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WO2023181869A1 - Cadre de pellicule, pellicule, plaque originale pour exposition, dispositif d'exposition et procédé de production de pellicule - Google Patents

Cadre de pellicule, pellicule, plaque originale pour exposition, dispositif d'exposition et procédé de production de pellicule Download PDF

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Publication number
WO2023181869A1
WO2023181869A1 PCT/JP2023/008184 JP2023008184W WO2023181869A1 WO 2023181869 A1 WO2023181869 A1 WO 2023181869A1 JP 2023008184 W JP2023008184 W JP 2023008184W WO 2023181869 A1 WO2023181869 A1 WO 2023181869A1
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WO
WIPO (PCT)
Prior art keywords
pellicle
frame member
adhesive layer
layer
modulus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/008184
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English (en)
Japanese (ja)
Inventor
彰 石川
真史 藤村
敦 大久保
一夫 高村
博文 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to CN202380027548.2A priority Critical patent/CN118974649A/zh
Priority to JP2024509928A priority patent/JPWO2023181869A1/ja
Priority to KR1020247030047A priority patent/KR20240141326A/ko
Publication of WO2023181869A1 publication Critical patent/WO2023181869A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • G03F1/64—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof characterised by the frames, e.g. structure or material, including bonding means therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/70983—Optical system protection, e.g. pellicles or removable covers for protection of mask

Definitions

  • the present disclosure relates to a pellicle frame, a pellicle, an exposure master, an exposure apparatus, and a method for manufacturing a pellicle.
  • a pellicle which is an original cover, is attached to the original in order to prevent foreign matter such as dust from adhering to the surface of the original.
  • the pellicle includes a support frame, a pellicle membrane supported on one end surface of the support frame, and an adhesive layer provided on the other end surface of the support frame (hereinafter referred to as "original side end surface") (for example, Patent Document 1).
  • original side end surface for example, Patent Document 1
  • the support frame and the adhesive layer provided on the other end surface of the support frame may be collectively referred to as a "pellicle frame.”
  • Patent Document 1 Japanese Patent Application Publication No. 2014-081454
  • a force directed toward the inside of the pellicle frame may act due to the tension of the pellicle membrane. If the support frame is soft, the tension of the pellicle membrane may cause the support frame to be distorted inward. When the support frame is warped inward, the usable exposure area is reduced accordingly. Therefore, there is a need for a pellicle frame that can suppress the amount of inward distortion of the support frame as small as possible.
  • the support frame is hard, when the pellicle is attached to the original using the adhesive layer, the original may be distorted due to deformation of the support frame. This may cause a positional shift of the circuit pattern on the original. Specifically, the support frame may be distorted in the thickness direction perpendicular to the surface direction of the pellicle membrane when it is a single support frame. When attaching the pellicle to the original, the support frame is pressed against the flat part of the original. As a result, the support frame is affixed to the original in a flat and corrected state.
  • the support frame When the support frame is corrected to be flat, the support frame has a restoring force that tends to return to the original distorted shape.
  • the stiffer the support frame that is, the higher the bending rigidity of the support frame
  • the greater the restoring force If the restoring force is large, the original plate may be distorted due to deformation of the support frame. Therefore, a pellicle frame with reduced bending rigidity is required.
  • the present disclosure has been made in view of the above circumstances.
  • the problem to be solved by an embodiment of the present disclosure is a pellicle frame, a pellicle, and a method for manufacturing a pellicle that can suppress distortion caused by tension in a pellicle membrane and distortion of an original caused by deformation of the pellicle frame.
  • the goal is to provide the following.
  • Means for solving the above problems include the following embodiments.
  • the flexible frame member has a base material layer and an adhesive layer alternately laminated in a thickness direction perpendicular to a surface direction of the pellicle membrane such that the adhesive layer is disposed at both ends,
  • the Young's modulus of the hard frame member is higher than the apparent Young's modulus of the soft frame member
  • ⁇ 3> The pellicle frame according to ⁇ 1> or ⁇ 2>, wherein the rigid frame member has a Young's modulus of 90 Gpa or more.
  • ⁇ 4> The pellicle frame according to any one of ⁇ 1> to ⁇ 3>, wherein the ratio of the height of the rigid frame member to the height of the pellicle frame is 15% to 65%.
  • ⁇ 5> The pellicle frame according to any one of ⁇ 1> to ⁇ 4>, wherein the total number of layers of the base layer and the number of adhesive layers is 5 or more.
  • ⁇ 6> The pellicle frame according to any one of ⁇ 1> to ⁇ 5>, wherein the thickness of each adhesive layer is 0.01 mm or more and 0.5 mm or less.
  • ⁇ 7> The above ⁇ 1, wherein the total thickness of the adhesive layer included in the flexible frame member is 0.2 times or more and 4 times or less the total thickness of the base material layer included in the flexible frame member.
  • ⁇ 8> The pellicle frame according to any one of ⁇ 1> to ⁇ 7>, wherein the Young's modulus of the base layer is 10,000 to 9,000,000 times the Young's modulus of the adhesive layer. . ⁇ 9>
  • [CNO - 2s ] is a time-of-flight secondary ion mass spectrometry analysis of the first deep part at the first depth from the surface of the adhesive layer, where the ion source is Bi 3 ++ ions and the irradiation area is It shows the normalized intensity of CNO - analyzed using a primary ion gun of 100 ⁇ m x 100 ⁇ m, The first depth is formed by irradiating a 600 ⁇ m square area of the surface with a sputter ion gun, which is an argon gas cluster ion beam with a beam voltage of 20 kV and a beam current of 20 nA, for a total of 2 seconds, [CNO - 50s ] indicates the normalized intensity of CNO - in which the second deep part at
  • ⁇ 12> The pellicle frame according to any one of ⁇ 1> to ⁇ 11> above, and a pellicle membrane supported by the rigid frame member.
  • An original plate having a pattern An exposure master plate, comprising: the pellicle according to ⁇ 12> above, which is attached to the surface of the master plate having a pattern.
  • a light source that emits exposure light The exposure original plate according to ⁇ 13> above, an optical system that guides the exposure light emitted from the light source to the exposure master;
  • the exposure device is such that the exposure master is arranged so that exposure light emitted from the light source passes through the pellicle film and is irradiated onto the master.
  • a method for manufacturing a pellicle according to ⁇ 12> comprising: a step of preparing the rigid frame member; a laminating step of alternately laminating at least one base layer sheet and a plurality of adhesive layer layers in the thickness direction to form a laminate; a punching step of punching through the laminate so that exposure through holes are formed along the thickness direction to form the soft frame member;
  • a method for manufacturing a pellicle comprising: connecting the hard frame member to the soft frame member.
