WO2021111362A1 - Infilling sheet for plasma device, part for plasma device comprising said infilling sheet, and plasma device comprising said infilling sheet - Google Patents

Infilling sheet for plasma device, part for plasma device comprising said infilling sheet, and plasma device comprising said infilling sheet Download PDF

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Publication number
WO2021111362A1
WO2021111362A1 PCT/IB2020/061450 IB2020061450W WO2021111362A1 WO 2021111362 A1 WO2021111362 A1 WO 2021111362A1 IB 2020061450 W IB2020061450 W IB 2020061450W WO 2021111362 A1 WO2021111362 A1 WO 2021111362A1
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WIPO (PCT)
Prior art keywords
infilling
sheet
substrate
plasma device
fluororesin
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PCT/IB2020/061450
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French (fr)
Inventor
Kazuki Noda
Daiki KOSEKI
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3M Innovative Properties Company
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Publication of WO2021111362A1 publication Critical patent/WO2021111362A1/en

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    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68318—Auxiliary support including means facilitating the separation of a device or wafer from the auxiliary support

Definitions

  • the present disclosure relates to an infilling sheet for a plasma device, a part for a plasma device, and a plasma device.
  • a plasma device has been used in various kinds of application such as chemical vapor deposition (CVD), physical vapor deposition (PVD), ion implantation, and etching.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • ion implantation ion implantation
  • etching etching
  • a treated substrate such as a semiconductor wafer is often held on a support member, for example, a susceptor, including heating and cooling means.
  • a support member for example, a susceptor, including heating and cooling means.
  • thermal conduction between the treated substrate and the support member can be promoted and heat generated in the treated substrate can be released through the support member, or necessary heat can be supplied from the support member to the treated substrate.
  • plasma treatment is a vacuum process, unlike an atmospheric pressure process, since the density of gas contributing to thermal conduction in a gap between two materials is low, there is a significant advantage in disposing a filler in the gap and promoting thermal conduction.
  • Patent Document 1 JP 2006-165136 A describes an “etching method in which a substrate to be etched is subjected to dry etching by using a dry etching device by plasma, the method including: providing a support substrate for supporting the substrate to be etched and a heat dissipation sheet formed of an elastic material; sandwiching the heat dissipation sheet between the substrate to be etched and the support substrate to form a laminate in which the heat dissipation sheet adheres to the substrate to be etched and the support substrate; setting the laminate on a substrate support member in the dry etching device such that the support substrate in the laminate faces the substrate support member, and subjecting the substrate to be etched to dry etching.”
  • Patent Document 2 JP 2013-008746 A describes a “substrate holding device that holds a substrate to be treated, the substrate holding device including: a base including cooling means; an insulating plate fixed to an upper surface of the base with the direction from the base toward the substrate facing up; and a chuck body installed in an upper surface of the insulating plate and including positive and negative electrodes and heating means, the chuck body being entirely formed of a dielectric material and including an upper surface on which a substrate is mounted, wherein a sheet member having a predetermined thickness is interposed between the upper surface of the base and a lower surface of the insulating plate, the sheet member adhering to the base and the plate to reduce thermal resistance.”
  • Patent Document 3 JP 2012-043928 A describes a “plasma treatment method in which a material to be treated is mounted on a tray, the tray is further mounted on a support table, and a surface of the material to be treated is treated by plasma, the method including bonding the tray and the material to be treated with a thermally releasing adhesive member provided with a thermally releasing adhesive layer in each of both sides of a sheet-like substrate.”
  • Examples of a filler that fills a gap between two materials include grease and a sheet that include an organic material.
  • the filler is exposed during plasma treatment to environment having high temperature such as from 150°C to 250°C, in which plasma excited gas and radical species are present.
  • environment having high temperature such as from 150°C to 250°C, in which plasma excited gas and radical species are present.
  • plasma excited gas and radical species are present.
  • the filler degrades or volatilizes during plasma treatment, a treated substrate and a chamber interior of a plasma device are contaminated, and thermal conduction efficiency between the treated substrate and a support member also decreases. Since an organic material that exhibits durability in such harsh environment is very limited, there is almost no option for a material that can be used in a plasma device.
  • a surface of the treated substrate or the support member may be processed, and is not necessarily a mirror surface.
  • the treated substrate is taken out of the support member, and transferred to the next step.
  • a residue of the filler is present on the treated substrate, it may be necessary to perform the washing step prior to the next step, and there is a risk that a manufacturing line may be contaminated by the residue of the filler.
  • the present disclosure provides a heat resistant filler that has high plasma resistance and high radical resistance, can promote thermal conduction between a treated substrate and a support member, and can be removed easily from the treated substrate.
  • an infilling sheet for a plasma device including: a fluororesin sheet substrate including a first side and a second side opposite to the first side; and a glassy coating disposed on at least the first side of the fluororesin sheet substrate, wherein the fluororesin sheet substrate has a storage elastic modulus from 3 c 10 6 Pa to 2 c 10 8 Pa in all the temperature range from 150°C to 250°C.
  • a part for a plasma device including the above-described infilling sheet is provided.
  • a plasma device including the above-described infilling sheet is provided.
  • An infilling sheet for a plasma device of the present disclosure has high plasma resistance and high radical resistance, can promote thermal conduction between a treated substrate and a support member, and can be removed easily from the treated substrate.
  • FIG. 1 is a schematic cross-sectional view of an infilling sheet for a plasma device according to an embodiment.
  • filling refers to coming into contact with two materials to fill a space or a gap between these materials and mediating thermal conduction between these materials, or refers to such properties of a matenal.
  • a “sheet” refers to a material having a shape such that a dimension (size) of the thickness is much smaller than other dimensions (sizes), such as 1/100 or less or 1/1000 or less, and a “film” is used interchangeably.
  • the “sheet” includes, in addition to a rectangular sheet, those having shapes other than a rectangular shape such as a round shape and an oval shape, for example, a ring gasket.
  • An infilling sheet for a plasma device of an embodiment (hereinafter, also referred to simply as an “infilling sheet”) includes a fluororesin sheet substrate including a first side and a second side opposite to the first side, and a glassy coating disposed on at least the first side of the fluororesin sheet substrate.
  • FIG. 1 illustrates a schematic cross-sectional view of an infilling sheet according to an embodiment.
  • An infilling sheet 10 includes a fluororesin sheet substrate 12 and a glassy coating 14 disposed on a first side (upper surface) of the fluororesin sheet substrate 12.
  • FIG. 1 illustrates an adhesive layer 16 disposed on a second side (lower surface) of the fluororesin sheet substrate 12 as an optional component.
  • the fluororesin sheet substrate is a main layer of the infilling sheet, and imparts plasma resistance and radical resistance to the infilling sheet.
  • the fluororesin sheet substrate can include a variety of fluororesins.
  • the fluororesin sheet substrate includes at least one selected from the group consisting of a tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and a tetrafluoroethylene -ethylene copolymer (ETFE).
  • PFA tetrafluoroethylene-perfluoroalkoxyethylene copolymer
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • ETFE tetrafluoroethylene -ethylene copolymer
  • the fluororesin sheet substrate preferably includes PFA, ETFE, PTFE, or combinations thereof, and more preferably includes PFA, ETFE, or combinations thereof
  • the fluororesin sheet substrate may be a sheet that does not include a resin other than the fluororesin.
  • the fluororesin sheet substrate may include a thermally conductive fdler such as boron nitride (BN).
  • BN boron nitride
  • the fluororesin sheet substrate does not include a fdler. In this embodiment, contamination of a chamber interior of a plasma device due to the fdler can be reduced.
  • the fluororesin sheet substrate can be obtained by extruding the fluororesin described above and molding the fluororesin by a known method such as casting.
  • the fluororesin sheet substrate has a storage elastic modulus from about 3 c 10 6 Pa to about 2 c 10 8 Pa in all the temperature range from 150°C to 250°C.
