1 PCT/JP2018/027360 JP2018027360W WO2019017489A1 WO 2019017489 A1 WO2019017489 A1 WO 2019017489A1 JP 2018027360 W JP2018027360 W JP 2018027360W WO 2019017489 A1 WO2019017489 A1 WO 2019017489A1
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Prior art keywords
resin
wafer
composite resin
nozzle
molded body
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PCT/JP2018/027360
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English (en)
Japanese (ja)
Inventor
弘和 山本
宏貴 伊丹
勇 野口
忠和 塚本
川戸　進
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東邦化成株式会社
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Priority to JP2019530624A priority Critical patent/JPWO2019017489A1/ja
Publication of WO2019017489A1 publication Critical patent/WO2019017489A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
    • H05F1/00—Preventing the formation of electrostatic charges

Definitions

  • the present invention relates to a semiconductor device manufacturing apparatus and a semiconductor device manufacturing method.
  • the solution When applying a cleaning solution, a resist solution, an etching solution, etc. to a semiconductor wafer, the solution is discharged onto the wafer surface while rotating the semiconductor wafer for the purpose of applying the solution uniformly and efficiently removing the excess solution.
  • the method is used.
  • the rotation stage, the chemical solution, and the semiconductor wafer are electrostatically charged by the friction between the air and the rotation stage, the friction between the chemical solution and the nozzle when the chemical solution passes through the nozzle, and the friction between the chemical solution and the wafer surface.
  • electrostatic discharge can cause electrostatic damage to the surface of the semiconductor wafer.
  • Patent Document 1 For the purpose of preventing the above-mentioned electrification, various studies are made on, for example, a cleaning step.
  • a light source is provided on the mounting surface of the cleaning stage, and the semiconductor substrate is irradiated with light from the light source to generate ionized air in the light irradiation area, thereby removing static electricity present on the stage mounting surface.
  • the method is described.
  • Patent Document 2 by using a device provided with a substrate vapor supply nozzle, vapor such as water or carbonated water is supplied to the surface of the substrate, whereby the ionized vapor causes the static electricity present on the surface of the substrate.
  • Patent Document 3 describes a method of manufacturing a semiconductor device in which the surface of a semiconductor wafer is cleaned using a first cleaning water and a second cleaning water having a specific resistance smaller than the first cleaning water. .
  • an object of the present invention is to provide a semiconductor device manufacturing apparatus and a semiconductor device manufacturing method that have an efficient static electricity removing effect, are excellent in cleanability, and are excellent in chemical resistance.
  • the present inventors diligently studied on parts used in a semiconductor device manufacturing apparatus. As a result, it is found that the above object can be achieved by using a manufacturing apparatus having a chuck pin and / or a wafer pin and a nozzle, which is a resin molded body containing a composite resin material containing a fluorocarbon resin and carbon nanotubes. Came to complete.
  • An apparatus for manufacturing a semiconductor device comprising at least a stage for holding a semiconductor wafer, comprising a chuck pin and / or a wafer pin; and a nozzle for supplying a cleaning solution, an etching solution or a resist solution,
  • the nozzle is a resin molded body containing a composite resin material containing at least one fluorocarbon resin and carbon nanotubes; and / or at least one (or one) selected from chuck pins, wafer pins and stages is at least one.
  • the manufacturing apparatus of the semiconductor element which is a resin molding which contains the composite resin material containing a kind of fluoro resin and a carbon nanotube.
  • the chuck pin and / or wafer pin is a resin molded body containing a composite resin material containing at least one fluorocarbon resin and carbon nanotube, and the nozzle is a composite resin containing at least one fluorocarbon resin and carbon nanotube
  • the manufacturing apparatus of the semiconductor element as described in said [1] which is a resin molding containing a material. ([2] can also be described as follows.
  • the stage includes chuck pins and / or wafer pins which are resin moldings including a composite resin material containing at least one fluorocarbon resin and carbon nanotubes,
  • Fluororesins are polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF)
  • PTFE polytetrafluoroethylene
  • modified PTFE modified polytetrafluoroethylene
  • PFA perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer
  • EFE ethylene / te
  • the resin molded body constituting the chuck pin and / or the wafer pin contains 0.01 to 2.0% by mass of carbon nanotubes based on the total amount of the resin molded body, according to the above [1] to [4]
  • the manufacturing apparatus in any one.
  • an apparatus for manufacturing a semiconductor device and a method for manufacturing a semiconductor device which have an efficient static electricity removing effect, are excellent in cleanability, and are excellent in chemical resistance.
  • the manufacturing apparatus of the present invention has at least a stage for holding a semiconductor wafer, and a nozzle for supplying a cleaning solution, an etching solution or a resist solution.
  • the semiconductor device is generally used in the steps of applying a resist solution on the surface of the semiconductor wafer, applying the etching solution, removing particles (impurities) on the semiconductor wafer before and after each treatment step, and used for each treatment.
  • the semiconductor wafer is manufactured through a process of cleaning the surface of the semiconductor wafer and the like.
  • the manufacturing apparatus of the present invention is a manufacturing apparatus used in the above-described process.
  • the manufacturing apparatus of the embodiment of the present disclosure can be used for any process for manufacturing a semiconductor device as long as the manufacturing apparatus can be used.
  • the process includes, for example, a wafer (or wafer) process process (process of processing a semiconductor wafer).
  • Wafer processes include device formation, electrode formation, and wafer inspection. These steps may include, for example, the following steps, more specifically, based on the order of processing the wafers.
  • the above-described processes include wafer cleaning processes as needed.
  • the above-described processes, including the wafer cleaning process can include, for example, the following processes based on the processes on the wafer.
  • Wafer cleaning process eg, wet cleaning, dry cleaning, etc.
  • Wafer heat treatment process eg, oxidation treatment, annealing treatment, etc.
  • Impurity introduction step to the wafer eg, ion implantation method, thermal diffusion method, ion doping method, etc.
  • Thin film formation process on wafer eg, epitaxial growth, CVD, PVD, coating film, plating method, etc.
  • Lithography process eg, resist processing, pattern etching, exposure, etc.
  • Planarization process for example, CMP, etch back, etc.
  • Exposure drawing apparatus contact proximity exposure apparatus, projection exposure apparatus, electron beam exposure apparatus, etc.
  • Resist processing apparatus coating apparatus, developing apparatus, resist peeling apparatus, ashing apparatus, baking apparatus, resist stabilization apparatus, wafer peripheral exposure apparatus, etc.
  • Etching equipment dry etching equipment etc.
  • Cleaning and drying apparatus wet etching apparatus, dry cleaning apparatus, wet cleaning apparatus, scrub cleaning apparatus, drying apparatus, high-pressure jet cleaning apparatus, etc.
  • Heat treatment apparatus oxidation apparatus, diffusion apparatus, annealing apparatus, etc.
  • Ion implantation apparatus high current ion implantation apparatus, medium current ion implantation apparatus, high energy ion implantation apparatus, doping apparatus, etc.
  • CVD apparatus atmospheric pressure CVD apparatus, SACVD apparatus, low pressure CVD apparatus, plasma CVD apparatus, metal CVD apparatus, ALD apparatus, etc.
  • Sputtering apparatus Other thin film forming devices (vacuum deposition)
  • CMP apparatus CMP apparatus, CMP cleaning apparatus, etc.
  • Other processing equipment wafer marking equipment, mark reader, back grinding machine, bump plating equipment, tape grinder for back grinder, back grinder, tape peeling machine for back grinder, etc.
  • the manufacturing apparatus of the present invention at least includes a stage and a nozzle, and the stage includes chuck pins for holding a semiconductor wafer and / or wafer pins in contact with the semiconductor wafer.
  • the semiconductor wafer can be held on the mounting surface of the stage by, for example, holding the outer edge of the semiconductor wafer by the chuck pins provided on the stage. Also, for example, a semiconductor wafer can be supported from the back side by a wafer pin provided on the stage.
  • a rotary drive shaft is attached to the stage. By rotating the rotation drive shaft, the semiconductor wafer can be rotated while being held by the mounting surface of the stage.
  • the resist solution or the etching solution can be uniformly applied to the wafer surface. It becomes possible to remove excess liquid efficiently. Similarly, by supplying the cleaning liquid from the nozzle, the semiconductor wafer can be cleaned efficiently.
  • the manufacturing apparatus of the present invention holds a semiconductor wafer using at least one (or one) selected from conductive chuck pins, wafer pins, and stages, and / or conductivity.
  • the cleaning liquid, the etching liquid or the resist liquid from the nozzle it is possible to reduce the charge of the semiconductor wafer while efficiently preventing the static electricity charged on the semiconductor wafer while avoiding the mixing of impurities.
  • the volume resistivity can be efficiently reduced with a small amount of carbon nanotubes, the conductivity of the semiconductor wafer in contact with at least one selected from the chuck pin, the wafer pin and the stage and / or the chemical solution passing through the nozzle can be reduced. It is possible to suppress the contamination of the chemical solution and the like due to the mixing of the volatile material.