  • ⁇ 16> Coating an inorganic layer on at least the inner wall surface of the adhesive layer, subjecting at least the inner wall surface of the adhesive layer to plasma nitriding treatment, and subjecting at least the inner wall surface of the adhesive layer to extreme ultraviolet irradiation treatment.
  • the soft frame member includes a ventilation passage passing through the soft frame member,
  • the adhesive layer layer is an adhesive layer sheet, Processing at least one raw sheet for base material layer and a plurality of unprocessed sheets for adhesive layer so that the ventilation passage is formed, and processing the at least one raw sheet for base material layer and the plurality of raw sheets for adhesive layer.
  • the flexible frame member includes the ventilation path and a ventilation filter disposed in the ventilation path, a filter fixing step of arranging the ventilation filter on a part of the at least one base layer sheet or the plurality of adhesive layer sheets so that the ventilation filter is disposed in the ventilation path;
  • a pellicle frame a pellicle, an exposure master, an exposure apparatus, and a method for manufacturing a pellicle, which can suppress distortion caused by tension in a pellicle film and suppress distortion of an original caused by deformation of the pellicle frame. It is to be.
  • FIG. 1 is a cross-sectional view of a laminate having a three-layer structure for explaining a method for calculating the apparent Young's modulus (E) of a laminate stacked horizontally.
  • FIG. 2 is a cross-sectional view of a laminate having a three-layer structure for explaining a method for calculating the apparent Young's modulus (E) of a laminate that is horizontally laminated.
  • FIG. 3 is a cross-sectional view of a calculation model having the same laminated structure as the pellicle frame according to the first embodiment of the present disclosure.
  • FIG. 4 is a cross-sectional view of a pellicle according to a second embodiment of the present disclosure.
  • FIG. 5 is a cross-sectional view of a pellicle according to a third embodiment of the present disclosure.
  • FIG. 6 is a cross-sectional view of a pellicle according to a fourth embodiment of the present disclosure.
  • FIG. 7 is a cross-sectional view of a pellicle according to a fifth embodiment of the present disclosure.
  • FIG. 8 is a cross-sectional view of a pellicle according to Reference Example 1.
  • a numerical range indicated using “ ⁇ ” means a range that includes the numerical values listed before and after " ⁇ " as the minimum and maximum values, respectively.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the amount of each component means the total amount of the multiple types of substances, unless otherwise specified.
  • the term "step” is used not only to refer to an independent step, but also to include a step in this term if the intended purpose of the step is achieved, even if the step cannot be clearly distinguished from other steps. It will be done.
  • the pellicle frame of the present disclosure includes a hard frame member for supporting a pellicle membrane and a soft frame member for being attached to an original having a pattern.
  • a soft frame member is connected to the hard frame member.
  • the flexible frame member is made up of a base material layer and an adhesive layer that are alternately laminated in a thickness direction perpendicular to a surface direction of the pellicle film such that the adhesive layer is disposed at both ends.
  • the Young's modulus of the hard frame member is higher than the apparent Young's modulus of the soft frame member.
  • the Young's modulus of the rigid frame member is 25 GPa or more.
  • “orthogonal” is not limited to the case where they intersect at 90 degrees, but includes the case where they intersect in the angular range of 90 ⁇ 5 degrees.
  • Young's modulus of the rigid frame member refers to the Young's modulus of the material of the rigid frame member having a single layer structure or the Young's modulus of the material of the rigid frame member having a multilayer structure. When the rigid frame member has a multilayer structure, this is the Young's modulus when the multiple materials of the rigid frame member with the multilayer structure are regarded as one material, and the calculation of the apparent Young's modulus (E) of the horizontally laminated laminate. Indicates the value calculated based on the method.
  • the "apparent Young's modulus of the soft frame member” refers to the Young's modulus when a plurality of materials of the flexible frame member having a multilayer structure are considered as one material, and the apparent Young's modulus of the horizontally laminated laminate. The value calculated based on the calculation method of rate (E) is shown. Details of the method for calculating the apparent Young's modulus will be described later.
  • the pellicle frame of the present disclosure has the above configuration, distortion caused by the tension of the pellicle membrane can be suppressed, and distortion of the original plate caused by deformation of the pellicle frame can be suppressed. This is presumed to be mainly due to the following reasons.
  • a force directed toward the inside of the pellicle frame may act due to the tension of the pellicle membrane.
  • the pellicle membrane is supported by the hard frame member that is harder than the soft frame member.
  • the Young's modulus of the rigid frame member is 25 GPa or more.
  • the pellicle frame of the present disclosure is less likely to be distorted inside the pellicle frame due to the tension of the pellicle membrane.
  • the pellicle frame of the present disclosure distortion caused by tension in the pellicle membrane is suppressed. Therefore, it is presumed that the pellicle frame of the present disclosure can prevent the exposure area from decreasing.
  • the pellicle frame When the pellicle frame is corrected to be flat, the pellicle frame has a restoring force that tends to return to its original distorted shape.
  • the soft frame member which is softer than the hard frame member, is directly attached to the flat surface of the original. Therefore, the restoring force is more relaxed than when the soft frame member has the same hardness as the hard frame member.
  • the pellicle frame of the present disclosure can reduce the restoring force caused by attachment to the original. Therefore, the pellicle frame of the present disclosure can suppress distortion of the original due to deformation of the pellicle frame attached to the original.
  • the pellicle frame is a rectangular cylindrical object.
  • the pellicle frame has an exposure through hole.
  • the exposure through hole is a hollow part of the pellicle frame, and indicates a space through which light transmitted through the pellicle film passes to reach the original plate.
  • the shape of the pellicle frame viewed from the thickness direction is rectangular.
  • the rectangular shape may be a square or a rectangle.
  • “Rectangle” refers to a right-angled quadrilateral.
  • a "square” refers to a rectangular shape in which all four sides are equal in length.
  • a rectangle refers to a rectangle excluding a square.
  • the rectangular shape of the pellicle frame viewed from the thickness direction is composed of four sides.
  • the length of one side in the longitudinal direction (hereinafter referred to as "length of one side”) is preferably 200 mm or less.
  • the size of the pellicle frame and the like are standardized depending on the type of exposure device.
  • the length of one side of the pellicle frame is 200 mm or less, which means that it is suitable for exposure using extreme ultraviolet (EUV) light (wavelength: 3 nm to 30 nm) (hereinafter referred to as "EUV exposure”).
  • EUV exposure extreme ultraviolet
  • the length of one side in the short direction (hereinafter referred to as "width of one side") can be, for example, 5 mm to 180 mm, preferably 80 mm to 170 mm, and more preferably 100 mm to 160 mm.
  • the height of the pellicle frame (that is, the length of the pellicle frame in the thickness direction) is preferably 2.5 mm or less, more preferably 2.4 mm or less. Thereby, the pellicle frame meets the standardized size for EUV exposure.