  • the storage elastic modulus of the fluororesin sheet substrate is set to be within the range described above, and thus, during operation of a plasma device, the infdling sheet is made adhere to a treated substrate or a support member that may include a rough surface and thermal conduction between the treated substrate and the support member can be promoted.
  • the fluororesin sheet substrate has a storage elastic modulus of about 5 c 10 6 Pa or greater, or about 8 c 10 6 Pa or greater, and about 1.5 c 10 8 Pa or less, or about 1 c 10 8 Pa or less in all the temperature range from 150°C to 250°C.
  • the storage elastic modulus is measured by using a dynamic viscoelasticity measurement device RSA3 (TA Instruments Japan Inc. (Shinagawa-ku, Tokyo, Japan)) under conditions of a frequency of 1 Hz, strain of 0.1%; and a rate of temperature increase of 5°C/minute.
  • the thickness of the fluororesin sheet substrate may vary according to application and required thermal conduction efficiency.
  • the thickness of the fluororesin sheet substrate is about 1 pm or greater, about 2 pm or greater, or about 5 pm or greater, and about 60 pm or less, about 50 pm or less, or about 30 pm or less.
  • the thickness of the fluororesin sheet substrate is set to be about 60 pm or less, and thus it is possible to increase the surface followability of the infilling sheet and reduce thermal resistance due to the fluororesin sheet substrate itself, and to increase the thermal conduction efficiency of the infilling sheet.
  • the thickness of the fluororesin sheet substrate is set to be about 1 pm or greater, and thus strength required to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet.
  • the glassy coating includes an organic-inorganic material having a Si-O-Si bond as a main component, and has high thermal resistance similar to thermal resistance of glass that is an inorganic material, while being softer than glass.
  • the glassy coating is disposed on at least the first side of the fluororesin sheet substrate, and thus even after the infilling sheet is exposed to high temperature in plasma treatment or the like, the infilling sheet can be removed easily from the treated substrate that is in contact with the glassy coating.
  • the glassy coating includes a condensate of an alkyl silicate partial hydrolysate.
  • alkyl silicate examples include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, and n-butyl silicate.
  • the partial hydrolysate of alkyl silicate can be obtained, as a solution of a mixed solvent of water and by-product alcohol, and optionally-used alcohol, by adding water and, as necessary, alcohol such as methanol, ethanol or isopropanol to alkyl silicate, and advancing hydrolysis and condensation reaction of the alkyl silicate in the presence of an acidic catalyst such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or an organic acid.
  • an acidic catalyst such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or an organic acid.
  • the alkyl silicate partial hydrolysate has a number average molecular weight of about 800 or greater, or about 1600 or greater, and about 4000 or less, or about 2500 or less.
  • a relatively soft film having excellent adhesion to the fluororesin sheet substrate can be formed.
  • the number average molecular weight of the alkyl silicate partial hydrolysate is determined by a gel permeation chromatography (GPC) method calibrated with a polystyrene standard.
  • the glassy coating including a condensate of an alkyl silicate partial hydrolysate can be formed by applying a coating composition including an alkyl silicate partial hydrolysate and, as necessary, alcohol such as methanol, ethanol and isopropanol, ketone such as acetone and ethyl methyl ketone, or ester such as ethyl acetate, as a solvent, to the first side of the fluororesin sheet substrate by bar coating, roll coating, casting coating, spraying, or the like, and subsequently heating at from about 60°C to about 150°C, for example, to further advance condensation reaction, and volatilizing water and the solvent.
  • a coating composition including an alkyl silicate partial hydrolysate and, as necessary, alcohol such as methanol, ethanol and isopropanol, ketone such as acetone and ethyl methyl ketone, or ester such as ethyl acetate as a solvent
  • surface treatment may be performed on the first side of the fluororesin sheet substrate by plasma treatment, corona treatment, flame treatment, or the like.
  • the adhesion of the glassy coating to the fluororesin sheet substrate can be increased by performing the surface treatment.
  • the surface treatment is plasma treatment.
  • a ratio [(Si Is) + (01s)]/(Cls) of concentration of Si atoms and O atoms to concentration of C atoms in the glassy coating is about 6.4 or less.
  • the atomic concentration ratio in the glassy coating can be set to be about 2 or more, or about 4 or more, and about 6.2 or less, or about 6 or less.
  • the atomic concentration ratio in the glassy coating is determined by X-ray photoelectron spectroscopic analysis (XPS or ESCA).
  • the atomic concentration ratio in the glassy coating is about 6.4 or less, and thus it is possible to suppress a crack of the glassy coating or peeling of the glassy coating from the fluororesin sheet substrate due to contraction of the glassy coating, and to maintain a form of the glassy coating without crack even when the sheet is bent. Accordingly, the removability of the infilling sheet can be ensured.
  • the atomic concentration ratio in the glassy coating is about 2 or greater, and thus it is possible to prevent sticking of the infilling sheet at high temperature.
  • X-ray photoelectron spectroscopic analysis is performed under the following conditions.
  • Electron gun voltage 15 kV
  • the thickness of the glassy coating can be set, for example, to be about 10 nm or greater, about 50 nm or greater, or about 100 nm or greater, and about 2 pm or less, about 1 pm or less, or about 0.5 pm or less.
  • the thickness of the glassy coating is set to be about 2 pm or less, and thus it is possible to avoid damage to the glassy coating associated with bending of the sheet.
  • the thickness of the glassy coating is set to be about 10 nm or greater, and thus releasability sufficient to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet.
  • the thickness of the glassy coating is about 100 nm or greater, or about 200 nm or greater to prevent a decrease in releasability due to damage to the glassy coating.
  • the glassy coating may be disposed on the second side opposite to the first side, in addition to the first side of the fluororesin sheet substrate.
  • the glassy coating is disposed on each of both the first side and the second side of the fluororesin sheet substrate, and thus even after the infilling sheet is exposed to high temperature in plasma treatment or the like, the infilling sheet can be removed easily from any of the treated substrate and the support member that sandwich the infilling sheet.
  • the infilling sheet includes the adhesive layer on the second side of the fluororesin sheet substrate.
  • the adhesive layer is provided on the second side of the fluororesin sheet substrate, and thus it is possible to bond and fix the infilling sheet to the support member, and to increase the contact area of the infilling sheet with the support member, and increase the thermal conduction efficiency between the support member and the infilling sheet.
  • a material for the adhesive layer can appropriately be determined in consideration of adhesive strength, thermal resistance, and the like.
  • the adhesive layer includes a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (THV) or a silicone resin. Due to high thermal resistance, high plasma resistance and high radical resistance, the adhesive layer advantageously includes THV.
  • the adhesive layer may be crosslinked by electron beam irradiation. The fluidity of the adhesive layer at high temperature can be reduced by electron beam crosslinking, and exudation of the adhesive layer during plasma treatment can be suppressed.
  • the adhesive layer can be formed by applying an adhesive composition to the second side of the fluororesin sheet substrate and curing or drying the adhesive composition by heating, ultraviolet irradiation, electron beam irradiation, or the like as necessary.
  • surface treatment may be performed on the second side of the fluororesin sheet substrate by plasma treatment, corona treatment, flame treatment, or the like.
  • the adhesive layer can be a pressure sensitive adhesive layer or a hot melt adhesive layer.
  • the adhesive layer is a hot melt adhesive layer including THV.
  • the infilling sheet can be heated to from about 40°C to about 80°C, for example, and then bond to the surface of the support member.
  • the thickness of the adhesive layer can be set to be about 0.1 mih or more, about 0.2 mhi or greater, or about 0.5 mih or greater, and about 10 mih or less, about 5 mhi or less, or about 3 mih or less.
  • the thickness of the infilling sheet is about 1 pm or greater, about 2 pm or greater, or about 5 pm or greater, and about 60 pm or less, about 50 pm or less, or about 30 pm or less.
  • the thickness of the infilling sheet is set to be about 60 pm or less, and thus it is possible to increase the surface followability of the infilling sheet and reduce thermal resistance due to the infilling sheet itself, and to increase the thermal conduction efficiency of the infilling sheet.
  • the thickness of the infilling sheet is set to be about 1 pm or more, and thus strength required to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet.
  • the infilling sheet has a storage elastic modulus from about 3 c 10 6 Pa to about 2 x 10 8 Pa in all the temperature range from 150°C to 250°C.
  • the storage elastic modulus of the infilling sheet is set to be within the range described above, and thus during operation of a plasma device, the infilling sheet is made adhere to the treated substrate or the support member that may include a rough surface, and thermal conduction between the treated substrate and the support member can be promoted.
  • the infilling sheet has a storage elastic modulus of about 5 c 10 6 Pa or greater, or about 8 x 10 6 Pa or greater, and about 1.5 c 10 8 Pa or less, or about 1 c 10 s Pa or less in all the temperature range from 150°C to 250°C.