  • the manufacturing apparatus of the present invention uses a conductive chuck pin and / or a wafer pin to hold a semiconductor wafer, and / or a conductive nozzle from a cleaning solution, an etchant or a resist.
  • a conductive chuck pin and / or a wafer pin to hold a semiconductor wafer, and / or a conductive nozzle from a cleaning solution, an etchant or a resist.
  • the cleaning solution, the etching solution, the resist solution, and the like are not particularly limited as long as they can be used in the manufacturing apparatus of the embodiment of the present disclosure.
  • Such cleaning solution, etching solution, resist solution and the like are, for example, organic solvents (eg, isopropyl alcohol etc.), flammable liquids (eg, isopropyl alcohol etc.), acidic liquids (eg, hydrofluoric acid, fluoro acid and nitric acid).
  • the manufacturing apparatus of the present invention holds a semiconductor wafer on the mounting surface of a rotary stage using conductive chuck pins, and uses a conductive nozzle to wash liquid, etching liquid or resist liquid.
  • a conductive nozzle to wash liquid, etching liquid or resist liquid.
  • the manufacturing apparatus of the present invention further includes a wafer pin for supporting the semiconductor wafer from the back side, static electricity can be removed also from the back side of the semiconductor wafer, so that a more efficient static electricity removing effect can be obtained.
  • the stage preferably has a chuck pin and / or a wafer pin which is a resin molded body containing a composite resin material containing at least one fluorocarbon resin and carbon nanotube.
  • the stage preferably includes at least either the chuck pin which is the resin molded body or the wafer pin which is the resin molded body.
  • the stage may or may not have a wafer pin, and the wafer pin may be the above-mentioned resin molded body, or It may not be a resin molded body.
  • the stage When the stage has a wafer pin which is the above-mentioned resin molded body, it may or may not have a chuck pin, and the chuck pin may be the above-mentioned resin molded body, or the above-mentioned resin molding It does not have to be the body.
  • the chuck pins are pins for holding the semiconductor wafer on the stage, and the number and shape thereof are not particularly limited as long as the semiconductor wafer can be held on the mounting surface of the stage.
  • the stage preferably includes three or more, and more preferably four or more chuck pins, from the viewpoint of easily fixing the semiconductor wafer on the stage.
  • the wafer pins are pins in contact with the semiconductor wafer, and the number and shape thereof are not particularly limited.
  • the volume resistivity of the chuck pin is preferably 1.0 ⁇ 10 8 as measured in accordance with JIS K6911 from the viewpoint of antistaticity. ⁇ ⁇ cm or less, more preferably 1.0 ⁇ 10 7 ⁇ ⁇ cm or less, and still more preferably 1.0 ⁇ 10 6 ⁇ ⁇ cm or less.
  • ⁇ ⁇ cm or less preferably 1.0 ⁇ 10 7 ⁇ ⁇ cm or less
  • 1.0 ⁇ 10 6 ⁇ ⁇ cm or less Favorable antistatic property is acquired as a volume resistivity is below the said upper limit.
  • the lower limit value of the volume resistivity of the chuck pin is not particularly limited and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the volume resistivity of the chuck pin is Xc ⁇ ⁇ cm
  • the amount of carbon nanotubes contained in the chuck pin based on the total amount of resin molded body constituting the chuck pin is Yc mass
  • Xc and Yc have the following formula (1): Xc / Yc -14 4 4 x 10 -10 (1) It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the chuck pin can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, the cleanness of the chuck pin can be easily improved.
  • Value calculated from the above equation (1) is the volume resistivity of the chuck pins from the viewpoint of easy effectively reduced, more preferably 10 -11 or less, more preferably 10 - It is 12 or less.
  • the lower limit value of the value (Xc / Yc -14 ) calculated from the above formula (1) is not particularly limited, but is usually 10 -18 or more, preferably 10 -16 or more.
  • the above relationship can be achieved by manufacturing a molded body by a manufacturing method to be described later, or manufacturing a chuck pin using composite resin particles that are preferable for efficiently reducing the volume resistivity.
  • the volume resistivity of the chuck pin is measured according to JIS K6911 using a chuck pin as a measurement sample with a resistivity meter (for example, "Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
  • a resistivity meter for example, "Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • the amount of carbon nanotubes contained in the chuck pin is measured by carbon component analysis.
  • the volume resistivity of the wafer pin is measured according to JIS K6911 from the viewpoint of antistaticity, preferably 1.0 ⁇ 10 8 ⁇ ⁇ . It is at most cm, more preferably at most 1.0 ⁇ 10 7 ⁇ ⁇ cm, even more preferably at most 1.0 ⁇ 10 6 ⁇ ⁇ cm.
  • Favorable antistatic property is acquired as a volume resistivity is below the said upper limit.
  • the lower limit of the volume resistivity of the wafer pin is not particularly limited, and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the stage has a wafer pin which is the above resin molded body
  • the volume resistivity of the wafer pin is Xw ⁇ ⁇ cm
  • the amount of carbon nanotubes contained in the wafer pin based on the total amount of resin molded body constituting the wafer pin is Yw mass% Xw and Yw have the following formula (2): Xw / Yw -14 4 4 x 10 -10 (2) It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the wafer pin can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, the cleanness of the wafer pin can be easily improved.
  • the value (Xw / Yw -14 ) calculated from the above equation (2) is more preferably 10 -11 or less, and still more preferably 10 -12 from the viewpoint of easily reducing the volume resistivity of the wafer pin. It is below.
  • the lower limit value of the value (Xc / Yc -14 ) calculated from the above formula (2) is not particularly limited, but is usually 10 -18 or more, preferably 10 -16 or more.
  • the above relationship can be achieved by manufacturing a molded body by a manufacturing method to be described later, or manufacturing a wafer pin using composite resin particles that are preferable for reducing the volume resistivity efficiently.
  • the volume resistivity of the wafer pin is measured according to JIS K6911 using a wafer pin as a measurement sample with a resistivity meter (for example, "Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Further, the amount of carbon nanotubes contained in the wafer pin is measured by carbon component analysis.
  • the resin molded body constituting the chuck pin and / or the wafer pin is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, and further more preferably based on the total amount of the resin molded body.
  • it contains 0.025 to 0.2% by mass of carbon nanotubes.
  • the amount of carbon nanotubes it is preferable for the amount of carbon nanotubes to be not less than the above lower limit, since it is easy to lower the volume resistivity in order to enhance the antistatic property or the conductivity. When the amount of carbon nanotubes is equal to or less than the above upper limit, the volume resistivity can be easily reduced efficiently, and the cleanness of the resin molded product can be easily improved.
  • the amount of carbon nanotubes contained in the resin molding is measured by carbon component analysis.
  • the chuck pins and / or the wafer pins are electrically connected to the housing of the manufacturing apparatus, and the static electricity flowing from the semiconductor wafer to the chuck pins and / or the wafer pins finally flows into the housing of the manufacturing apparatus, It is removed outside the device.
  • a rotary drive shaft having a metal portion is used, the chuck pin and / or the wafer pin and the metal portion of the rotary drive shaft are connected to ground, and the metal portion of the rotary drive shaft and the casing of the manufacturing apparatus are grounded. By connecting, static electricity can be removed from the housing of the manufacturing apparatus to the outside of the apparatus.
  • stage In the manufacturing apparatus of the present invention, a stage is provided to hold a semiconductor wafer on its surface.
  • the semiconductor wafer may be directly mounted on the stage, or may be mounted via chuck pins and / or wafer pins provided on the stage.
  • the material of the stage is not particularly limited, and may be appropriately selected from the viewpoint of chemical resistance, mechanical properties and the like, and may be, for example, a molded product of fluorocarbon resin, polypropylene, vinyl chloride or the like.
  • the size of the stage may be appropriately determined according to the size of the semiconductor wafer to be processed, and is not particularly limited. For example, when the diameter of the semiconductor wafer is 300 mm, the thickness is 15 to 30 mm and the outer diameter 330 to It is about 350 mm in size.
  • the stage in view of easy removal of static electricity from a semiconductor wafer more efficiently, is a resin molded body including a composite resin material containing at least one fluorocarbon resin and carbon nanotube.
  • the volume resistivity of the stage is preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, more preferably 1.0 ⁇ 10 7 ⁇ ⁇ , as measured in accordance with JIS K 6911 from the viewpoint of antistatic property. It is at most cm, still more preferably at most 1.0 ⁇ 10 6 ⁇ ⁇ cm.
  • the volume resistivity of the stage is less than the above upper limit, better antistatic properties of the production apparatus of the present invention can be obtained.
  • the lower limit value of the volume resistivity of the stage is not particularly limited, and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the volume resistivity of the rotary stage is measured by a resistivity meter (for example, "Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using the stage as a measurement sample according to JIS K6911.
  • the resin molded product constituting the stage is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, and still more preferably, based on the total amount of the resin molded product. It contains 0.025 to 0.2% by mass of carbon nanotubes.
  • the amount of carbon nanotubes prefferably be not less than the above lower limit, since it is easy to lower the volume resistivity in order to enhance the antistatic property or the conductivity.