  • the height of the pellicle frame standardized for EUV exposure is, for example, 2.375 mm.
  • the mass of the pellicle frame is preferably 15 g or less. This makes the pellicle frame suitable for use in EUV exposure.
  • the pellicle frame of the present disclosure includes a hard frame member and a soft frame member.
  • the hard frame member and the soft frame member are laminated in the thickness direction.
  • the material, shape, etc. of the rigid frame member are not particularly limited as long as they can support the pellicle membrane.
  • the rigid frame member is made of a single material.
  • a part of the support base material is removed by etching to form a support base to which the pellicle film is connected.
  • the rigid frame member to which the pellicle membrane is connected can be prepared with high productivity.
  • the Young's modulus of the rigid frame member is 25 Pa or more. Thereby, the rigid frame member has sufficient hardness. Therefore, even if the pellicle membrane is stretched over the rigid frame member, the pellicle frame is unlikely to be distorted by the tension of the pellicle membrane.
  • the Young's modulus of the rigid frame member is more preferably 50 GPa or more. Since the Young's modulus of the rigid frame member is 50 GPa or more, even if the pellicle membrane is stretched over the rigid frame member, the pellicle frame is less likely to be distorted inward by the tension of the pellicle membrane. It is further preferable that the Young's modulus of the rigid frame member is 90 GPa or more.
  • the Young's modulus of the rigid frame member is 90 GPa or more, even if the pellicle membrane is stretched over the rigid frame member, the pellicle frame is less likely to be distorted inward by the tension of the pellicle membrane.
  • the Young's modulus of the rigid frame member is more preferably 90 GPa to 300 GPa, and still more preferably 150 GPa to 300 GPa.
  • Examples of materials having a Young's modulus of 25 GPa or more include glass, aluminum, titanium, titanium alloy, silicon, stainless steel, polyethylene, acrylic resin, vinyl chloride resin, polystyrene resin, and the like.
  • Examples of materials having a Young's modulus of 50 GPa or more include glass, aluminum, titanium, titanium alloy, silicon, stainless steel, and the like.
  • Examples of materials having a Young's modulus of 90 GPa or more include titanium, titanium alloy, silicon, stainless steel, and the like.
  • Examples of materials having a Young's modulus of 150 GPa or more include silicon, stainless steel, and the like.
  • the Young's modulus of the rigid frame member is measured using a tensile test (JIS G0567J). However, if the material of the rigid frame member is resin, the value is measured by a three-point bending test (JIS K7171). Whether the material of the rigid frame member is resin is determined by whether or not the material of the rigid frame member is thermally decomposed at 550°C.
  • Materials for the rigid frame member include metal materials (e.g., aluminum, titanium, stainless steel, etc.), ceramic materials (e.g., silicone, glass, etc.), and resins (e.g., polyethylene resin, acrylic resin, vinyl chloride resin, polystyrene resin). etc.) etc.
  • the material of the rigid frame member preferably contains aluminum, titanium, stainless steel, silicon, or glass, from the viewpoint of not containing a large amount of water and suppressing the amount of outgas, and preferably contains aluminum, titanium, or silicon. It is more preferable.
  • the surface of the rigid frame member may be subjected to a known surface treatment to make the surface of the rigid frame member hydrophobic, from the viewpoint of reducing the water content and suppressing the amount of outgas generated. It may also be coated with a material with a low content (eg, baseless material, ceramic material, etc.).
  • a material with a low content eg, baseless material, ceramic material, etc.
  • the height of the rigid frame member (that is, the length of the rigid frame member in the thickness direction) is not particularly limited, and is determined from the viewpoint of suppressing distortion of the original plate caused by deformation of the pellicle frame and distortion caused by the tension of the pellicle membrane. , preferably 0.3 mm to 1.5 mm, more preferably 0.5 mm to 1.0 mm.
  • the ratio of the height of the rigid frame member to the height of the pellicle frame (hereinafter referred to as "height ratio of the rigid frame member”) is not particularly limited, and is determined from the viewpoint of suppressing distortion of the original plate due to deformation of the pellicle frame. , preferably 65% or less, more preferably 60% or less, further preferably 50% or less, particularly preferably 45% or less. From the viewpoint of suppressing distortion caused by the tension of the pellicle membrane, the height ratio of the rigid frame member is preferably 15% or more, more preferably 20% or more, and still more preferably 25% or more. From these viewpoints, the height ratio of the rigid frame member is preferably 15% to 65%, more preferably 20% to 65%, even more preferably 25% to 65%, particularly preferably 25% to 50%. and more preferably 28% to 45%.
  • Soft Frame Member The soft frame member is used to attach a pellicle to an original plate having a pattern.
  • the soft frame member is connected to the hard frame member.
  • the original version will be discussed later.
  • Soft in a soft frame member indicates having soft properties in relative comparison with a hard frame member.
  • the soft frame member is made up of a base material layer and an adhesive layer that are alternately laminated in the thickness direction perpendicular to the surface direction of the pellicle membrane such that the adhesive layer is placed at both ends.
  • the material and shape of the soft frame member are not particularly limited as long as they can support the pellicle membrane.
  • the apparent Young's modulus of the soft frame member is less than 25 GPa. Thereby, the soft frame member is sufficiently soft. Therefore, even if the pellicle is attached to the original, the restoring force is further reduced.
  • the apparent Young's modulus of the soft frame member is more preferably 1 GPa to 15 GPa, and still more preferably 3 GPa to 10 GPa.
  • the apparent Young's modulus of the pellicle frame is calculated based on the method of calculating the apparent Young's modulus (E) of a horizontally laminated laminate. Specifically, first, a calculation model having the same laminated structure as the pellicle frame is introduced. Then, the apparent Young's modulus of the calculation model is calculated based on the method for calculating the apparent Young's modulus (E) of a horizontally laminated laminate. The calculated apparent Young's modulus of the calculation model is regarded as the apparent Young's modulus of the pellicle frame of the present disclosure.
  • the apparent Young's modulus of the soft frame member of the calculated calculation model is regarded as the apparent Young's modulus of the soft frame member in the present disclosure.
  • a method for calculating the apparent Young's modulus (E) of a horizontally laminated laminate and a method for calculating the apparent Young's modulus of a calculation model will be described in this order.
  • FIGS. 1 and 2 are cross-sectional views of a laminate having a three-layer structure for explaining a method for calculating the apparent Young's modulus (E) of a laminate that is horizontally laminated. Specifically, FIG. 2 shows the strain distribution of the laminate shown in FIG.
  • the flexural rigidity (EI) of the laminate can be calculated by summing the flexural rigidity (E i I i ) of each board. In order to obtain the moment of inertia (I i ) of each laminated and bonded laminated board, the neutral axis position ( ⁇ ) of the laminate is determined. From the basic assumption of beam bending in FIGS. 1 and 2, equation (i) holds within the elastic limit.