  • the infilling sheet of the present disclosure can be used not only between the treated substrate and the support member, but also to promote thermal conduction between parts constituting a plasma device or inside the parts. Since the infilling sheet includes the glassy coating, the infilling sheet can be removed easily from a part that is in contact with at least the glassy coating, for example, during part replacement.
  • a part for a plasma device including the infilling sheet is provided. Examples of the part for a plasma device include a susceptor.
  • the infilling sheet can be disposed in a surface of the part or inside the part.
  • a plasma device including the infilling sheet is provided.
  • the plasma device include a plasma CVD device, a plasma PVD device, a plasma ion injection device, and a plasma etcher.
  • a first side of a PFA film was plasma-treated by using a plasma dry cleaner PDC210 (Y amato Scientific Co., Ltd. (Chuo-ku, Tokyo, Japan)).
  • An 18 mass% solution (HAS-6) of a partial hydrolysate of ethyl silicate was applied to the plasma-treated first side of the PFA film, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Example 1 was made.
  • Example 2
  • a 12.5 mass% THY solution was applied to a second side of the infilling sheet of Example 1, and dried for 5 minutes at 100°C to form a 2 pm thick THV adhesive layer. In this way, an infilling sheet of Example 2 was made.
  • Example 3 An infilling sheet of Example 3 was made in the same manner as in Example 1 except that the PFA film of Example 1 was changed to an FEP film.
  • Example 4 An infilling sheet of Example 4 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to an FEP film.
  • Example 5 An infilling sheet of Example 5 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to a 25 pm thick ETFE film.
  • Example 6 An infilling sheet of Example 6 was made in the same manner as in Example 1 except that the PFA film of Example 1 was changed to a 50 pm thick ETFE film.
  • Example 7 An infilling sheet of Example 7 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to a 50 pm thick ETFE film.
  • a PFA film, an FEP film, and a 50 pm thick ETFE film were used as infilling sheets of Comparative Examples 1 to 3, respectively.
  • the 12.5 mass% THV solution used in Example 2 was applied onto a PTFE substrate, and dried for 5 minutes at 100°C to form a 50 pm thick THV layer. Subsequently, the THV layer was irradiated with an electron beam (EB) by using an electron beam irradiation device (PCT ENGINEERED SYSTEMS, LLC (Davenport, Iowa, USA) under conditions of an accelerating voltage of 200 keV, a beam current of 12.2 mA, an irradiation amount of 150 kGy, and line speed of 5 m/min. After the irradiation, the PTFE substrate was peeled from the THV layer. In this way, an infilling sheet of Comparative Example 4 was made.
  • EB electron beam irradiation device
  • a polyimide (PI) film and a PET film were used as infilling sheets of Comparative Examples 6 and 7, respectively.
  • a 20 mass% solution of a partial hydrolysate of ethyl silicate was applied to one side of the PET film of Comparative Example 7, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Comparative Example 8 was made.
  • PCPU polycarbonate polyurethane
  • a 20 mass% solution of a partial hydrolysate of ethyl silicate was applied to one side of the PCPU film of Comparative Example 10, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Comparative Example 11 was made.
  • the thickness of the infilling sheet was measured by using ID-SI 12 Digimatic Indicator (Mitutoyo Corporation (Kawasaki-shi, Kanagawa, Japan)). Pressure applied vertically to the sheet by a tip (17 mm 2 ) of the thickness indicator for thickness measurement was 200 kPa, as measured by using a pressure measurement film prescale for ultra low pressure (Fuji Film Co., Ltd. (Minato-ku, Tokyo,
  • the infilling sheet was die cut to make a 4 cm c 4 cm square piece, and the piece was weighed by an electronic balance.
  • the piece was placed inside a chamber of a plasma dry cleaner PDC210 (Y amato Scientific Co., Ltd. (Chuo-ku, Tokyo, Japan)), and was plasma-treated under the following conditions. Mode: RIE (reactive ion etching)
  • Plasma treatment was ended after 10 minutes, and the plasma-treated piece was weighed.
  • a ratio [(Si Is) + (01s)]/(Cls) of concentration of Si atoms and O atoms to concentration of C atoms in the glassy coating was determined by X-ray photoelectron spectroscopic analysis.
  • the x-ray photoelectron spectroscopic analysis was performed under the following conditions.
  • a 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm.
  • the infilling sheet die cut to have the same size as the size of the aluminum piece was prepared.
  • a stack was made by placing the infilling sheet on one aluminum piece (lower side) with a first side of the infilling sheet (or a glassy coating forming surface) facing up, and placing another aluminum piece (upper side) on the infilling sheet to sandwich the piece of infilling sheet between the two aluminum pieces.
  • An obtained stack was placed as it was without being vertically inverted on a hot plate controlled to 170°C, 220°C or 250°C, and a 1-kg weight was placed on the stack. After 10 minutes, the weight was removed, and the stack was taken out of the hot plate.
  • the removability of the upper side aluminum piece from the infilling sheet was evaluated. The case where there was no stress to remove the aluminum piece was evaluated as “good.” The case where stress was required to remove the aluminum piece, but the aluminum piece was easily removable was evaluated as “acceptable.” The case where it was difficult or impossible to remove the aluminum piece was evaluated as “poor.”
  • a 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm, and the piece was placed on a hot plate maintained at 60°C.
  • the infilling sheet die cut to have the same size as the size of the aluminum piece was placed on the aluminum piece, and subjected to roller brushing to make a laminate.
  • the aluminum piece on which the infilling sheet was laminated was taken out of the hot plate, and then the adhesiveness of the infilling sheet to an aluminum surface was evaluated. The case where the infilling sheet was bonded to the aluminum piece was evaluated as “good.” The case where the infilling sheet could not bond to the aluminum piece at 60°C was evaluated as “poor.”
  • Thermal Interface Material Tester Analysis Tech, Inc. (Wakefield, Massachusetts, USA) was used to measure thermal resistance. In this measurement, a sample of a material was held under a compressive load between two thermally conductive surfaces, and the two thermally conductive surfaces were each controlled to different temperature to measure a heat flow through the sample of the material. Both the thermally conductive surfaces were mirror finished.
  • the thermal resistance between the two thermally conductive surfaces that were in contact with silicone oil was measured at a load of 100 kPa. In this way, the thermal resistance between the two mirror finished thermally conductive surfaces of the device was obtained as R m -m.
  • thermal resistance R a satisfies Equation (1) below
  • thermal resistance R AI of the aluminum piece can be expressed by Equation (2) below.
  • Rin-m thermal resistance of mirror surface/mirror surface interface
  • R AI thermal resistance of aluminum piece
  • Rb Rill-in + RAI + Rin-Sli + Rsh + Rm-sh (3)
  • R m-Sh thermal resistance of mirror surface/sheet interface
  • R si thermal resistance of infilling sheet
  • a 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm, and one side of the piece was polished to be mirror finished, and the other side was roughened by sandblasting. Surface roughness Ra of the mirror surface of the aluminum plate was 0.032 pm, and surface roughness Ra of the rough surface was 0.92 pm.
  • the mirror finished side of the aluminum piece was coated with silicone oil, and the aluminum piece was placed on the lower side thermally conductive surface of the device such that the silicone oil was in contact with the lower side thermally conductive surface.
  • the infilling sheet die cut to have the same size as the size of the aluminum piece was placed on the aluminum piece.
  • the upper side thermally conductive surface of the device was pulled down until the surface came into contact with an upper surface of the infilling sheet.
  • Thermal resistance was measured at a load of 100 kPa. Since obtained thermal resistance R c satisfies Equation (5) below, thermal resistance R2 of the infilling sheet sandwiched between the mirror surface and the rough surface can be expressed by Equation (6) below.
  • Rc Rm-m + RAI + Rr-Sh + Rsh +Rm-sh (5)
  • the surface followability of the infilling sheet can be expressed by a difference AR between Ri and R2, as represented by Equation (7) below. As a value of AR is smaller, the surface followability to the rough surface of the infilling sheet is higher.
  • a storage elastic modulus of the infilling sheet was measured by using a dynamic viscoelasticity measurement device RSA3 (TA Instruments Japan Inc. (Shinagawa-ku, Tokyo, Japan)) under conditions of a frequency of 1 Hz, strain of 0.1%, and a rate of temperature increase of 5°C/minute.
  • RSA3 TA Instruments Japan Inc. (Shinagawa-ku, Tokyo, Japan)
  • Tables 2 and 3 indicate configurations and evaluation results of the infilling sheets of the examples and the comparative examples.
  • the glassy coating was cracked, and thus an exposed portion of the FEP film and the aluminum piece were in direct contact and stuck, and the aluminum piece could not be removed. Note that none of the thermal resistance, the shape followability, and a storage elastic modulus of the infilling sheet of Comparative
  • Example 12 was measured or determined, and thus “n.a.” is indicated in Table 3, but these properties are considered to be equivalent to those of the infilling sheet of Example 3 including the same fluororesin sheet substrate.