  • the amount of carbon nanotubes is equal to or less than the above upper limit, the volume resistivity can be easily reduced efficiently, and the cleanness of the resin molded product can be easily improved.
  • the amount of carbon nanotubes contained in the resin molded product constituting the stage is measured by carbon component analysis.
  • the volume resistivity of the stage is Xs ⁇ ⁇ cm
  • the total amount of resin molded bodies constituting the stage is Assuming that the amount of carbon nanotubes contained in the stage based on Ys mass%, Xs and Ys have the following formula (3): Xs / Ys -14 4 4 x 10 -10 (3) It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the stage can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, it is easy to improve the cleanness of the stage.
  • the value (Xs / Ys -14 ) calculated from the above equation (3) is more preferably 10 -11 or less, and further preferably 10 -12 from the viewpoint of easily reducing the volume resistivity of the stage. It is below.
  • the lower limit of the value (Xs / Ys- 14 ) calculated from the above equation (3) is not particularly limited, but is usually 10-18 or more, preferably 10-16 or more.
  • the above relationship can be achieved by manufacturing a molded product by a manufacturing method to be described later, or manufacturing a stage using composite resin particles that are preferable for effectively reducing the volume resistivity. The method of measuring the volume resistivity and the amount of carbon nanotubes in the stage is as described above.
  • the nozzle is a tube for supplying a cleaning solution, an etching solution or a resist solution to the surface of the semiconductor wafer held on the stage, usually.
  • the nozzle is preferably provided such that the liquid supply port of the nozzle is located above the semiconductor wafer held on the stage.
  • the diameter and length of the nozzle, and the position of the liquid supply port of the nozzle may be appropriately determined according to the size of the semiconductor wafer to be processed, the required liquid supply amount, and the like, and are not particularly limited.
  • the diameter of the nozzle is, for example, 1/2 inch or less, preferably 1/4 to 3/8 inch, and the nozzle length is, for example, 200 mm or more
  • the setting position of the liquid supply port of the nozzle can be 150 mm or more above the surface of the semiconductor wafer.
  • the nozzle is preferably a resin molded body containing a composite resin material containing at least one fluorocarbon resin and carbon nanotube.
  • the volume resistivity of the nozzle is preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, more preferably 1.0 ⁇ 10 7 ⁇ ⁇ cm or less, further preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, as measured in accordance with JIS K 6911, from the viewpoint of antistatic properties.
  • it is 1.0 * 10 ⁇ 6 > ohm * cm or less.
  • Favorable antistatic property is acquired as a volume resistivity is below the said upper limit.
  • the lower limit value of the volume resistivity of the nozzle is not particularly limited, and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the volume resistivity of the nozzle is measured according to JIS K6911 using a nozzle as a measurement sample with a resistivity meter (for example, "Loresta” or "Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
  • the resin molded body constituting the nozzle is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, still more preferably 0.025 to 2.5% by mass, based on the total amount of the resin molded body. It contains 0.2% by mass of carbon nanotubes.
  • the amount of carbon nanotubes prefferably be not less than the above lower limit, since it is easy to lower the volume resistivity in order to enhance the antistatic property or the conductivity.
  • the amount of carbon nanotubes is equal to or less than the above upper limit, the volume resistivity can be easily reduced efficiently, and the cleanness of the resin molded product can be easily improved.
  • the amount of carbon nanotubes contained in the resin molding constituting the nozzle is measured by carbon component analysis.
  • the volume resistivity of the nozzle is X n ⁇ ⁇ cm
  • the amount of carbon nanotubes contained in the nozzle based on the total amount of resin moldings constituting the nozzle is Yn mass%
  • Xn and Yn Formula (4) Xn / Yn -14 4 4 x 10 -10 (4) It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the nozzle can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, it is easy to improve the cleanness of the nozzle.
  • the value (Xn / Yn -14 ) calculated from the above equation (4) is more preferably 10 -11 or less, and still more preferably 10 -12 from the viewpoint of easily reducing the volume resistivity of the nozzle efficiently. It is below.
  • the lower limit of the value (Xn / Yn- 14 ) calculated from the above formula (4) is not particularly limited, but is usually 10-18 or more, preferably 10-16 or more.
  • the above relationship can be achieved by manufacturing a molded body by a manufacturing method to be described later, or manufacturing a nozzle using composite resin particles preferable for effectively reducing the volume resistivity.
  • the method for measuring the volume resistivity and the amount of carbon nanotubes in the nozzle is as described above.
  • the nozzle being a resin molded body containing a composite resin material containing a fluorocarbon resin and a carbon nanotube.
  • the resin molded body containing a composite resin material is excellent in cleanness and excellent in chemical resistance, it is possible to avoid the mixing of impurities into the liquid from the inner surface of the nozzle.
  • the nozzle is electrically connected, for example, to the housing of the manufacturing apparatus, and static electricity generated by friction between the inner surface of the nozzle and the liquid finally flows into the housing of the manufacturing apparatus and is removed to the outside of the apparatus.
  • Ru for example, by providing a metal portion on the outer peripheral portion of the nozzle, the nozzle and the housing of the manufacturing apparatus can be electrically connected, and static electricity can be removed from the housing of the manufacturing apparatus to the outside of the apparatus.
  • the nozzles are used to supply the cleaning solution.
  • a cleaning solution generally used for cleaning a semiconductor wafer can be mentioned, and specifically, water, isopropyl alcohol (IPA), hydrofluoric acid (hydrofluoric acid aqueous solution) and the like can be mentioned.
  • IPA isopropyl alcohol
  • hydrofluoric acid hydrofluoric acid aqueous solution
  • a nozzle is used to supply the etchant.
  • the etchant include etchants commonly used in the etching of semiconductor wafers.
  • strong acid aqueous solutions such as hydrofluoric acid and hydrofluoric-nitric acid (mixed aqueous solution of hydrofluoric acid and nitric acid), and potassium hydroxide
  • An aqueous solution, a strong base aqueous solution such as tetramethyl ammonium hydroxide aqueous solution, and the like can be mentioned.
  • a nozzle is used to supply a resist solution.
  • the resist solution include resist solutions generally used for resisting semiconductor wafers, and specific examples include mixed solutions of a polymer, a photosensitizer, and a solvent (tetramethylammonium hydroxide).
  • the manufacturing apparatus of the present invention may further be provided with a cup body, for example, so as to surround a semiconductor wafer held on a stage.
  • the cup body is provided for the purpose of receiving a liquid that is scattered when removing the liquid such as the cleaning liquid from the semiconductor wafer.
  • a cup body the thing of the structure which has an outer cup and an inner cup, for example is mentioned.
  • the upper side of the cup body may be open.
  • the outer cup has a rectangular shape on the upper side and a cylindrical shape on the lower side.
  • a step may be provided on the lower side of the outer cup, and in this case, an elevating part for raising and lowering the outer cup may be connected to the step.
  • the inner cup may be cylindrical in shape, for example its upper side sloped inwards.
  • the inner cup may be configured to be pushed upward by bringing the lower end surface of the inner cup into contact with the step of the outer cup when the outer cup is lifted.
  • the cup body (outer cup and inner cup) can be lifted to receive the liquid scattered from the semiconductor wafer.
  • the cup body (for example, the outer cup and / or the inner cup) is a resin molded body containing a composite resin material containing at least one fluorocarbon resin and carbon nanotubes.
  • the volume resistivity of the cup body is preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, more preferably 1.0 ⁇ 10 7 ⁇ ⁇ or less, as measured in accordance with JIS K 6911, from the viewpoint of antistaticity. It is at most cm, still more preferably at most 1.0 ⁇ 10 6 ⁇ ⁇ cm.
  • Favorable antistatic property is acquired as a volume resistivity is below the said upper limit.
  • the lower limit of the volume resistivity of the cup body is not particularly limited, and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the volume resistivity of the cup body is measured according to JIS K6911 using a cup body as a measurement sample with a resistivity meter (for example, "Loresta” or "Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
  • the resin molded body constituting the cup body is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, and still more preferably 0.025% by mass, based on the total amount of the resin molded body. It contains ⁇ 0.2 mass% of carbon nanotubes.
  • the amount of carbon nanotubes prefferably be not less than the above lower limit, since it is easy to lower the volume resistivity in order to enhance the antistatic property or the conductivity.
  • the amount of carbon nanotubes is equal to or less than the above upper limit, the volume resistivity can be easily reduced efficiently, and the cleanness of the resin molded product can be easily improved.
  • the amount of carbon nanotubes contained in the resin molding that constitutes the cup body is measured by carbon component analysis.
  • the volume resistivity of the cup body is Xc ⁇ ⁇ cm
  • the amount of carbon nanotubes contained in the cup body based on the total amount of resin moldings forming the cup body is Yc mass%
  • Xc and Yc Is the following equation (5): Xc / Yc -14 4 4 x 10 -10 (5) It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the cup can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, it is easy to enhance the cleanness of the cup body.