  • ⁇ is the radius of curvature due to the bending moment (see Figure 2)
  • ⁇ is the distance from the upper edge of the laminate to the neutral axis (see Figure 1)
  • y is the upper edge of the laminate (see FIG. 1)
  • ⁇ y is the normal strain in y
  • ⁇ y is the normal stress in y
  • E is the apparent Young's modulus of the laminate.
  • E x is the Young's modulus of each layer (the Xth layer counted from one end surface of the laminate), and "h x " is the Young's modulus of each layer (the The length between the X-th layer and the other end surface of the laminate (see FIG. 1), and "b” indicates the width of the laminate (see FIG. 1).
  • X represents an integer from 1 to 3.
  • the bending stiffness (EI) of the laminate is expressed by the following formula (v) by taking the sum of the bending stiffness of each board, E i I i , regarding the determined neutral axis position.
  • Equation (e) The apparent Young's modulus (E) of the laminate is calculated by dividing equation (v) by the moment of inertia of area (bh 3 /12), and is expressed by equation (vi) below.
  • the bending rigidity of the soft frame member can be calculated from equation (v).
  • the apparent Young's modulus of the soft frame member can be calculated from equation (vi).
  • the bending rigidity of the pellicle frame can be calculated from equation (v).
  • the apparent Young's modulus of the pellicle frame can be calculated from equation (vi).
  • FIG. 3 is a cross-sectional view of a calculation model having the same laminated structure as the pellicle frame according to the first embodiment of the present disclosure.
  • the pellicle frame according to the first embodiment is a rectangular cylindrical object.
  • the pellicle frame according to the first embodiment is an assembled product, and includes a soft frame member 11X and a hard frame member 12A.
  • the soft frame member 11X and the hard frame member 12A are stacked in the thickness direction of the pellicle frame according to the first embodiment.
  • the Young's modulus of the hard frame member 12A is higher than the apparent Young's modulus of the soft frame member 11X.
  • the Young's modulus of the rigid frame member 12A is 25 GPa or more.
  • the soft frame member 11X has (m+1) adhesive layers 111 and m base material layers 112 alternately laminated in the thickness direction of the pellicle frame according to the first embodiment such that the adhesive layers 111 are arranged at both ends. It will be done.
  • m represents a natural number.
  • the total number of layers of the base material layer 112 and the number of layers of the adhesive layer 111 is (2m+1).
  • the number of layers constituting the rigid frame member 12A is one. In other words, the number of layers constituting the pellicle according to the first embodiment is (2m+2).
  • the calculation model 10X is a horizontally laminated model similar to the horizontally laminated laminate shown in FIG.
  • the laminated structure of the calculation model 10X is the same as the laminated structure of the pellicle frame according to the first embodiment.
  • the symbol “h 1 " is the thickness of the first layer counted from the surface S13 on the opposite side to the contact surface S12 with which the soft frame member 11X of the hard frame member 12A contacts in the thickness direction of the calculation model 10X. (that is, the thickness of one adhesive layer 111).
  • the code “t 1 ” indicates the length of the code “h 1 ”.
  • the code “h 2 ” indicates the thickness of the second layer counting from the surface S13 opposite to the contact surface S12 (that is, the total thickness of one adhesive layer 111 and one base material layer 112). It is the length shown.
  • the code “t 2 ” indicates the length obtained by subtracting h 1 from h 2 .
  • the code “h 2m ” is the thickness of the layer up to the (2m)th layer counting from the surface S13 on the opposite side to the contact surface S12 (i.e., the sum of the thickness of m adhesive layers 111 and the thickness of m base material layers 112) ).
  • the code “h 2m+1 ” is a length indicating the thickness of the layer up to the (2m+1)th layer counting from the surface S13 on the opposite side to the contact surface S12 (that is, the thickness of the soft frame member 11X).
  • the code “t 2m+1 " indicates the length obtained by subtracting h 2m from h 2m+1 .
  • the number n of layers of the pellicle frame (that is, the calculation model 10X) according to the first embodiment is the sum of the number of layers of the hard frame member 12A and the number of layers of the soft frame member 11X. n represents a natural number.
  • the number of layers of the hard frame member 12A is p
  • p represents a natural number.
  • the rigid frame member 12A may be formed of two or more layers.
  • the neutral axis position ( ⁇ ) is calculated using equation (iv).
  • "n" in formula (iv) corresponds to the number of layers of the calculation model 10X.
  • “h 1 to h n ” correspond to h 1 to h 2m+1+p of the calculation model 10X when the number of layers of the rigid frame member 12A is p.
  • “t 1 to t n ” corresponds to t 1 to t 2m+1+p of the calculation model 10X.
  • “h 1 to h n ” correspond to h 1 to h 2m+2 of the calculation model 10X when the number of layers of the rigid frame member 12A is one.
  • t 1 to t n corresponds to t 1 to t 2m+2 of the calculation model 10X.
  • the number of layers of the rigid frame member 12A is one will be described.
  • “Ei when i is an odd number” corresponds to the Young's modulus of the adhesive layer 111 of the calculation model 10X.
  • “Ei when i is an even number” basically corresponds to the Young's modulus of the base layer 112 of the calculation model 10X.
  • "Ei when i is 2m+2" corresponds to the Young's modulus of the rigid frame member 12A of the calculation model 10X.
  • Equation (vi) the apparent Young's modulus (E) of the calculation model 10X is calculated using equation (vi).
  • "h” in formula (vi) corresponds to h 2m+2 (that is, the sum of the thickness of the soft frame member 11X and the hard frame member 12A) of the calculation model 10X.
  • "n” corresponds to (2m+2) of the calculation model 10X.
  • E i when i is an odd number corresponds to the Young's modulus of the adhesive layer 111 of the calculation model 10X.
  • “E i when i is an even number” basically corresponds to the Young's modulus of the base layer 112 of the calculation model 10X.
  • E i when i is 2m+2 corresponds to the Young's modulus of the rigid frame member 12A of the calculation model 10X.
  • h 1 to h n correspond to h 1 to h 2m+2 of the calculation model 10X.
  • ⁇ corresponds to the neutral axis position ( ⁇ ) of the calculation model 10X calculated using equation (iv).
  • the calculated apparent Young's modulus (E) of the calculation model 10X is regarded as the apparent Young's modulus of the pellicle frame.
  • the bending stiffness (EI) of the calculation model 10X is calculated using equation (v).
  • "b" in formula (v) corresponds to the width of the calculation model 10X.
  • the width of the calculation model 10X indicates the width of one side of the pellicle frame according to the first embodiment.
  • the width of one side (short side) of the soft frame member 11X is the same as the width of one side (short side) of the hard frame member 12A.