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Abstract

An infilling sheet for a plasma device is described. In particular, an infilling sheet for a plasma device including a fluororesin sheet substrate including a first side and a second side opposite to the first side, and a glassy coating disposed on at least the first side of the fluororesin sheet substrate, and the fluororesin sheet substrate has a storage elastic modulus from 3 × 106 Pa to 2 × 108 Pa in all the temperature range from 150°C to 250°C is described.

Description

INFILLING SHEET FOR PLASMA DEVICE, PART FOR PLASMA DEVICE COMPRISING SAID INFILLING SHEET, AND PLASMA DEVICE COMPRISING SAID INFILLING SHEET
Technical Field
The present disclosure relates to an infilling sheet for a plasma device, a part for a plasma device, and a plasma device.
Background
A plasma device has been used in various kinds of application such as chemical vapor deposition (CVD), physical vapor deposition (PVD), ion implantation, and etching. In these kinds of plasma treatment, a treated substrate such as a semiconductor wafer is often held on a support member, for example, a susceptor, including heating and cooling means. In this case, it is desirable to quickly exchange heat between the treated substrate and the support member to keep the temperature of the treated substrate within the desired range during plasma treatment.
When a filler that fills a gap that can be generated between the treated substrate and the support member is used, thermal conduction between the treated substrate and the support member can be promoted and heat generated in the treated substrate can be released through the support member, or necessary heat can be supplied from the support member to the treated substrate. In a case where plasma treatment is a vacuum process, unlike an atmospheric pressure process, since the density of gas contributing to thermal conduction in a gap between two materials is low, there is a significant advantage in disposing a filler in the gap and promoting thermal conduction.
Patent Document 1 (JP 2006-165136 A) describes an “etching method in which a substrate to be etched is subjected to dry etching by using a dry etching device by plasma, the method including: providing a support substrate for supporting the substrate to be etched and a heat dissipation sheet formed of an elastic material; sandwiching the heat dissipation sheet between the substrate to be etched and the support substrate to form a laminate in which the heat dissipation sheet adheres to the substrate to be etched and the support substrate; setting the laminate on a substrate support member in the dry etching device such that the support substrate in the laminate faces the substrate support member, and subjecting the substrate to be etched to dry etching.”
Patent Document 2 (JP 2013-008746 A) describes a “substrate holding device that holds a substrate to be treated, the substrate holding device including: a base including cooling means; an insulating plate fixed to an upper surface of the base with the direction from the base toward the substrate facing up; and a chuck body installed in an upper surface of the insulating plate and including positive and negative electrodes and heating means, the chuck body being entirely formed of a dielectric material and including an upper surface on which a substrate is mounted, wherein a sheet member having a predetermined thickness is interposed between the upper surface of the base and a lower surface of the insulating plate, the sheet member adhering to the base and the plate to reduce thermal resistance.”
Patent Document 3 (JP 2012-043928 A) describes a “plasma treatment method in which a material to be treated is mounted on a tray, the tray is further mounted on a support table, and a surface of the material to be treated is treated by plasma, the method including bonding the tray and the material to be treated with a thermally releasing adhesive member provided with a thermally releasing adhesive layer in each of both sides of a sheet-like substrate.”
Summary Technical Problem
Examples of a filler that fills a gap between two materials include grease and a sheet that include an organic material. However, the filler is exposed during plasma treatment to environment having high temperature such as from 150°C to 250°C, in which plasma excited gas and radical species are present. When the filler degrades or volatilizes during plasma treatment, a treated substrate and a chamber interior of a plasma device are contaminated, and thermal conduction efficiency between the treated substrate and a support member also decreases. Since an organic material that exhibits durability in such harsh environment is very limited, there is almost no option for a material that can be used in a plasma device.
A surface of the treated substrate or the support member may be processed, and is not necessarily a mirror surface. To increase thermal conduction efficiency, it is desirable to increase the contact area of the filler as much as possible with respect to such a non-mirror or rough surface.
After plasma treatment, the treated substrate is taken out of the support member, and transferred to the next step. When a residue of the filler is present on the treated substrate, it may be necessary to perform the washing step prior to the next step, and there is a risk that a manufacturing line may be contaminated by the residue of the filler. Thus, it is desirable that the filler be easily removable from the treated substrate without any residue.
The present disclosure provides a heat resistant filler that has high plasma resistance and high radical resistance, can promote thermal conduction between a treated substrate and a support member, and can be removed easily from the treated substrate.
Solution to Problem
According to an embodiment of the present disclosure, provided is an infilling sheet for a plasma device, including: a fluororesin sheet substrate including a first side and a second side opposite to the first side; and a glassy coating disposed on at least the first side of the fluororesin sheet substrate, wherein the fluororesin sheet substrate has a storage elastic modulus from 3 c 106 Pa to 2 c 108 Pa in all the temperature range from 150°C to 250°C.
According to another embodiment of the present disclosure, a part for a plasma device, including the above-described infilling sheet is provided.
According to yet another embodiment of the present disclosure, a plasma device including the above-described infilling sheet is provided. Advantageous Effects of Invention
An infilling sheet for a plasma device of the present disclosure has high plasma resistance and high radical resistance, can promote thermal conduction between a treated substrate and a support member, and can be removed easily from the treated substrate.
Note that the above description is not to be construed to mean that all embodiments of the present invention and all advantages related to the present invention are disclosed.
Brief Description of the Drawings
FIG. 1 is a schematic cross-sectional view of an infilling sheet for a plasma device according to an embodiment.
Detailed Description
Although representative embodiments of the present invention will be described below in more detail for the purpose of exemplification with reference to the drawings, the present invention is not limited to these embodiments.
In the present disclosure, “infilling” refers to coming into contact with two materials to fill a space or a gap between these materials and mediating thermal conduction between these materials, or refers to such properties of a matenal.
In the present disclosure, a “sheet” refers to a material having a shape such that a dimension (size) of the thickness is much smaller than other dimensions (sizes), such as 1/100 or less or 1/1000 or less, and a “film” is used interchangeably. The “sheet” includes, in addition to a rectangular sheet, those having shapes other than a rectangular shape such as a round shape and an oval shape, for example, a ring gasket.
An infilling sheet for a plasma device of an embodiment (hereinafter, also referred to simply as an “infilling sheet”) includes a fluororesin sheet substrate including a first side and a second side opposite to the first side, and a glassy coating disposed on at least the first side of the fluororesin sheet substrate.
FIG. 1 illustrates a schematic cross-sectional view of an infilling sheet according to an embodiment. An infilling sheet 10 includes a fluororesin sheet substrate 12 and a glassy coating 14 disposed on a first side (upper surface) of the fluororesin sheet substrate 12. FIG. 1 illustrates an adhesive layer 16 disposed on a second side (lower surface) of the fluororesin sheet substrate 12 as an optional component.