  • Value calculated from the above equation (5) is the volume resistivity of the cup body from the viewpoint of easy effectively reduced, more preferably 10 -11 or less, more preferably 10 - It is 12 or less.
  • the lower limit value of the value (Xc / Yc -14 ) calculated from the above formula (5) is not particularly limited, but is usually 10 -18 or more, preferably 10 -16 or more.
  • the above relationship can be achieved by manufacturing a molded body by a manufacturing method to be described later, or manufacturing a cup body using composite resin particles preferable for effectively reducing the volume resistivity. The methods for measuring the volume resistivity and the amount of carbon nanotubes in the cup body are as described above.
  • the manufacturing apparatus of the present invention may further include a configuration for discharging a liquid such as a cleaning liquid, an etching liquid, or a resist liquid removed from the semiconductor wafer from the apparatus.
  • a liquid receiving unit may be provided, a waste liquid pipe may be connected to the bottom of the liquid receiving part, and the liquid may finally flow to the waste liquid tank.
  • At least one selected from the chuck pin, the wafer pin, and the stage, and / or the nozzle is a resin molded body including a composite resin material including at least one fluorocarbon resin and carbon nanotube.
  • the resin molded article contains a composite resin material which also contains at least one fluorocarbon resin and carbon nanotube as the stage.
  • the composite resin material is a molded article of composite resin particles containing at least one fluorocarbon resin and carbon nanotubes.
  • the composite resin particle is a material in which fluorocarbon resin particles and carbon nanotubes are complexed, and carbon nanotubes exist on at least the surface and / or surface layer of the fluorocarbon resin particles.
  • at least a part of the carbon nanotube is supported or buried on the particle surface of the fluorine resin.
  • the carbon nanotubes may be attached to and supported on the particle surface of the fluorocarbon resin, or a part may be buried and supported, or may be completely embedded in the surface layer of the particles of the fluorocarbon resin .
  • a composite resin material which is a molded product of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, and the composite resin particles are integrated to form a composite resin material. It may be done.
  • the average particle diameter of the composite resin particles is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, particularly preferably 100 ⁇ m or less, very preferably 50 ⁇ m or less, most preferably 30 ⁇ m or less.
  • the lower limit of the average particle size of the composite resin particles is not particularly limited, but is usually 5 ⁇ m or more.
  • the average particle size of the composite resin particles giving the composite resin material contained in the chuck pin, the wafer pin and at least one selected from the wafer pin and the stage and / or the nozzle, preferably the chuck pin and / or the wafer pin May be the average particle size of the composite resin particles used for producing the above chuck pins etc.
  • the average particle size means the particle size at 50% of the integrated value in the particle size distribution determined by laser diffraction / scattering method Median diameter (D 50 ), which is measured using a laser diffraction scattering particle size distribution apparatus.
  • a molded article such as a chuck pin is made of a composite resin material which is a molded article of composite resin particles having the above average particle diameter.
  • the composite resin material in the state of being contained therein may be a composite resin particle having a particle diameter in the above-mentioned preferable range, or the composite resin particles are integrated to form a composite resin material, and the particle shape is not maintained. It is also good.
  • the amount of the fluorine resin contained in the composite resin material is preferably 98.0% by mass or more, more preferably 99.5% by mass or more, still more preferably 99.0% by mass or more, based on the total amount of the composite resin material. Particularly preferably, it is 99.8% by mass or more.
  • the upper limit of the amount of the fluorine resin is not particularly limited, but is about 99.99% by mass or less.
  • the amount of the fluorine resin contained in the composite resin material is measured by carbon component analysis. In the manufacturing apparatus of the present invention, the above-mentioned preferable statement about the amount of fluorine resin applies similarly to the amount of fluorine resin contained in the chuck pin and / or the wafer pin and the nozzle and optionally the stage.
  • the preferable description regarding the amount of the fluorocarbon resin is at least one selected from a chuck pin, a wafer pin and a stage and / or a nozzle, preferably a chuck pin and / or a wafer pin The same applies to the amount of
  • the composite resin material is a molded article of composite resin particles, and the specific surface area of the composite resin particles is preferably 0.5 to 9.0 m 2 / g, more preferably 0.8, as measured in accordance with JIS Z8830. It is -4.0 m 2 / g, still more preferably 1.0 to 3.0 m 2 / g. It is preferable from the viewpoint of easily improving the adhesion between the fluorine resin and the carbon nanotube that the specific surface area is the above lower limit or more, and it is preferable from the viewpoint of easiness of producing the composite resin material that it is the above upper limit.
  • the specific surface area of the resin particles used in the manufacture of the chuck pin or the like may be the specific surface area, which is specifically a specific surface area / pore distribution measuring apparatus which is a fixed capacity gas adsorption method (for example, Japan It is measured by BET method which is a general measurement method of specific surface area using Bell made BELSORP-miniII).
  • a molded body such as a chuck pin is made of a composite resin material which is a molded body of composite resin particles having the above specific surface area.
  • the composite resin material in the state of being contained in may be a composite resin particle having a specific surface area in the above-mentioned preferable range, or the composite resin particles are integrated to form a composite resin material, and the above specific surface area is maintained. You do not have to.
  • the volume resistivity of the composite resin particles is preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or less, more preferably 1.0 ⁇ 10 7 ⁇ ⁇ cm or less, as measured in accordance with JIS K 6911 from the viewpoint of antistatic properties. Still more preferably, it is 1.0 ⁇ 10 6 ⁇ ⁇ cm or less.
  • Favorable antistatic property is acquired as a volume resistivity is below the said upper limit.
  • the lower limit value of the volume resistivity of the composite resin material is not particularly limited, and may be 0 or more, but is usually 10 ⁇ ⁇ cm or more.
  • the volume resistivity of the composite resin material is measured by a resistivity meter (for example, "Loresta” or “Hyresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using a molding material or a cut test piece according to JIS K6911.
  • a resistivity meter for example, "Loresta” or “Hyresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • the composite resin particles exhibit the above-mentioned volume resistivity when measured using a test piece of ⁇ 110 ⁇ 10 mm produced by compression molding (compression molding).
  • the fluorine resin contained in the composite resin material is not particularly limited.
  • PTFE polytetrafluoroethylene
  • modified polytetrafluoroethylene modified polytetrafluoroethylene
  • PFA perfluoroalkyl vinyl ether copolymer
  • FEP tetratetra Fluoroethylene / hexafluoropropylene copolymer
  • ETFE ethylene / tetrafluoroethylene copolymer
  • ECTFE ethylene / chlorotrifluoroethylene copolymer
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • the fluorine resin is preferably selected from the group consisting of PTFE, modified PTFE, PFA, PCTFE and PVDF from the viewpoints of mechanical strength properties and molding processability, and from the viewpoint of easily enhancing the conductivity, preferably PTFE. It is selected from the group consisting of modified PTFE and PCTFE, and is more preferably modified PTFE or PCTFE from the viewpoint of facilitating the improvement of the conductivity efficiently as well as mechanical strength properties and molding processability.
  • At least one of the chuck pin, the wafer pin and the stage and / or the nozzle selected from the stage, preferably the chuck pin and / or the wafer pin and the nozzle are manufactured from the same composite resin material It may be manufactured from different composite resin materials, each of which contains different fluorocarbon resin or carbon nanotube.
  • Polytetrafluoroethylene is a homopolymer of tetrafluoroethylene.
  • Modified polytetrafluoroethylene is a compound of formula (I) derived from tetrafluoroethylene: In addition to the tetrafluoroethylene units represented by [Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group] And the amount of the perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene Some modified polytetrafluoroethylenes can be mentioned.
  • Examples of X in the formula (II) include a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms.
  • Examples of the perfluoroalkyl group having 1 to 6 carbon atoms include perfluoromethyl group, perfluoroethyl group, perfluorobutyl group, perfluoropropyl group, perfluorobutyl group and the like.
  • Examples of the perfluoroalkoxyalkyl group having 4 to 9 carbon atoms include perfluoro 2-methoxypropyl group and perfluoro 2-propoxypropyl group.
  • X is preferably a perfluoropropyl group, a perfluoroethyl group, or a perfluoromethyl group, more preferably a perfluoropropyl group.
  • the modified PTFE may have one type of perfluorovinylether unit represented by the formula (II) or may have two or more perfluorovinylether units represented by the formula (II) Good.
  • the amount of the perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is less than 1 mol%, preferably 0.001 mol% or more, based on the amount of all structural units contained in the modified PTFE It is less than 1 mol%.
  • the amount of the perfluorovinyl ether unit represented by the formula (II) is increased, the melting point of the fluorine resin is increased, the weldability and the flexibility are improved, and the melt flowability of the fluorine resin is increased, so that the formability Tend to improve.
  • the amount of units is too high, the adhesion at the time of welding may be reduced.
  • the amount of the perfluorovinyl ether unit represented by the formula (II) is equal to or more than the above lower limit, the flowability becomes higher compared to PTFE, and the moldability becomes good. Moreover, it is easy to improve the adhesiveness at the time of welding as the quantity of the said unit is below the said upper limit.