  • "n” corresponds to (2m+2) of the calculation model 10X.
  • E i when i is an odd number corresponds to the Young's modulus of the adhesive layer 111 of the calculation model 10X.
  • E i when i is an even number basically corresponds to the Young's modulus of the base layer 112 of the calculation model 10X. However, "E i when i is 2m+2" corresponds to the Young's modulus of the rigid frame member 12A of the calculation model 10X. “h 1 to h n ” correspond to h 1 to h 2m+2 of the calculation model 10X. “ ⁇ ” corresponds to the neutral axis position ( ⁇ ) of the calculation model 10X calculated using equation (iv).
  • the calculated bending stiffness (EI) of the calculation model 10X is regarded as the bending stiffness of the pellicle frame.
  • the apparent Young's modulus of the soft frame member 11X and the bending rigidity of the soft frame member 11X are determined by not considering the hard frame member in the above-described method of calculating the Young's modulus of the pellicle frame and the method of calculating the bending rigidity of the pellicle frame (i.e., The calculation can be performed in the same manner except that the calculation model 10Y is used instead of the calculation model 10X.
  • the calculation model 10Y has the same configuration as the calculation model 10X except that it does not include the rigid frame member 12A.
  • the Young's modulus of the rigid frame member 12A and the bending rigidity of the rigid frame member 12A are calculated using the soft frame member 11X of the calculation model 10X using the method of calculating the Young's modulus of the pellicle frame and the method of calculating the bending rigidity of the pellicle frame described above. It can be calculated using the same method except that it is not taken into consideration.
  • the flexible frame member preferably includes a ventilation path, or a ventilation path and a ventilation filter.
  • the ventilation passage passes through the flexible frame member.
  • the ventilation passage passes through the flexible frame member.
  • a ventilation filter is placed in the ventilation path.
  • the ventilation passage communicates the interior space of the pellicle with the exterior space of the pellicle.
  • the "internal space of the pellicle” refers to the space surrounded by the pellicle and the original plate.
  • Space outside the pellicle refers to a space that is not surrounded by the pellicle and the original.
  • a pressure difference may occur between the interior space of the pellicle and the exterior space of the pellicle.
  • the pellicle membrane may sag or swell.
  • the soft frame member includes the ventilation passage, it is possible to suppress the generation of a pressure difference between the internal space of the pellicle and the external space of the pellicle.
  • the soft frame member includes a ventilation path and a ventilation filter, thereby suppressing the generation of a pressure difference between the internal space of the pellicle and the external space of the pellicle, and preventing foreign matter from entering the internal space of the pellicle from the external space of the pellicle. Contamination can be suppressed.
  • EUV exposure is performed under a vacuum atmosphere. If the area of the ventilation filter is sufficiently large, the time required to evacuate the internal space of the pellicle during EUV exposure will be shortened.
  • the number of ventilation passages is not particularly limited. At least one ventilation path may be formed on each of the four sides of the pellicle frame.
  • a ventilation filter is a filter that allows gas to pass through but does not allow foreign matter such as dust to pass through. There are no restrictions on the ventilation filter as long as it can prevent foreign matter from entering the pellicle's internal space from the external space of the pellicle, such as HEPA ventilation filter (High Efficiency Particulate Air Filter), ULPA ventilation filter (Ultra Low Penetration Air Filter), etc. Examples include membrane ventilation filters, nonwoven fabric ventilation filters, ceramic ventilation filters, glass ventilation filters, metal sintered ventilation filters, ceramic ventilation filters, glass ventilation filters, metal sintered ventilation filters, hollow paper ventilation filters, and the like.
  • the ventilation filter preferably has an initial pressure loss of 100 Pa to 550 Pa, and a particle repair rate of 99.7% to 100% for particles having a particle size of 0.15 ⁇ m to 0.3 ⁇ m.
  • the method of fixing the ventilation filter is not particularly limited, and it is preferable that the ventilation filter is fixed to the soft frame member so as to cover the ventilation passage, and examples thereof include a first fixing method to a fourth fixing method.
  • the first fixing method is a method of fixing the ventilation filter by dividing one adhesive layer into two in the thickness direction of the pellicle frame and sandwiching the ventilation filter between the divided adjoining adhesive layers.
  • the second fixing method is a method of fixing the ventilation filter by bringing the ventilation filter into contact with at least one adhesive layer exposed within the ventilation path.
  • the third fixing method is a method of fixing the ventilation filter by bringing the ventilation filter into contact with the same surface of one adhesive layer exposed in the ventilation path.
  • a fourth fixing method is a method of fixing the ventilation filter by welding the ventilation filter onto the same surface of one base material layer exposed within the ventilation path.
  • the third fixing method and the fourth fixing method are preferable in order to suppress the risk that a portion not covered by the ventilation filter will occur in the ventilation passage (that is, a gap will be formed) due to the unevenness of the ventilation filter.
  • the fourth fixing method is more preferred in order to further reduce the generation of outgas.
  • the height of the soft frame member (that is, the length of the soft frame member in the thickness direction) is not particularly limited.
  • the height of the soft frame member is preferably 0.9 mm to 2.0 mm, more preferably 1.4 mm, from the viewpoint of suppressing distortion caused by the tension of the pellicle membrane and distortion of the original plate caused by deformation of the pellicle frame. ⁇ 1.9mm.
  • the ratio of the height of the soft frame member to the height of the pellicle frame (hereinafter referred to as "height ratio of the soft frame member”) is not particularly limited.
  • the height ratio of the soft frame member is preferably 40% to 90%, more preferably 60% to 80%, from the viewpoint of suppressing distortion caused by the tension of the pellicle membrane and suppressing distortion of the original plate caused by deformation of the pellicle frame. %.
  • the total number of base material layers and the number of adhesive layers included in the flexible frame member (hereinafter referred to as the "total number of layers") is:
  • the number of layers is not particularly limited as long as it is three or more layers, and is appropriately selected depending on the thickness of the base layer, the thickness of the adhesive layer, the size required for the pellicle frame, etc. If there is variation in the flatness of each of the base material layer and the adhesive layer, the variation in the flatness of each of the base material layer and the adhesive layer is canceled out by laminating these base material layers and the adhesive layer. This improves the flatness of the soft frame member. By not making the adhesive layer too thick, variations in the flatness of the adhesive layer are reduced.
  • the total number of layers is preferably 5 or more, more preferably 10 or more.
  • the total number of layers is not particularly limited and can be 40 or less. From the viewpoint of simplifying the manufacturing process, the total number of layers is more preferably 30 layers or less, and still more preferably 20 layers or less. From these viewpoints, the number of layers is preferably 3 or more and 40 or less, more preferably 5 or more and 30 or less, and even more preferably 10 or more and 20 or less. From the viewpoint of providing ventilation passages in the region of the soft member, seven or more layers are more preferable, and nine or more layers are even more preferable. From these viewpoints, 7 to 40 layers are preferred, 7 to 30 layers are more preferred, and 9 to 20 layers are even more preferred.