The fluororesin sheet substrate is a main layer of the infilling sheet, and imparts plasma resistance and radical resistance to the infilling sheet.
The fluororesin sheet substrate can include a variety of fluororesins. In an embodiment, the fluororesin sheet substrate includes at least one selected from the group consisting of a tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and a tetrafluoroethylene -ethylene copolymer (ETFE). In a wide temperature range of, for example, from about 150°C to about 250°C, a shape of the infilling sheet can be maintained, and thermal conduction between plasma parts can effectively be promoted. Thus, the fluororesin sheet substrate preferably includes PFA, ETFE, PTFE, or combinations thereof, and more preferably includes PFA, ETFE, or combinations thereof The fluororesin sheet substrate may be a sheet that does not include a resin other than the fluororesin.
The fluororesin sheet substrate may include a thermally conductive fdler such as boron nitride (BN). In an embodiment, the fluororesin sheet substrate does not include a fdler. In this embodiment, contamination of a chamber interior of a plasma device due to the fdler can be reduced.
The fluororesin sheet substrate can be obtained by extruding the fluororesin described above and molding the fluororesin by a known method such as casting.
The fluororesin sheet substrate has a storage elastic modulus from about 3 c 106 Pa to about 2 c 108 Pa in all the temperature range from 150°C to 250°C. The storage elastic modulus of the fluororesin sheet substrate is set to be within the range described above, and thus, during operation of a plasma device, the infdling sheet is made adhere to a treated substrate or a support member that may include a rough surface and thermal conduction between the treated substrate and the support member can be promoted. In an embodiment, the fluororesin sheet substrate has a storage elastic modulus of about 5 c 106 Pa or greater, or about 8 c 106 Pa or greater, and about 1.5 c 108 Pa or less, or about 1 c 108 Pa or less in all the temperature range from 150°C to 250°C. In the present disclosure, the storage elastic modulus is measured by using a dynamic viscoelasticity measurement device RSA3 (TA Instruments Japan Inc. (Shinagawa-ku, Tokyo, Japan)) under conditions of a frequency of 1 Hz, strain of 0.1%; and a rate of temperature increase of 5°C/minute.
The thickness of the fluororesin sheet substrate may vary according to application and required thermal conduction efficiency. In an embodiment, the thickness of the fluororesin sheet substrate is about 1 pm or greater, about 2 pm or greater, or about 5 pm or greater, and about 60 pm or less, about 50 pm or less, or about 30 pm or less. The thickness of the fluororesin sheet substrate is set to be about 60 pm or less, and thus it is possible to increase the surface followability of the infilling sheet and reduce thermal resistance due to the fluororesin sheet substrate itself, and to increase the thermal conduction efficiency of the infilling sheet. The thickness of the fluororesin sheet substrate is set to be about 1 pm or greater, and thus strength required to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet.
The glassy coating includes an organic-inorganic material having a Si-O-Si bond as a main component, and has high thermal resistance similar to thermal resistance of glass that is an inorganic material, while being softer than glass. The glassy coating is disposed on at least the first side of the fluororesin sheet substrate, and thus even after the infilling sheet is exposed to high temperature in plasma treatment or the like, the infilling sheet can be removed easily from the treated substrate that is in contact with the glassy coating.
In an embodiment, the glassy coating includes a condensate of an alkyl silicate partial hydrolysate. Examples of alkyl silicate include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, and n-butyl silicate. The partial hydrolysate of alkyl silicate can be obtained, as a solution of a mixed solvent of water and by-product alcohol, and optionally-used alcohol, by adding water and, as necessary, alcohol such as methanol, ethanol or isopropanol to alkyl silicate, and advancing hydrolysis and condensation reaction of the alkyl silicate in the presence of an acidic catalyst such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or an organic acid.
In an embodiment, the alkyl silicate partial hydrolysate has a number average molecular weight of about 800 or greater, or about 1600 or greater, and about 4000 or less, or about 2500 or less. When the number average molecular weight of the alkyl silicate partial hydrolysate is within the range described above, a relatively soft film having excellent adhesion to the fluororesin sheet substrate can be formed. The number average molecular weight of the alkyl silicate partial hydrolysate is determined by a gel permeation chromatography (GPC) method calibrated with a polystyrene standard.
The glassy coating including a condensate of an alkyl silicate partial hydrolysate can be formed by applying a coating composition including an alkyl silicate partial hydrolysate and, as necessary, alcohol such as methanol, ethanol and isopropanol, ketone such as acetone and ethyl methyl ketone, or ester such as ethyl acetate, as a solvent, to the first side of the fluororesin sheet substrate by bar coating, roll coating, casting coating, spraying, or the like, and subsequently heating at from about 60°C to about 150°C, for example, to further advance condensation reaction, and volatilizing water and the solvent.
Before the formation of the glassy coating, surface treatment may be performed on the first side of the fluororesin sheet substrate by plasma treatment, corona treatment, flame treatment, or the like. The adhesion of the glassy coating to the fluororesin sheet substrate can be increased by performing the surface treatment. In an embodiment, the surface treatment is plasma treatment.
In an embodiment, a ratio [(Si Is) + (01s)]/(Cls) of concentration of Si atoms and O atoms to concentration of C atoms in the glassy coating is about 6.4 or less. The atomic concentration ratio in the glassy coating can be set to be about 2 or more, or about 4 or more, and about 6.2 or less, or about 6 or less. In the present disclosure, the atomic concentration ratio in the glassy coating is determined by X-ray photoelectron spectroscopic analysis (XPS or ESCA). The atomic concentration ratio in the glassy coating is about 6.4 or less, and thus it is possible to suppress a crack of the glassy coating or peeling of the glassy coating from the fluororesin sheet substrate due to contraction of the glassy coating, and to maintain a form of the glassy coating without crack even when the sheet is bent. Accordingly, the removability of the infilling sheet can be ensured. The atomic concentration ratio in the glassy coating is about 2 or greater, and thus it is possible to prevent sticking of the infilling sheet at high temperature. In the present disclosure, X-ray photoelectron spectroscopic analysis is performed under the following conditions.
(1) Analyzer
Pass energy: 117.4 eY
Time per step: 100 ms eV change amount per step: 0.2 eV
Measurement range (binding energy): 0 eV to 1100 eV
(2) X-ray irradiation X-ray output: 25 W X-ray spot size: 100 pm®
Electron gun voltage: 15 kV
The thickness of the glassy coating can be set, for example, to be about 10 nm or greater, about 50 nm or greater, or about 100 nm or greater, and about 2 pm or less, about 1 pm or less, or about 0.5 pm or less. The thickness of the glassy coating is set to be about 2 pm or less, and thus it is possible to avoid damage to the glassy coating associated with bending of the sheet. The thickness of the glassy coating is set to be about 10 nm or greater, and thus releasability sufficient to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet. In a case where the roughness of a surface of the support member to which the infilling sheet is applied is high, it is advantageous to set the thickness of the glassy coating to be about 100 nm or greater, or about 200 nm or greater to prevent a decrease in releasability due to damage to the glassy coating.
The glassy coating may be disposed on the second side opposite to the first side, in addition to the first side of the fluororesin sheet substrate. The glassy coating is disposed on each of both the first side and the second side of the fluororesin sheet substrate, and thus even after the infilling sheet is exposed to high temperature in plasma treatment or the like, the infilling sheet can be removed easily from any of the treated substrate and the support member that sandwich the infilling sheet.