  • the amount of the perfluorovinyl ether unit is measured, for example, by performing infrared spectroscopy in the range of 1040 to 890 cm ⁇ 1 characteristic absorption.
  • the amount of perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is 0.01 to 1% by mass, preferably 0.03 to 0.2% by mass, based on the total mass of the modified PTFE is there.
  • the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) is a compound of formula (I) derived from tetrafluoroethylene: In addition to the tetrafluoroethylene units represented by [Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group] And a compound having an amount of perfluorovinylether unit represented by the formula (II) is more than 1% by mass based on the total mass of PFA.
  • Examples of X in the formula (II) include the groups described above for the modified PTFE, and the same applies to the preferred descriptions.
  • PFA may have one type of perfluorovinylether unit represented by formula (II), or may have two or more perfluorovinylether units represented by formula (II) .
  • the amount of the perfluorovinyl ether unit represented by the formula (II) contained in PFA is 1 mol% or more, preferably 1 to 3 mol%, based on the amount of all the structural units contained in PFA.
  • the amount of the perfluorovinyl ether unit represented by the formula (II) is measured, for example, by performing infrared spectroscopy in the range of 1040 to 890 cm ⁇ 1 characteristic absorption.
  • PCTFE Polychlorotrifluoroethylene
  • the melting point of the fluororesin is preferably 130 to 380 ° C., more preferably 150 to 380 ° C., still more preferably 180 to 350 ° C., and particularly preferably 200 to 350 ° C.
  • the melting point of the fluorine resin is a value determined as the temperature of the heat of fusion peak which can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D 4591.
  • the fluororesin when the fluororesin is PCTFE, its melting point is preferably 130 to 290 ° C., more preferably 160 to 270 ° C., and still more preferably 180 to 250 ° C.
  • the melting point is the above lower limit or more, the formability is preferably improved, and the melting point is preferably the above upper limit or the like because the optimum mechanical properties of the resin are easily obtained.
  • the melting point of PCTFE is measured using a differential scanning calorimeter (DSC) according to ASTM-D 4591.
  • the fluororesin when the fluororesin is a modified PTFE, its melting point is preferably 300 to 380 ° C., more preferably 320 to 380 ° C., and still more preferably 320 to 350 ° C.
  • the melting point is the above lower limit or more, the formability is preferably improved, and the melting point is preferably the above upper limit or the like because the optimum mechanical properties of the resin can be easily obtained.
  • the melting point of the modified PTFE is a value determined as the temperature of the heat of fusion peak which can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D 4591.
  • the heat of crystallization is preferably 18.0 to 25.0 J / g, more preferably 18.0 to 23.5 J / g.
  • the heat of crystallization is measured by a differential scanning calorimeter (for example, "DSC-50" manufactured by Shimadzu Corporation). Specifically, the temperature is raised to 250 ° C. at a rate of 50 ° C./min, and temporarily held, and then the crystal is melted by raising the temperature to 380 ° C. at a rate of 10 ° C./min. After that, the peak of the crystallization point measured when the temperature is lowered at a rate of 10 ° C./min is measured in terms of heat.
  • a carbon nanotube (hereinafter also referred to as “CNT”) contained in the composite resin material has a structure in which one or a plurality of graphene sheets composed of six-membered rings of carbon atoms are cylindrically wound.
  • the CNT is a single-walled CNT (single-walled carbon nanotube) in which one graphene sheet is concentrically wound, or a multilayer CNT (multi-walled carbon nanotube) in which two or more graphene sheets are concentrically wound. It is.
  • the above carbon nanomaterials may be used alone or in combination. It is more preferable that the carbon nanotube is a multi-walled carbon nanotube from the viewpoint of being easily complexed with the modified PTFE particles and easily lowering the volume resistivity.
  • the composite resin material is a material obtained by combining a fluorocarbon resin and a carbon nanotube.
  • the method for producing the composite resin material is not particularly limited as long as a material having a physical property as described above and in which a fluorocarbon resin and a carbon nanotube are composited is obtained.
  • the composite resin material is manufactured from composite resin particles in which a fluorocarbon resin and a carbon nanotube are composited.
  • the method for producing composite resin particles is not particularly limited as long as composite resin particles in which carbon nanotubes exist on at least the surface and / or surface layer of the fluorocarbon resin can be obtained.
  • composite resin particles can be produced by combining the particles of the fluorocarbon resin and the carbon nanotube.
  • carbon nanotubes are dispersed in a solvent to prepare a carbon nanotube dispersion.
  • a solvent water, alcohol solvents (ethanol, n-butyl alcohol, isopropyl alcohol, ethylene glycol etc.), ester solvents (ethyl acetate etc.), ether solvents (diethyl ether, dimethyl ether etc.), ketone solvents (methyl ethyl ketone) , Acetone, diethyl ketone, methyl propyl ketone, cyclohexanone etc., aliphatic hydrocarbon solvents (hexane, heptane etc), aromatic hydrocarbon solvents (toluene, benzene etc), chlorinated hydrocarbon solvents (dichloromethane, chloroform) , Chlorobenzene, etc.).
  • One type of solvent may be used, or two or more types of solvents may be used in combination. From the viewpoint of easily forming a fluorocarbon resin and a carbon nanotube, it is preferable to use a solvent which easily swells the particle surface of the fluorocarbon resin. Specifically, it is preferable to use a ketone-based solvent.
  • the amount of the solvent contained in the carbon nanotube dispersion is preferably 20,000 to 1, relative to 100 parts by mass of the carbon nanotubes contained in the carbon nanotube dispersion, from the viewpoint of facilitating single dispersion of the carbon nanotubes in the solvent.
  • 000, 000 parts by weight more preferably 30,000 to 300,000 parts by weight, even more preferably 50,000 to 200,000 parts by weight.
  • the carbon nanotubes used for producing the composite resin particles preferably have an average length of 50 to 600 ⁇ m, more preferably 50 to 300 ⁇ m, and still more preferably 100 to 200 ⁇ m.
  • the average length of the carbon nanotubes is measured by a scanning electron microscope (SEM, FE-SEM) or a transmission electron microscope (TEM).
  • Carbon nanotubes can be produced by conventional production methods. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, vapor phase growth method such as CVD method, gas phase flow method, carbon monoxide is reacted with iron catalyst at high pressure and high pressure to be a gas phase Such as the HiPco method to grow by Commercially available carbon nanotubes such as "NC7000" from Nanocyl may be used.
  • a dispersant When dispersing carbon nanotubes in a solvent, a dispersant may be used for the purpose of enhancing the dispersibility of carbon nanotubes.
  • the dispersant include acrylic dispersants, synthetic polymers such as polyvinyl pyrrolidone and polyaniline sulfonic acid, DNA, peptides, organic amine compounds and the like.
  • One dispersant may be used, or two or more dispersants may be used in combination. From the viewpoint of easily reducing the amount of the dispersant remaining in the finally obtained molded article, the dispersant preferably has a boiling point at a temperature lower than the molding temperature of the composite resin particles preferred for the present invention.
  • the amount of the dispersant contained in the carbon nanotube dispersion may be appropriately selected according to the type and the amount of the carbon nanotube, the solvent and the dispersant.
  • the amount of dispersant used is preferably 100 to 6,000 parts by mass, more preferably 200 to 3,000 parts by mass, and still more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of carbon nanotubes. It is.
  • the carbon nanotube dispersion is mixed with an alcohol solvent or the like before the second step described later. This is because the affinity between the fluororesin and water to be added in the subsequent second step is low, and it is difficult to disperse the particles of the fluororesin in the carbon nanotube dispersion using water as a solvent. Then, the affinity of the particles of the fluorocarbon resin and the carbon nanotube dispersion liquid can be enhanced by mixing the alcohol solvent.
  • particles of a fluorocarbon resin are added to the carbon nanotube dispersion and stirred to prepare a mixed slurry in which carbon nanotube and fluorocarbon resin particles are dispersed.
  • carbon nanotubes in the dispersion liquid are gently adsorbed on the fluorocarbon resin particle surfaces.
  • the carbon nanotube and the fluorocarbon resin particles are maintained while maintaining a high dispersion state of the carbon nanotubes and fluorocarbon resin. It can be adsorbed on the surface.
  • the addition of the fluorine resin may be performed by adding the particles of the fluorine resin as it is or in the form of a dispersion in which the particles of the fluorine resin are previously dispersed in a solvent.
  • the particles of the fluorocarbon resin used for producing the composite resin particles of the present invention are preferably 5 to 500 ⁇ m, more preferably 10 to 250 ⁇ m, still more preferably 10 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m, and most preferably 15 to It has an average particle size of 30 ⁇ m. It is easy to enhance the dispersibility of carbon nanotubes in a molded article (composite resin material) produced from composite resin particles and that the average particle diameter of the fluorine resin is not more than the above upper limit, and to enhance the antistatic properties uniformly and efficiently Because it is preferable. It is preferable from the viewpoint of easiness of production of the composite resin particles that the average particle diameter of the fluorine resin is not less than the above lower limit.