  • the total thickness of the adhesive layer included in the flexible frame member is preferably 0.2 times or more and 4 times or less the total thickness of the base material layer included in the flexible frame member. This further reduces the restoring force caused by pasting onto the original. In other words, distortion of the original due to deformation of the pellicle frame can be further suppressed.
  • the ratio of the total thickness of the adhesive layers included in the flexible frame member to the total thickness of the base material layers included in the flexible frame member will be referred to as "total thickness ratio of adhesive layers.”
  • the total thickness ratio of the adhesive layer is preferably 4 times or less, more preferably 3 times or less, with respect to the total thickness of the base material layer included in the flexible frame member. It is not more than twice, more preferably not more than twice.
  • the total thickness ratio of the adhesive layer is preferably 0.2 times or more of the total thickness of the base layer included in the soft frame member.
  • the total thickness ratio of the adhesive layer is preferably 0.2 to 3 times, more preferably 0.6 to 3 times, the total thickness of the base layer included in the flexible frame member. times, more preferably 0.8 times to 2 times.
  • Adhesive layer has the following functions (a) to (c). (a) The adhesive layer placed between two adjacent base material layers in the thickness direction connects the base material layers. (b) The adhesive layer of one of the adhesive layers placed at both ends in the thickness direction (c) The other adhesive layer of the adhesive layers arranged at both ends in the thickness direction connects the pellicle frame and the original plate.
  • each adhesive layer (hereinafter referred to as "single layer thickness of adhesive layer”) is preferably 0.01 mm or more and 0.5 mm or less. .
  • single layer thickness of adhesive layer is preferably 0.01 mm or more and 0.5 mm or less.
  • the single layer thickness of the adhesive layer is preferably 0.5 mm or less, more preferably 0.25 mm or less, and even more preferably 0. .2 mm or less is more preferable.
  • the single layer thickness of the adhesive layer is preferably 0.01 mm or more, more preferably 0.03 mm or more, More preferably, it is 0.05 mm or more.
  • the Young's modulus of the adhesive layer is preferably 0.01 MPa to 1.0 MPa. Thereby, the rigidity of the adhesive layer is further reduced, and distortion of the original plate due to deformation of the pellicle frame can be further suppressed.
  • the Young's modulus of the adhesive layer is more preferably 0.8 MPa or less, and even more preferably 0.6 MPa or less, from the viewpoint of further reducing the rigidity of the adhesive layer and further suppressing the restoring force caused by pasting to the original plate. .
  • the Young's modulus of the adhesive layer is not particularly limited, but is more preferably 0.02 MPa or more, still more preferably 0.04 MPa or more.
  • Examples of materials having a Young's modulus of 1.0 MPa or less include acrylic resin, silicone resin, styrene-butadiene resin, and the like.
  • Examples of materials having a Young's modulus of 0.8 MPa or less include acrylic resin, silicone resin, and styrene-butadiene resin.
  • Examples of materials having a Young's modulus of 0.6 MPa or less include acrylic resin, silicone resin, styrene-butadiene resin, and the like.
  • the method for measuring the Young's modulus of the adhesive layer is a three-point bending test (JIS K7171).
  • the material of the adhesive layer is not particularly limited, and examples thereof include acrylic resin, silicone resin, styrene-butadiene resin, urethane resin, olefin resin, epoxy resin, polyimide resin, hydrogenated styrene resin, and the like.
  • the material of the adhesive layer preferably contains acrylic resin or silicone resin from the viewpoint of lowering the rigidity of the flexible frame member, and preferably contains acrylic resin from the viewpoint of further suppressing the amount of outgas generated. .
  • [CNO - 2s ] is a first deep part having a first depth from the surface of the adhesive layer using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS).
  • TOF-SIMS Time-of-Flight Secondary Ion Mass Spectrometry
  • a sputter ion gun which is an argon gas cluster ion beam (Ar-GCIB) with a beam voltage of 20 kV and a beam current of 20 nA, is applied to a 600 ⁇ m square area of the surface. Formed by irradiation for 2 seconds.
  • Ar-GCIB argon gas cluster ion beam
  • the sputter ion gun which is an argon gas cluster ion beam with a beam voltage of 20 kV and a beam current of 20 nA, will be simply referred to as a "sputter ion gun (Ar-GCIB).
  • [CNO - 50s ] indicates the normalized intensity of CNO - obtained by analyzing the second deep part at the second depth by TOF-SIMS, The second depth is formed by irradiating the area with the sputter ion gun for a total of 50 seconds.
  • the normalized intensity is the ratio of the peak intensity of the corresponding component to the total intensity value of peaks whose intensity peak positions are between 45 (m/z) and 2000 (m/z) detected by TOF-SIMS.
  • Formula (2) ([C 3 ⁇ 2s ]/[C 3 ⁇ 50s ]) ⁇ 1.10
  • [C 3 - 2s ] indicates the normalized intensity of C 3 - analyzed by TOF-SIMS of the first deep part
  • [C 3 - 50s ] indicates the normalized intensity of C 3 - obtained by analyzing the second deep part by TOF-SIMS.
  • the "surface of the adhesive layer” includes the inner wall surface of the adhesive layer and the outer wall surface of the adhesive layer.
  • TOF-SIMS irradiates a solid sample with a primary ion gun (primary ions) and uses the difference in flight time to mass separate the ions (secondary ions) released from the surface of the solid sample by a collision cascade. It is a method.
  • a sputtering gun Ar-GCIB
  • TOF-SIMS has high mass resolution and can, for example, separate and analyze C 3 H 3 O + and C 4 H 7 + .
  • outgas is less likely to be generated from the pellicle of the present disclosure, which will be described later.
  • the outgas includes gas derived from water and gas derived from components contained in the adhesive layer.
  • the outgas includes volatile hydrocarbons (molecular weight: 45 to 100) and nonvolatile hydrocarbons (molecular weight: 101 to 200). This is presumed to be mainly due to the following reasons. Outgas occurs, for example, when the adhesive layer is damaged when the adhesive layer is directly exposed to EUV light. In EUV exposure, EUV light may be scattered on the surface of the original.
  • condition (A) the scattered EUV light directly hits the inorganic layer and does not directly hit the inner wall surface of the adhesive layer.
  • the pellicle of the present disclosure can suppress the generation of outgas more than when the inorganic layer is not formed on the inner wall surface of the adhesive layer.
  • satisfying formula (1) indicates that the surface layer of the adhesive layer has been surface-modified with a compound derived from a nitrogen functional group.