In an embodiment, as illustrated in FIG. 1, the infilling sheet includes the adhesive layer on the second side of the fluororesin sheet substrate. The adhesive layer is provided on the second side of the fluororesin sheet substrate, and thus it is possible to bond and fix the infilling sheet to the support member, and to increase the contact area of the infilling sheet with the support member, and increase the thermal conduction efficiency between the support member and the infilling sheet.
A material for the adhesive layer can appropriately be determined in consideration of adhesive strength, thermal resistance, and the like. In an embodiment, the adhesive layer includes a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (THV) or a silicone resin. Due to high thermal resistance, high plasma resistance and high radical resistance, the adhesive layer advantageously includes THV. The adhesive layer may be crosslinked by electron beam irradiation. The fluidity of the adhesive layer at high temperature can be reduced by electron beam crosslinking, and exudation of the adhesive layer during plasma treatment can be suppressed.
The adhesive layer can be formed by applying an adhesive composition to the second side of the fluororesin sheet substrate and curing or drying the adhesive composition by heating, ultraviolet irradiation, electron beam irradiation, or the like as necessary. Before the formation of the adhesive layer, surface treatment may be performed on the second side of the fluororesin sheet substrate by plasma treatment, corona treatment, flame treatment, or the like.
The adhesive layer can be a pressure sensitive adhesive layer or a hot melt adhesive layer. In an embodiment, the adhesive layer is a hot melt adhesive layer including THV. In this embodiment, the infilling sheet can be heated to from about 40°C to about 80°C, for example, and then bond to the surface of the support member. The thickness of the adhesive layer can be set to be about 0.1 mih or more, about 0.2 mhi or greater, or about 0.5 mih or greater, and about 10 mih or less, about 5 mhi or less, or about 3 mih or less.
Dimensions and a shape of the infilling sheet can vary according to a shape of the treated substrate or the support member. In an embodiment, the thickness of the infilling sheet is about 1 pm or greater, about 2 pm or greater, or about 5 pm or greater, and about 60 pm or less, about 50 pm or less, or about 30 pm or less. The thickness of the infilling sheet is set to be about 60 pm or less, and thus it is possible to increase the surface followability of the infilling sheet and reduce thermal resistance due to the infilling sheet itself, and to increase the thermal conduction efficiency of the infilling sheet. The thickness of the infilling sheet is set to be about 1 pm or more, and thus strength required to remove the infilling sheet from the treated substrate without any residue or damage can be imparted to the infilling sheet.
In an embodiment, the infilling sheet has a storage elastic modulus from about 3 c 106 Pa to about 2 x 108 Pa in all the temperature range from 150°C to 250°C. The storage elastic modulus of the infilling sheet is set to be within the range described above, and thus during operation of a plasma device, the infilling sheet is made adhere to the treated substrate or the support member that may include a rough surface, and thermal conduction between the treated substrate and the support member can be promoted.
In an embodiment, the infilling sheet has a storage elastic modulus of about 5 c 106 Pa or greater, or about 8 x 106 Pa or greater, and about 1.5 c 108 Pa or less, or about 1 c 10s Pa or less in all the temperature range from 150°C to 250°C.
The infilling sheet of the present disclosure can be used not only between the treated substrate and the support member, but also to promote thermal conduction between parts constituting a plasma device or inside the parts. Since the infilling sheet includes the glassy coating, the infilling sheet can be removed easily from a part that is in contact with at least the glassy coating, for example, during part replacement. In an embodiment, a part for a plasma device including the infilling sheet is provided. Examples of the part for a plasma device include a susceptor. The infilling sheet can be disposed in a surface of the part or inside the part.
In an embodiment, a plasma device including the infilling sheet is provided. Examples of the plasma device include a plasma CVD device, a plasma PVD device, a plasma ion injection device, and a plasma etcher.
Examples
Specific embodiments of the present disclosure will be exemplified in the following examples, but the present invention is not limited to these embodiments. All parts and percentages are based on mass unless otherwise specified.
Materials used to make infilling sheets of the present examples are indicated in Table 1. [Table 1] Table 1
Figure imgf000009_0001
Example 1
A first side of a PFA film was plasma-treated by using a plasma dry cleaner PDC210 (Y amato Scientific Co., Ltd. (Chuo-ku, Tokyo, Japan)). An 18 mass% solution (HAS-6) of a partial hydrolysate of ethyl silicate was applied to the plasma-treated first side of the PFA film, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Example 1 was made. Example 2
A 12.5 mass% THY solution was applied to a second side of the infilling sheet of Example 1, and dried for 5 minutes at 100°C to form a 2 pm thick THV adhesive layer. In this way, an infilling sheet of Example 2 was made.
Example 3
An infilling sheet of Example 3 was made in the same manner as in Example 1 except that the PFA film of Example 1 was changed to an FEP film. Example 4 An infilling sheet of Example 4 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to an FEP film.
Example 5
An infilling sheet of Example 5 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to a 25 pm thick ETFE film.
Example 6
An infilling sheet of Example 6 was made in the same manner as in Example 1 except that the PFA film of Example 1 was changed to a 50 pm thick ETFE film.
Example 7
An infilling sheet of Example 7 was made in the same manner as in Example 2 except that the PFA film of Example 1 was changed to a 50 pm thick ETFE film.
Comparative Examples 1 to 3
A PFA film, an FEP film, and a 50 pm thick ETFE film were used as infilling sheets of Comparative Examples 1 to 3, respectively.
Comparative Example 4
The 12.5 mass% THV solution used in Example 2 was applied onto a PTFE substrate, and dried for 5 minutes at 100°C to form a 50 pm thick THV layer. Subsequently, the THV layer was irradiated with an electron beam (EB) by using an electron beam irradiation device (PCT ENGINEERED SYSTEMS, LLC (Davenport, Iowa, USA) under conditions of an accelerating voltage of 200 keV, a beam current of 12.2 mA, an irradiation amount of 150 kGy, and line speed of 5 m/min. After the irradiation, the PTFE substrate was peeled from the THV layer. In this way, an infilling sheet of Comparative Example 4 was made.
Comparative Example 5
A 20 mass% solution of a partial hydrolysate of ethyl silicate was applied to one side of the THV layer of Comparative Example 4, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Comparative Example 5 was made.
Comparative Examples 6 and 7
A polyimide (PI) film and a PET film were used as infilling sheets of Comparative Examples 6 and 7, respectively.
Comparative Example 8
A 20 mass% solution of a partial hydrolysate of ethyl silicate was applied to one side of the PET film of Comparative Example 7, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Comparative Example 8 was made.
Comparative Example 9
A 75 pm thick silicone rubber sheet was used as an infilling sheet of Comparative Example 9. Comparative Example 10
An aqueous polycarbonate polyurethane (PCPU) dispersion UW5003 was applied onto a PET substrate, and dried at 60°C for 5 minutes and at 120°C for 10 minutes to form a 50 pm thick PCPU layer. Subsequently, the PET substrate was peeled from the PCPU layer. In this way, an infilling sheet of Comparative Example 10 was made.
Comparative Example 11
A 20 mass% solution of a partial hydrolysate of ethyl silicate was applied to one side of the PCPU film of Comparative Example 10, and dried for 2 minutes at 100°C to form a 0.5 pm thick glassy coating. In this way, an infilling sheet of Comparative Example 11 was made.
1. Thickness measurement
The thickness of the infilling sheet was measured by using ID-SI 12 Digimatic Indicator (Mitutoyo Corporation (Kawasaki-shi, Kanagawa, Japan)). Pressure applied vertically to the sheet by a tip (17 mm2) of the thickness indicator for thickness measurement was 200 kPa, as measured by using a pressure measurement film prescale for ultra low pressure (Fuji Film Co., Ltd. (Minato-ku, Tokyo,
Japan)) and a dedicated pressure image analysis system FPD-100 (Fuji Film Co., Ltd. (Minato-ku, Tokyo, Japan)).
2. Mass retention rate - plasma resistance and radical resistance