  • the average particle diameter of the fluorine resin is a median diameter (D 50 ) which means the particle diameter at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method, and is measured using a laser diffraction scattering type particle size distribution device Be done.
  • D 50 median diameter
  • the particles of the fluorocarbon resin used for producing the composite resin particles are preferably 0.5 to 9.0 m 2 / g, more preferably 0.8 to 4.0 m 2 / g, still more preferably, as measured according to JIS Z8830. Is from 1.0 to 3.0. It has a specific surface area of m 2 / g.
  • the specific surface area is preferably not more than the above upper limit from the viewpoint of easily improving the adhesion between the particles of the fluorocarbon resin and the carbon nanotube, and it is preferably not less than the above lower limit from the viewpoint of easiness of producing the composite resin particles preferable.
  • the specific surface area of the fluorine resin particles is measured by the BET method, which is a general measurement method of the specific surface area, using a specific surface area / pore distribution measuring apparatus which is a fixed capacity gas adsorption method. .
  • the method for producing the particles of the fluorine resin having an average particle diameter and specific surface area in the above preferable range is not particularly limited, and the fluorine resin is produced by a conventionally known polymerization method, preferably suspension polymerization, Method of spray-drying a dispersion containing a polymer, method of mechanically pulverizing the obtained fluororesin using a grinder such as a hammer mill, turbo mill, cutting mill, jet mill or the like, the obtained fluororesin less than room temperature
  • a grinder such as a hammer mill, turbo mill, cutting mill, jet mill or the like
  • the obtained fluororesin less than room temperature examples of the method include freeze grinding which mechanically grinds at a temperature. From the viewpoint of easily obtaining particles of the fluorine resin having a desired average particle diameter and specific surface area, it is preferable to produce particles of the fluorine resin using a pulverizer such as a jet mill.
  • the particles of the fluorocarbon resin having an average particle diameter in the above preferable range may be manufactured by adjusting the average particle diameter by a classification step using a sieve or an air stream.
  • the mixed slurry obtained in the second step is supplied to the pressure container, and the carbon dioxide is specified while maintaining the temperature and pressure at which carbon dioxide becomes subcritical or supercritical in the pressure container.
  • carbon dioxide any of liquefied carbon dioxide, carbon dioxide in gas-liquid mixture, and gaseous carbon dioxide may be used.
  • carbon dioxide in the supercritical state refers to a temperature above the critical point and a pressure above the critical point, specifically, a temperature above 31.1 ° C. and a pressure above 72.8 atmospheres I say the state.
  • a subcritical state means the state which exists in the pressure below a critical point, and the temperature below a critical point.
  • the solvent and dispersant contained in the mixed slurry dissolve in carbon dioxide, and carbon nanotubes dispersed in the mixed slurry adhere to the particles of the fluorocarbon resin.
  • the feed rate of carbon dioxide is preferably 0.25 g with respect to, for example, 1 mg of the dispersing agent contained in the mixed slurry, from the viewpoint of suppressing aggregation of carbon nanotubes and allowing carbon nanotubes to adhere uniformly to the particle surface of the fluorocarbon resin.
  • / Min or less more preferably 0.07 g / min or less, still more preferably 0.05 g / min or less.
  • carbon dioxide is discharged from the pressure container together with the solvent and dispersant dissolved in carbon dioxide while maintaining the temperature and pressure at which carbon dioxide is in the subcritical or supercritical state for a predetermined time.
  • the entrainer having high affinity to the dispersant is added to the pressure container while maintaining the state of the fourth step. Thereby, the remaining dispersant can be efficiently removed.
  • the solvent used in preparing the carbon nanotube dispersion in the first step may be used.
  • the same organic solvent may be used as an entrainer.
  • water is used as the solvent in the first step, it is preferable to use an alcohol solvent as the entrainer.
  • the fifth step is an optional step for efficiently removing the dispersant, and is not an essential step. It is also possible to remove the dispersant, for example by maintaining the fourth step without adding an entrainer.
  • the pressure of the pressure resistant container is lowered to remove carbon dioxide in the pressure resistant container to obtain composite resin particles.
  • carbon dioxide and a solvent may remain in the composite resin particles. Therefore, residual carbon dioxide and a solvent can be efficiently removed by exposing the composite resin particles obtained to vacuum or heating.
  • At least one of the chuck pin, the wafer pin, and the stage and / or the nozzle is a resin molded body including a composite resin material including at least one fluorocarbon resin and carbon nanotube.
  • a resin molded body including a composite resin material including at least one fluorocarbon resin and carbon nanotube is preferably a molded product of the composite resin particles described above.
  • a method of producing a composite resin material from composite resin particles and manufacturing a chuck pin, which is a resin molded body containing the composite resin material will be described as an example.
  • a resin molded body having the shape of a chuck pin may be manufactured, for example, by melting composite resin particles and forming the shape into a chuck pin shape, or the composite resin particles may be chuck pin by compression molding, for example.
  • the shape may be formed into the shape of (1), or the shape of the chuck pin may be cut out from the composite resin material obtained by the compression molding.
  • the composite resin particles are molded into a shape of the chuck pin by compression molding, and the molded body obtained by the compression molding is cut. It is preferable to manufacture a chuck pin by this. The reason why the conductivity of the chuck pin can be efficiently enhanced by the above preferred manufacturing method is not clear, but is considered to be due to the following mechanism.
  • the manufacturing apparatus of the present invention is not limited to the mechanism described later.
  • carbon nanotubes are present on at least the surface and / or surface layer of the fluorine resin, and these carbon nanotubes are considered to form a conductive network.
  • the conductive network of the carbon nanotube is considered to be easily cut when the carbon nanotube is cut by the external force applied to the composite resin particles or the carbon nanotube is aggregated. Therefore, when manufacturing a chuck pin or the like from composite resin particles, it is considered that the conductivity of the chuck pin or the like can be efficiently enhanced by using a method in which the network is not cut as much as possible.
  • a method of manufacturing a chuck pin or the like by forming composite resin particles into a shape of a chuck pin by compression molding, and a method of manufacturing a chuck pin or the like by cutting a composite resin material obtained by the compression molding are composites.
  • a resin molded body a resin molded body containing a composite resin material containing a fluorocarbon resin and a carbon nanotube is manufactured by mixing the composite resin particles and other resin particles and melting or compression molding or the like. May be
  • a polytetrafluoroethylene (PTFE) is included as a fluorine resin contained in a composite resin material from the viewpoint of facilitating production of a chuck pin or the like through compression molding of composite resin particles and facilitating efficient improvement of the conductivity of the chuck pin or the like. It is preferable to use a fluorocarbon resin selected from the group consisting of modified polytetrafluoroethylene (modified PTFE) and polychlorotetrafluoroethylene (PCTFE).
  • modified PTFE modified polytetrafluoroethylene
  • PCTFE polychlorotetrafluoroethylene
  • a composite resin material having a predetermined shape may be produced, or composite resin particles are produced by molding into a predetermined shape by compression molding, but they are produced by cutting from the composite resin material obtained by the compression molding.
  • the fluorine resin is a PTFE resin and a modified PTFE resin
  • a method of subjecting a preform obtained by compressing the composite resin particles to a firing treatment is mentioned as a method of producing the composite resin material by compression molding the composite resin particles.
  • the preformed body before firing is produced by subjecting the composite resin particles to a suitable pretreatment (eg, preliminary drying, granulation, etc.) as necessary, and then placing the composite resin particles in a mold and compressing it.
  • the pressure applied during compression to produce a preform before firing is preferably 0.1 to 100 MPa, more preferably 1 to 80 MPa, and still more preferably 5 to 50 MPa.
  • the preformed body obtained as described above is fired, for example, at a temperature equal to or higher than the melting point of the resin contained in the composite resin particles to produce a molded body.
  • the firing temperature is preferably 345 to 400 ° C., more preferably 360 to 390 ° C., although it depends on the size of the preform before firing and the firing time.
  • the preform before firing is placed in a firing furnace, and preferably fired at the above-mentioned firing temperature to produce a formed product.
  • the obtained molded product may be used as it is as a chuck pin, a nozzle, a stage or the like, or may be cut from the molded product to manufacture a chuck pin, a nozzle, a stage or the like.
  • the fluorocarbon resin is PCTFE resin, PFA resin, FEP resin, ETFE resin, ECTFE resin, PVDF resin and PVF resin (other than PTFE resin and modified PTFE resin)
  • a method of compression molding the composite resin particles to produce a composite resin material As the heat treatment, appropriate pre-treatment such as pre-drying is performed according to the size of the molding, and after pre-treatment, the mold is heated to 200 ° C. or higher, preferably 200 to 400 ° C., more preferably 210 to 380 ° C. The resin is melted by heating in a circulating electric furnace for 2 hours or more, preferably 2 to 12 hours.
  • the mold After heating for a predetermined time, the mold is taken out of the electric furnace, and the mold is cooled to around normal temperature while pressing and compressing with a hydraulic pressure and a surface pressure of 25 kg / cm 2 or more, preferably 50 kg / cm 2 or more.