  • a compound derived from a nitrogen functional group contributes to immobilization of hydrocarbons (increases the boiling point) or becomes a gas barrier film that inhibits gas permeation from inside the adhesive layer. Therefore, it is presumed that the generation of outgas can be suppressed.
  • the present inventors analyzed the surface of the surface-treated adhesive layer in the depth direction using TOF-SIMS. As a result, the present inventors found that the normalized intensity of secondary ions changes significantly up to a depth of approximately 80 nm from the surface of the adhesive layer, and that at a depth deeper than approximately 80 nm from the surface of the adhesive layer, secondary ions It was experimentally confirmed that the normalized strength of The depth of about 80 nm from the surface of the adhesive layer is formed by, for example, irradiating the surface of the adhesive layer with a sputtering gun (Ar-GCIB) for a total of 10 seconds.
  • Ar-GCIB sputtering gun
  • the surface of the adhesive layer is irradiated with a sputtering gun (Ar-GCIB) for a total of 2 seconds, the surface of the adhesive layer is etched, and the depth of the first deep portion becomes approximately 16 nm from the surface of the adhesive layer.
  • a sputtering gun Ar-GCIB
  • the surface of the adhesive layer is etched, and the depth of the first deep portion becomes approximately 16 nm from the surface of the adhesive layer.
  • satisfying formula (2) indicates that the surface layer of the inner wall surface of the adhesive layer is carbonized.
  • the surface layer of the inner wall surface of the carbonized adhesive layer becomes a gas barrier film that inhibits gas permeation from inside the adhesive layer. Therefore, it is presumed that the generation of outgas can be suppressed.
  • the inorganic layer may be formed on the inner wall surface of the adhesive layer, and may be formed on the inner wall surface and the outer wall surface of the adhesive layer.
  • the material of the inorganic layer is not limited as long as it can suppress outgassing, and for example, any material (metal, ceramic, etc.) with low transmittance of EUV light may be used.
  • Metals that can be used as the inorganic layer include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconia, niobium, molybdenum, ruthenium, and rhodium. , palladium, silver, hafnium, tantalum, tungsten, platinum, and gold.
  • the inorganic layer may be an alloy using two or more elements selected from these, or may be an oxide.
  • Condition (B) The inner wall surface of the adhesive layer may satisfy the formula (1), and the inner wall surface and the outer wall surface of the adhesive layer may satisfy the formula (1).
  • the CNO - normalized strength of the adhesive layer analyzed by TOF-SIMS depends on the material of the adhesive layer, whether plasma nitriding treatment has been performed, etc. It is assumed that CNO - is mainly derived from amide bonds or urethane bonds contained in the adhesive layer and nitrogen functional groups introduced into the adhesive layer by plasma nitriding treatment.
  • ([CNO - 2s ]/[CNO - 50s ]) in formula (1) can be set to, for example, 500 or less, preferably 300 or less, more preferably is 100 or less, more preferably 10 or less.
  • ([CNO - 2s ]/[CNO - 50s ]) in formula (1) is, for example, from the viewpoint of modifying the surface layer of the adhesive layer to a compound derived from a nitrogen functional group to further suppress the generation of outgas. It can be 2.00 or more, preferably 3.00 or more, more preferably 10.0 or more, even more preferably 100 or more.
  • the content ratio of [CNO - 2s ] is determined by the total amount detected by TOF-SIMS measurement at the first depth. It is preferably at least 0.001%, more preferably at least 0.010%, even more preferably at least 0.100%, particularly preferably at least 1.000%, based on the fragment. From the viewpoint of suppressing the cost increase of plasma nitriding treatment, the content ratio of [CNO - 2s ] is preferably 5.000% or less, more preferably 1.000% or less, and even more preferably 0.1%. 00% or less, particularly preferably 0.010% or less.
  • the normalized strength of [CNO - 2s ] is preferably 0.01 or more, more preferably 0.03 or more, More preferably it is 0.10 or more, particularly preferably 1.00 or more.
  • the content ratio of [CNO - 2s ] is preferably 3.00 or less, more preferably 1.00 or less, even more preferably 0.30 or less, Particularly preferably, it is 0.03 or less.
  • An example of a method for making the inner wall surface of the adhesive layer satisfy formula (1) is a method of subjecting the inner wall surface of the adhesive layer to plasma nitriding treatment.
  • the adhesive layer does not contain nitrogen atoms
  • plasma nitriding is performed on the inner wall surface of the adhesive layer, ([CNO - 2s ]/[CNO - 50s ]) increases dramatically.
  • ([CNO - 2s ]/[CNO - 50s ]) is 10 or more.
  • the inner wall surface of the adhesive layer may satisfy the formula (2), and the inner wall surface and the outer wall surface of the adhesive layer may satisfy the formula (2).
  • the C 3 ⁇ normalized strength of the adhesive layer analyzed by TOF-SIMS depends on the material of the adhesive layer, whether EUV irradiation treatment has been performed, etc. It is assumed that C 3 ⁇ is mainly derived from carbonization of the inner wall surface of the adhesive layer due to surface treatment.
  • the surface treatment includes plasma nitriding treatment or extreme ultraviolet irradiation treatment (hereinafter referred to as "EUV irradiation treatment").
  • the surface layer of the adhesive layer is carbonized, the generation of outgas is suppressed, and the permeation of gas from inside the adhesive layer can be suppressed.
  • ([C 3 - 2s ]/[C 3 - 50s ]) can be set to, for example, 10.0 or less, preferably 5.0 or less, more preferably is 3.0 or less, more preferably 2.0 or less.
  • ([C 3 - 2s ]/[C 3 - 50s ]) can be set to 1.10 or more, for example, from the viewpoint of carbonizing and modifying the surface layer of the adhesive layer and suppressing the generation of outgas. Preferably it is 1.20 or more, more preferably 1.40 or more, still more preferably 2.00 or more.
  • An example of a method for making the inner wall surface of the adhesive layer satisfy formula (2) is a method of subjecting the inner wall surface of the adhesive layer to EUV irradiation treatment.
  • the inner wall surface or the like of the adhesive layer absorbs the EUV and becomes high temperature.
  • surfaces such as the inner wall surface that have been subjected to EUV irradiation treatment are likely to be carbonized.
  • the base material layer can form a flexible frame member without forming a thick adhesive layer by applying a thick adhesive. Since the flexible frame member includes at least one base material layer, the thickness of the adhesive layer included in the flexible frame member is thinner than the thick adhesive layer formed by thickly coating the adhesive. Therefore, the adhesive layer included in the flexible frame member is formed by drying in a shorter time. Furthermore, since large deformation of the pellicle frame can be suppressed, the pellicle can be easily transported and handled.
  • the upper limit of the thickness of one commercially available optical adhesive sheet OCA: Optical Clear Adhesive
  • OCA Optical Clear Adhesive
  • each base layer (hereinafter referred to as "single layer thickness of base layer”) is preferably 2.5 mm or less.