The infilling sheet was die cut to make a 4 cm c 4 cm square piece, and the piece was weighed by an electronic balance. The piece was placed inside a chamber of a plasma dry cleaner PDC210 (Y amato Scientific Co., Ltd. (Chuo-ku, Tokyo, Japan)), and was plasma-treated under the following conditions. Mode: RIE (reactive ion etching)
Gas: CF Flow: 29 seem RF output: 150 W Pressure: about 50 Pa
Plasma treatment was ended after 10 minutes, and the plasma-treated piece was weighed. A ratio of the mass of the piece after the plasma treatment to the mass of the piece before the plasma treatment (= mass of piece after plasma treatment/mass of piece before plasma treatment c 100%) was defined as a mass retention rate (%).
3. Atomic concentration ratio
A ratio [(Si Is) + (01s)]/(Cls) of concentration of Si atoms and O atoms to concentration of C atoms in the glassy coating was determined by X-ray photoelectron spectroscopic analysis. The x-ray photoelectron spectroscopic analysis was performed under the following conditions.
(1) Analyzer
Pass energy: 117.4 eV
Time per step: 100 ms eV change amount per step: 0.2 eV
Measurement range (binding energy): 0 eV to 1100 eV
(2) X-ray irradiation X-ray output: 25 W X-ray spot size: 100 pm® Electron gun voltage: 15 kV
4. Removability from A1 plate
A 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm. The infilling sheet die cut to have the same size as the size of the aluminum piece was prepared. A stack was made by placing the infilling sheet on one aluminum piece (lower side) with a first side of the infilling sheet (or a glassy coating forming surface) facing up, and placing another aluminum piece (upper side) on the infilling sheet to sandwich the piece of infilling sheet between the two aluminum pieces. An obtained stack was placed as it was without being vertically inverted on a hot plate controlled to 170°C, 220°C or 250°C, and a 1-kg weight was placed on the stack. After 10 minutes, the weight was removed, and the stack was taken out of the hot plate. After the stack was left to stand until the temperature of the stack returned to around room temperature, the removability of the upper side aluminum piece from the infilling sheet was evaluated. The case where there was no stress to remove the aluminum piece was evaluated as “good.” The case where stress was required to remove the aluminum piece, but the aluminum piece was easily removable was evaluated as “acceptable.” The case where it was difficult or impossible to remove the aluminum piece was evaluated as “poor.”
5. Adhesiveness to A1 plate
A 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm, and the piece was placed on a hot plate maintained at 60°C. The infilling sheet die cut to have the same size as the size of the aluminum piece was placed on the aluminum piece, and subjected to roller brushing to make a laminate. The aluminum piece on which the infilling sheet was laminated was taken out of the hot plate, and then the adhesiveness of the infilling sheet to an aluminum surface was evaluated. The case where the infilling sheet was bonded to the aluminum piece was evaluated as “good.” The case where the infilling sheet could not bond to the aluminum piece at 60°C was evaluated as “poor.”
6. Thermal resistance - surface followability
Thermal Interface Material Tester (Analysis Tech, Inc. (Wakefield, Massachusetts, USA) was used to measure thermal resistance. In this measurement, a sample of a material was held under a compressive load between two thermally conductive surfaces, and the two thermally conductive surfaces were each controlled to different temperature to measure a heat flow through the sample of the material. Both the thermally conductive surfaces were mirror finished.
(1) Baseline determination
The thermal resistance between the two thermally conductive surfaces that were in contact with silicone oil was measured at a load of 100 kPa. In this way, the thermal resistance between the two mirror finished thermally conductive surfaces of the device was obtained as Rm-m.
A 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm, and both sides of the piece were polished to be mirror finished. Surface roughness Ra of the mirror surface of the aluminum plate was 0.032 pm. Both the sides of the aluminum piece were coated with silicone oil, and thermal resistance was measured while the aluminum piece was kept between the two thermally conductive surfaces of the device at a load of 100 kPa. Since obtained thermal resistance Ra satisfies Equation (1) below, thermal resistance RAI of the aluminum piece can be expressed by Equation (2) below.
Ra — Rm-m t RAI Rm-m (1)
Rin-m: thermal resistance of mirror surface/mirror surface interface, and RAI: thermal resistance of aluminum piece
RAI = R, - 2Rm-m (2)
(2) Thermal resistance Ri of infdling sheet sandwiched between two mirror surfaces
One side of an aluminum piece including both sides mirror finished was coated with silicone oil, and the aluminum piece was placed on a lower side thermally conductive surface of the device such that the silicone oil was in contact with the lower side thermally conductive surface. The infilling sheet die cut to have the same size as the size of the aluminum piece was placed on the aluminum piece. An upper side thermally conductive surface of the device was pulled down until the surface came into contact with an upper surface of the infilling sheet. Thermal resistance was measured at a load of 100 kPa. Since obtained thermal resistance Rt> satisfies Equation (3) below, thermal resistance Ri of the infilling sheet sandwiched between the two mirror surfaces can be expressed by Equation (4) below.
Rb = Rill-in + RAI + Rin-Sli + Rsh + Rm-sh (3)
Rm-Sh: thermal resistance of mirror surface/sheet interface, and Rsi,: thermal resistance of infilling sheet
Rl = Rm-sh + Rsh + Rm-sh = Rb - Rm-m - RAI (4)
(3) Thermal resistance R2 of infilling sheet sandwiched between mirror surface and rough surface
A 1 mm thick aluminum plate was die cut into a piece having a diameter of 33 mm, and one side of the piece was polished to be mirror finished, and the other side was roughened by sandblasting. Surface roughness Ra of the mirror surface of the aluminum plate was 0.032 pm, and surface roughness Ra of the rough surface was 0.92 pm. The mirror finished side of the aluminum piece was coated with silicone oil, and the aluminum piece was placed on the lower side thermally conductive surface of the device such that the silicone oil was in contact with the lower side thermally conductive surface. The infilling sheet die cut to have the same size as the size of the aluminum piece was placed on the aluminum piece. The upper side thermally conductive surface of the device was pulled down until the surface came into contact with an upper surface of the infilling sheet. Thermal resistance was measured at a load of 100 kPa. Since obtained thermal resistance Rc satisfies Equation (5) below, thermal resistance R2 of the infilling sheet sandwiched between the mirror surface and the rough surface can be expressed by Equation (6) below.
Rc = Rm-m + RAI + Rr-Sh + Rsh +Rm-sh (5)
Rr-sh: thermal resistance of rough surface/sheet interface
R2 — Rr-sh + Rsh + Rm-sh = Rc " Rm-m - RAI (6)
(4) Surface followability
The surface followability of the infilling sheet can be expressed by a difference AR between Ri and R2, as represented by Equation (7) below. As a value of AR is smaller, the surface followability to the rough surface of the infilling sheet is higher. AR = Rj - Rl = (Rr-sh + Rh + Rrn-Sh) - (Rm-sh + Rh + Rrn-sh) = Rr-sh - Rin-sli (7)
7. Storage elastic modulus
A storage elastic modulus of the infilling sheet was measured by using a dynamic viscoelasticity measurement device RSA3 (TA Instruments Japan Inc. (Shinagawa-ku, Tokyo, Japan)) under conditions of a frequency of 1 Hz, strain of 0.1%, and a rate of temperature increase of 5°C/minute.
Tables 2 and 3 indicate configurations and evaluation results of the infilling sheets of the examples and the comparative examples. As for the infilling sheet of Comparative Example 12, the glassy coating was cracked, and thus an exposed portion of the FEP film and the aluminum piece were in direct contact and stuck, and the aluminum piece could not be removed. Note that none of the thermal resistance, the shape followability, and a storage elastic modulus of the infilling sheet of Comparative
Example 12 was measured or determined, and thus “n.a.” is indicated in Table 3, but these properties are considered to be equivalent to those of the infilling sheet of Example 3 including the same fluororesin sheet substrate.
[Table 2] Table 2
Figure imgf000015_0001
1) SiO: glassy coating, aTHV: THY adhesive layer
[Table 3]
Table 3
Figure imgf000016_0001
1) SiO: glassy coating, aTHV: THY adhesive layer It is obvious to those skilled in the art that various modifications and changes of the present invention can be made without departing from the scope and spirit of the present invention.