  • a molded article (resin material) of composite resin particles was obtained.
  • the obtained molded product may be used as it is as a chuck pin, a nozzle, a stage or the like, or may be cut from the molded product to manufacture a chuck pin, a nozzle, a stage or the like.
  • the present specification can be obtained from a composite resin material obtained by compression molding composite resin particles (for example, fluororesin particles having an average particle diameter of 5 ⁇ m to 500 ⁇ m) including fluorocarbon resin particles and carbon nanotubes.
  • a semiconductor device manufacturing apparatus can be provided that includes at least one selected from a chuck pin, a wafer pin, and a stage and / or a nozzle.
  • the present invention also provides a step of supplying a cleaning liquid from the nozzle to the surface of the semiconductor wafer using the manufacturing apparatus of the present invention described above to clean the semiconductor wafer, and supplying an etching solution from the nozzle to the surface of the semiconductor wafer.
  • a method of manufacturing a semiconductor device including at least one step selected from the group consisting of: etching a semiconductor wafer; and supplying a resist solution from a nozzle to the surface of the semiconductor wafer to resist the semiconductor wafer.
  • FIG. 1 is a longitudinal sectional view of the manufacturing apparatus of the present embodiment
  • FIG. 2 is a top view of the manufacturing apparatus of the present embodiment.
  • the manufacturing apparatus of the present embodiment includes a stage 2, a chuck pin 3, a nozzle 4 and a cup body 10.
  • the semiconductor wafer 1 is held on the stage 2 by fixing its outer periphery with four chuck pins 3.
  • the stage 2 is rotated together with the semiconductor wafer 1 held by the stage 2 in the direction indicated by the arrow in FIG. It can be done.
  • the nozzle 4 and the chuck pin 3 are a resin molded body including a composite resin material including at least one fluorocarbon resin and carbon nanotube.
  • the chuck pin 3 is electrically connected to, for example, the apparatus housing 7. Since the nozzle 4 is the resin molded body, charging of the liquid supplied to the surface of the semiconductor wafer 1 from the liquid supply port 6 through the nozzle 4 is prevented, and contamination of the liquid is also avoided. Since the chuck pin 3 is the above resin molded body, static electricity charged on the front surface, side surface, back surface, etc. of the semiconductor wafer 1 flows into the chuck pin 3 and finally flows into the device housing 7 and flows out of the device. .
  • the stage 2 may or may not be a resin molding containing a composite resin material containing at least one fluorocarbon resin and carbon nanotubes.
  • static electricity flowing into the chuck pin 3 may be designed to flow from the stage 2 to the rotary drive shaft 5 and finally to flow out of the apparatus.
  • the apparatus shown in FIGS. 1 and 2 includes four chuck pins, the number and position of the chuck pins may be changed as appropriate.
  • at least one of the four chuck pins may be the resin molded body.
  • a liquid such as a cleaning liquid is scattered to the outside of the semiconductor wafer 1.
  • the liquid scattered from the semiconductor wafer 1 can be received.
  • the semiconductor wafer 1 can be placed on the stage or taken out of the stage.
  • the outer cup 10a and the inner cup 10b may or may not be resin moldings each including a composite resin material including at least one fluorocarbon resin and carbon nanotube.
  • the apparatus shown in FIG. 1 may further have a wafer pin which is the above-mentioned resin molded body. In that case, more efficient removal of static electricity is possible.
  • the manufacturing apparatus of the present embodiment includes a stage 2, a chuck pin 3, a wafer pin 8 and a nozzle 4.
  • the semiconductor wafer 1 is held on the stage 2 by fixing its outer periphery with the chuck pin 3 and supporting it from the back side with the wafer pin 8.
  • the stage 2 can be rotated together with the semiconductor wafer 1 held by the stage 2 by rotating the rotational drive shaft 5 attached to the stage 2 in the direction indicated by the arrow in FIG.
  • the numbers and positions of chuck pins and wafer pins are not limited and may be selected as appropriate.
  • At least one of the nozzle 4, the chuck pin 3 and the wafer pin 8 is a resin molded body including a composite resin material including at least one fluorocarbon resin and carbon nanotube.
  • at least one of the plurality of chuck pins 3 and wafer pins 8 may be the resin molded body. Since the nozzle 4 is the resin molded body, charging of the liquid supplied to the surface of the semiconductor wafer 1 from the liquid supply port 6 through the nozzle 4 is prevented, and contamination of the liquid is also avoided.
  • the chuck pin 3 is the above-mentioned resin molded body, although not shown, by electrically connecting the chuck pin 3 and the device housing 7, static electricity charged on the semiconductor wafer 1 flows into the chuck pin 3.
  • the wafer pin 8 is the above-mentioned resin molded body
  • static electricity charged on the semiconductor wafer 1 can be obtained by connecting the rotary drive shaft 5 made of metal, for example, to the wafer pin 8 as illustrated.
  • the stage 2 may or may not be a resin molding containing a composite resin material containing at least one fluorocarbon resin and carbon nanotubes.
  • stage 2 is the above-mentioned resin molded body
  • static electricity which has flowed into the chuck pin 3 and / or the wafer pin 8 is flowed from the stage 2 to the rotary drive shaft 5 and finally designed to flow out of the apparatus.
  • the manufacturing apparatus of the present embodiment includes a stage 2, a chuck pin 3 and a nozzle 4.
  • the semiconductor wafer 1 is held on the stage 2 by fixing its outer periphery with chuck pins 3.
  • the semiconductor wafer 1 is in contact with the mounting surface of the stage 2.
  • the stage 2 can be rotated together with the semiconductor wafer 1 held by the stage 2 by rotating the rotational drive shaft 5 attached to the stage 2 in the direction indicated by the arrow in FIG. 4, for example.
  • the number and position of the chuck pins are not limited and may be selected as appropriate.
  • At least the nozzle 4 and the chuck pin 3 are a resin molded body including a composite resin material containing at least one fluorocarbon resin and carbon nanotube.
  • at least one of the plurality of chuck pins 3 may be the resin molded body. Since the nozzle 4 is the resin molded body, charging of the liquid supplied to the surface of the semiconductor wafer 1 from the liquid supply port 6 through the nozzle 4 is prevented, and contamination of the liquid is also avoided.
  • the chuck pin 3 is the above-mentioned resin molded body, although not shown, by electrically connecting the chuck pin 3 and the device housing 7, static electricity charged on the semiconductor wafer 1 flows into the chuck pin 3. Finally, it flows to the device case 7 and flows to the outside of the device.
  • the stage 2 may or may not be a resin molding containing a composite resin material containing at least one fluorocarbon resin and carbon nanotubes.
  • the stage 2 when the stage 2 is the above-described resin molded body, static electricity is removed more efficiently from the entire back side of the semiconductor wafer 1 because the back surface of the semiconductor wafer 1 and the mounting surface of the stage 2 are in contact. Is possible.
  • the static electricity flowing into the chuck pin 3 may be designed to flow from the stage 2 to the rotary drive shaft 5 and finally to flow out of the apparatus.
  • the composite resin particles obtained in the production example described later were subjected to pretreatment (eg, preliminary drying, granulation, etc.) as necessary, and then uniformly filled in a predetermined amount in a molding die.
  • the preparation procedure after filling varies depending on the type of fluororesin.
  • the fluorocarbon resin was a PTFE resin and a modified PTFE resin
  • the composite resin particles were compressed by pressing at 15 MPa and holding for a certain period of time to obtain a preformed body.
  • the obtained preform is taken out of the molding die, fired in a hot air circulating electric furnace set at 345 ° C.
  • the fluorocarbon resin is PCTFE resin, PFA resin, FEP resin, ETFE resin, ECTFE resin, PVDF resin, and PVF resin (other than PTFE resin and modified PTFE resin), appropriate pre-drying etc. depending on the size of the molded product
  • the resin is melted by heating for 2 hours or more in a hot air circulating electric furnace in which the mold is set to 200 ° C. or more. After heating for a predetermined time, the mold is taken out of the electric furnace, and the mold is cooled to around normal temperature while pressing and compressing with a hydraulic press at a surface pressure of 25 kg / cm 2 or more. The material was obtained.
  • a test piece of ⁇ 110 ⁇ 10 mm was produced from the resin material (molded body) obtained as described above from the composite resin particles, and used as a measurement sample.
  • the measurement of volume resistivity was performed using a resistivity meter ("Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS K6911.
  • the degree of detachment of carbon nanotubes from the molded body was evaluated by measuring TOC using a total organic carbon meter (“TOCvwp” manufactured by Shimadzu Corporation). Specifically, a 10 mm ⁇ 20 mm ⁇ 50 mm test piece obtained by cutting the resin material obtained as described above is immersed in 0.5 L of 3.6% hydrochloric acid (EL-UM grade made by Kanto Chemical) for about 1 hour. After immersion for 1 hour, take out and wash with ultra pure water (specific resistance: 118.0 M ⁇ ⁇ cm), and immerse the entire test piece in ultra pure water for 24 hours and 168 hours at room temperature. saved. After the specified time elapsed, the entire amount of the immersion liquid was recovered, and the total organic carbon analysis was performed on the immersion liquid.