Claims

What is claimed is:
1. An infilling sheet for a plasma device, comprising: a fluororesin sheet substrate including a first side and a second side opposite to the first side; and a glassy coating disposed on at least the first side of the fluororesin sheet substrate, wherein the fluororesin sheet substrate has a storage elastic modulus from 3 c 106 Pa to 2 c 108 Pa in all the temperature range from 150°C to 250°C.
2. The infilling sheet according to claim 1, wherein the fluororesin sheet substrate includes at least one selected from the group consisting of a tetrafluoroethylene- perfluoroalkoxyethylene copolymer (PFA), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and a tetrafluoroethylene-ethylene copolymer (ETFE).
3. The infilling sheet according to claim 1 or 2, comprising an adhesive layer on the second side.
4. The infilling sheet according to claim 3, wherein the adhesive layer includes a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer (THV).
5. The infilling sheet according to claim 3 or 4, wherein the adhesive layer is electron beam crosslinked.
6. The infilling sheet according to any one of claims 1 to 5, having a thickness of 60 pm or less.
7. The infilling sheet according to any one of claims 1 to 6, wherein the infilling sheet has a storage elastic modulus from 3 c 106 Pa to 2 c 108 Pa in all the temperature range from 150°C to 250°C.
8. The infilling sheet according to any one of claims 1 to 7, wherein the glassy coating includes a condensate of an alkyl silicate partial hydrolysate.
9. The infilling sheet according to any one of claims 1 to 8, wherein a ratio [(Si Is) +
(01s)]/(Cls) of concentration of Si atoms and O atoms to concentration of C atoms in the glassy coating is 6.4 or less.
10. A part for a plasma device, comprising the infilling sheet according to any one of claims 1 to 9.
11 A plasma device comprising the infilling sheet according to any one of claims 1 to 9.
PCT/IB2020/061450 2019-12-06 2020-12-03 Infilling sheet for plasma device, part for plasma device comprising said infilling sheet, and plasma device comprising said infilling sheet WO2021111362A1 (en)

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JP2019-221262 2019-12-06
JP2019221262A JP2021091102A (en) 2019-12-06 2019-12-06 Infilling sheet for plasma device, component for plasma device, and plasma device

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030215578A1 (en) * 2002-04-09 2003-11-20 Tomohiro Okumura Plasma processing method and apparatus and tray for plasma processing
JP2006165136A (en) 2004-12-06 2006-06-22 Konica Minolta Holdings Inc Etching method
JP2012043928A (en) 2010-08-18 2012-03-01 Samco Inc Plasma processing method and plasma processing apparatus
JP2013008746A (en) 2011-06-22 2013-01-10 Ulvac Japan Ltd Substrate holding apparatus
US20190019716A1 (en) * 2017-07-13 2019-01-17 Tokyo Electron Limited Heat transfer sheet and substrate processing apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030215578A1 (en) * 2002-04-09 2003-11-20 Tomohiro Okumura Plasma processing method and apparatus and tray for plasma processing
JP2006165136A (en) 2004-12-06 2006-06-22 Konica Minolta Holdings Inc Etching method
JP2012043928A (en) 2010-08-18 2012-03-01 Samco Inc Plasma processing method and plasma processing apparatus
JP2013008746A (en) 2011-06-22 2013-01-10 Ulvac Japan Ltd Substrate holding apparatus
US20190019716A1 (en) * 2017-07-13 2019-01-17 Tokyo Electron Limited Heat transfer sheet and substrate processing apparatus

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JP2021091102A (en) 2021-06-17

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