  • TOCvwp total organic carbon meter
  • the weight of the piece was measured using an electronic balance in the same manner as before immersion.
  • the weight change before and after immersion was calculated by the following equation and used as an index of chemical resistance.
  • Weight change (%) [(weight after immersion-weight before immersion) / weight before immersion] x 100
  • SPM treatment sulfuric acid soaking treatment
  • a sulfuric acid / hydrogen peroxide solution was prepared by mixing 98% sulfuric acid and 30% hydrogen peroxide water at a weight ratio of 2: 1 in a glass beaker.
  • a dumbbell test piece made according to JIS K7137-2-A prepared by cutting from the composite resin particles obtained by the above method is put in a place where the temperature of the prepared sulfuric acid / hydrogen peroxide reaches the maximum temperature by the reaction heat, and it is immersed for 24 hours The After immersion for 24 hours, preparation of sulfuric acid / hydrogen peroxide was repeated, immersion for 24 hours was repeated, and measurement of volume resistivity was performed according to JIS K6911 for test pieces immersed for 30 days by accumulation.
  • modified PTFE particles or polychlorotetrafluoroethylene (PCTFE) particles shown in the following Table 1 were used.
  • Modified PTFE particles 1 and 2 shown in Table 1 are represented by the tetrafluoroethylene unit represented by the above formula (I) and the above formula (II) (wherein X is a perfluoropropyl group). It was confirmed that the amount of perfluorovinyl ether unit was 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene.
  • Production Example 3 Production of CNT Composite Resin Particles 3
  • a CNT composite resin particle 3 was obtained in the same manner as in Production Example 1 except that the amount of CNT was set to 0.1% by mass based on the total amount of the composite resin particle.
  • Production Example 4 Production of CNT Composite Resin Particles 4
  • a CNT composite resin particle 4 was obtained in the same manner as in Production Example 1 except that the modified PTFE particle 2 was used in place of the modified PTFE particle 1.
  • a CNT composite resin particle 5 was obtained in the same manner as in Production Example 4 except that the amount of CNT was set to 0.05% by mass based on the total amount of the composite resin particle.
  • Production Example 6 Production of CNT Composite Resin Particles 6
  • a CNT composite resin particle 6 was obtained in the same manner as in Production Example 1 except that PCTFE particles 2 were used instead of the modified PTFE 1.
  • Production Example 7 Production of CNT Composite Resin Particles 7
  • a CNT composite resin particle 7 was obtained in the same manner as in Production Example 2 except that PCTFE particles 2 were used instead of the modified PTFE 1.
  • Production Example 8 Production of CNT Composite Resin Particles 8
  • the CNT composite resin particles 8 were obtained in the same manner as in Production Example 7 except that the amount of CNTs was 0.1% by mass based on the total amount of the composite resin particles.
  • Production Example 9 Production of CNT Composite Resin Particles 9
  • the CNT composite resin particles 9 were obtained in the same manner as in Production Example 7 except that the amount of CNTs was 0.125% by mass based on the total amount of the composite resin particles.
  • a CNT composite resin particle 10 was obtained in the same manner as in Production Example 7 except that the amount of CNT was set to 0.15% by mass based on the total amount of the composite resin particle.
  • Production Example 11 Production of CNT Composite Resin Particles 11 CNT composite resin particles 11 were obtained in the same manner as in Production Example 8 except that PCTFE particles 3 were used instead of PCTFE particles 2.
  • Production Example 12 Production of CNT Composite Resin Particles 12 CNT composite resin particles 12 were obtained in the same manner as in Production Example 8 except that PCTFE particles 1 were used instead of PCTFE particles 2.
  • X is the volume resistivity [ ⁇ ⁇ cm] of the resin material
  • Y is the amount of CNT contained in the resin material [mass%] (equal to the amount of CNT used for the production of the resin material) is there.
  • composite resin materials prepared according to the above method from composite resin particles 1-12 are also referred to as composite resin materials 1-12, respectively, and composite resin materials prepared according to the above method from comparative resin particles 13-15 Also referred to as composite resin materials 13 to 15, respectively.
  • the amount of CNTs in the composite resin particles is equal to the amount of CNTs in the resin material obtained from the composite resin particles and the amount of CNTs in the chuck pins obtained from the resin material.
  • the metal elution amount and the carbon dropout were evaluated.
  • the obtained results are shown in Table 3.
  • the metal elution amount is not shown in Table 3 as the measurements were taken but at the instrument detection limit (ND).
  • all the results in Table 3 are the results after immersion for 24 hours.
  • the composite resin particles 2, 7 and 8 prepared according to the above method using the composite resin particles obtained in the above Example 2, 7 and 8 are subjected to sulfuric acid / hydrogen peroxide immersion treatment (SPM treatment) under the above conditions, The volume resistivity after treatment was measured. As a result, as shown in Table 5 below, it was confirmed that the resin material used in the apparatus of the present invention does not increase in volume resistivity even when SPM treatment is performed.
  • the surface potential after DIW cleaning The ultrapure water was discharged from the liquid supply port 6 through the nozzle 4, and the ultrapure water was supplied to the upper surface of the semiconductor wafer 1, and the semiconductor wafer 1 was cleaned for 1 minute. Then, the surface potential (after DIW cleaning) of the semiconductor wafer 1 was measured by an electrostatic measuring instrument.
  • the nozzle made from PFA was used in the present Example, the static elimination effect can be further heightened by making a nozzle also into the said composite resin material.
  • the nozzle can be manufactured by cutting using a device such as a CNC common lathe from the molded product of the composite resin material obtained as described above.
  • N 2 is sprayed from the nozzle 4 onto the semiconductor wafer 1 and the ultrapure water remaining on the surface of the wafer 1 is flushed through the chuck pin 3 and the stage 2 to the apparatus casing 7 to carry out the semiconductor wafer 1. It was allowed to dry. Then, the surface potential (after N 2 drying) of the semiconductor wafer 1 was measured by an electrostatic measuring instrument.
  • Table 6 shows the results obtained by measuring the charge removal effect of wafer charging during the above chemical solution cleaning.
  • test pieces of 10 mm ⁇ 10 mm ⁇ thickness 2 mm were obtained.
  • the test pieces were immersed in various chemical solutions shown in Table 7, and weight changes before and after immersion for about 1 week (1 W) and about 1 month (1 M) were measured.
  • the obtained results are shown in Table 7.
  • the immersion test to APM in Table 7 was performed on temperature conditions of 80 degreeC, and the immersion test to another chemical
  • the details of each chemical solution in Table 7 are as shown in Table 8.

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Abstract

La présente invention concerne un dispositif de fabrication d'élément à semi-conducteurs et un procédé de fabrication d'élément à semi-conducteurs qui ont un effet d'élimination statique efficace, et présentent une excellente propreté et une excellente résistance chimique. Ce dispositif de fabrication d'élément à semi-conducteurs comprend : un plateau qui est équipé d'une broche de mandrin et/ou d'une broche de tranche, et qui est utilisé pour maintenir une tranche de semi-conducteur ; et une buse qui est utilisée pour fournir une solution de lavage, une solution de gravure ou une solution de réserve. La buse est un corps moulé en résine qui comprend un matériau de résine composite comprenant des nanotubes de carbone et au moins une résine fluorée, et/ou au moins un élément choisi parmi la broche de mandrin, la broche de tranche, et le plateau étant un corps moulé en résine qui comprend un matériau de résine composite comprenant des nanotubes de carbone et au moins une résine fluorée.
PCT/JP2018/027360 2017-07-21 2018-07-20 Dispositif de fabrication d'élément à semi-conducteurs et procédé de fabrication d'éléments à semi-conducteurs WO2019017489A1 (fr)

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JP2020184590A (ja) * 2019-05-09 2020-11-12 株式会社Ｓｃｒｅｅｎホールディングス 基板処理装置、チャック部材
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JP2022036902A (ja) * 2020-08-24 2022-03-08 セメス カンパニー，リミテッド 基板処理装置、イオン注入処理装置、及びイオン注入処理方法
KR20230129409A (ko) 2021-01-06 2023-09-08 미쯔비시 케미컬 주식회사 유기 전계 발광 소자용 조성물, 유기 전계 발광 소자,표시 장치 및 조명 장치
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JP2022036902A (ja) * 2020-08-24 2022-03-08 セメス カンパニー，リミテッド 基板処理装置、イオン注入処理装置、及びイオン注入処理方法
JP7379419B2 (ja) 2020-08-24 2023-11-14 セメス カンパニー，リミテッド 基板処理装置、イオン注入処理装置、及びイオン注入処理方法
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KR20230129409A (ko) 2021-01-06 2023-09-08 미쯔비시 케미컬 주식회사 유기 전계 발광 소자용 조성물, 유기 전계 발광 소자,표시 장치 및 조명 장치

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