  • the single layer thickness of the base material layer is preferably 2.5 mm or less, more preferably 2.0 mm or less, and even more preferably 1.0 mm or less. , particularly preferably 0.5 mm or less.
  • the single layer thickness of the base material layer is preferably 0.01 mm or more, more preferably 0.05 mm or more, and even more preferably 0.10 mm or more. It is.
  • the Young's modulus of the base layer is preferably 2 GPa to 200 GPa. This makes it easier to carry out the punching process of the pellicle manufacturing method, suppresses large deformation of the pellicle frame, and makes it easier to transport and handle the pellicle. From the viewpoint of suppressing distortion of the original plate caused by deformation of the pellicle frame, the Young's modulus of the base layer is preferably 200 GPa or less, more preferably 110 GPa or less, still more preferably 50 GPa or less, particularly preferably 10 GPa or less.
  • the Young's modulus of the base material layer is preferably 0.1 GPa from the viewpoint of facilitating the execution of the punching step of the pellicle manufacturing method and suppressing large deformation of the pellicle frame, making it easier to transport and handle the pellicle. Above, it is more preferably 0.5 GPa or more, still more preferably 1 GPa or more. From these viewpoints, the Young's modulus of the base material layer is preferably 0.1 GPa to 110 GPa, more preferably 0.5 GPa to 50 GPa, and particularly preferably 1 GPa to 10 GPa.
  • Examples of materials with a Young's modulus of 110 GPa or less include glass, stainless steel, aluminum, titanium, titanium alloy, silicone, polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polyethylene naphthalate resin, polycarbonate resin, and polyphenylene sulfide resin. , fluororesin, polyetheretherketone resin, polyethersulfone resin, and the like.
  • Examples of materials with a Young's modulus of 50 GPa or less include polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polyethylene naphthalate resin, polycarbonate resin, polyphenylene sulfide resin, fluororesin, polyether ether ketone resin, and polyether sulfone. Examples include resin. Examples of materials with a Young's modulus of 10 GPa or less include polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polyethylene naphthalate resin, polycarbonate resin, polyphenylene sulfide resin, fluororesin, polyether ether ketone resin, and polyether sulfone.
  • Examples include resin, aramid resin, and the like.
  • the Young's modulus of the base material layer was measured using a tensile test (JIS G0567J). However, when the material of the base material layer is resin, the value is measured by a three-point bending test (JIS K7171). Whether or not the material of the base layer is resin is determined by whether the material of the rigid frame member is thermally decomposed at 550°C. When evaluating stacked frames, the stacked frames may be peeled off and analyzed.
  • the Young's modulus of the base material layer is preferably 10,000 to 9,000,000 times the Young's modulus of the adhesive layer.
  • the ratio of the Young's modulus of the base material layer to the Young's modulus of the adhesive layer will be referred to as "Young's modulus ratio of the base material layer.”
  • the Young's modulus ratio of the base layer is more preferably 3 million times or less (for example, when the material of the base layer is titanium), and even more preferably It is 1,000,000 times or less, particularly preferably 200,000 times or less (for example, when the material of the base layer is polyethylene terephthalate resin).
  • the Young's modulus ratio of the base material layer is more preferably 50,000 times or more, and still more preferably 300,000 times or more. From the viewpoint of further reducing the restoring force caused by pasting to the original plate, and from the viewpoint of facilitating the execution of the lamination step of the pellicle manufacturing method, it is preferably 50,000 to 3 million times, more preferably 50,000 to 3 million times. It is 200,000 times more. If there are multiple base material layers with different Young's moduli among the multiple base material layers included in the soft frame member, the Young's modulus of the base material layer with the smallest Young's modulus among the multiple base material layers with different Young's moduli.
  • the Young's modulus of the base layer If there are multiple adhesive layers with different Young's modulus among the multiple adhesive layers included in the flexible frame member, the Young's modulus of the adhesive layer with the largest Young's modulus among the multiple adhesive layers with different Young's moduli is referred to as the "adhesive layer”. 'Young's modulus'.
  • the material of the base layer is not particularly limited, and examples thereof include metals, ceramics, resins, and the like.
  • metals that can be used for the base layer include aluminum, titanium, stainless steel, and the like.
  • ceramics that can be used for the base layer include silicon and glass.
  • resins that can be used for the base layer include polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polyimide resin, polyethylene naphthalate resin, polystyrene resin, acrylic resin, polycarbonate resin, polyimide resin, polyphenylene sulfide resin, and fluororesin. , polyetheretherketone resin, polyethersulfone resin, aramid resin, and the like.
  • the material of the base layer is preferably a material that can be slit coated or spin coated, and examples of these materials include acrylic resin, silicone resin, and styrene butadiene resin. is preferred.
  • the material of the base layer is preferably resin. If the material of the base material layer is resin, cutouts and openings can be formed by punching. Among these, the material of the base layer preferably contains polyethylene terephthalate resin, polyethylene naphthalate resin, or polyimide resin.
  • the pellicle of the present disclosure includes the pellicle frame of the present disclosure and a pellicle membrane supported by a rigid frame member.
  • the pellicle of the present disclosure is suitably used for EUV exposure.
  • the pellicle film prevents foreign matter from adhering to the surface of the original plate, and also allows exposure light to pass through during exposure. Foreign matter includes dust. Examples of the exposure light include deep ultraviolet (DUV) light, EUV, and the like.
  • DUV deep ultraviolet
  • the pellicle film covers the entire opening of the exposure through hole of the pellicle frame on the hard frame member side.
  • the pellicle membrane may be supported directly by the pellicle frame member, or may be supported via an adhesive layer.
  • the adhesive layer may be a cured product of a known adhesive.
  • the thickness of the pellicle film is preferably 2 nm or more and 200 nm or less.
  • the material of the pellicle film is not particularly limited, and examples thereof include carbon-based materials, SiN, polysilicon, and a laminated structure in which a plurality of these layers are deposited. Carbon-based materials include graphene and carbon nanotubes (hereinafter referred to as "CNTs"). Among these, it is preferable that the material of the pellicle film contains CNT.
  • the CNTs may be single-walled CNTs or multi-walled CNTs.
  • the pellicle film can be connected to the rigid frame member by van der Waals force without using an adhesive layer.
  • the pellicle membrane may be a non-woven structure. The nonwoven structure is formed by, for example, CNTs in the form of fibers.
  • the pellicle of the present disclosure may include a protective film (liner) as necessary.
  • the protective film protects at least the surface of the adhesive layer that comes into contact with the original.
  • the protective film can be peeled off from the adhesive layer.
  • the thickness of the protective film is preferably 5 ⁇ m to 500 ⁇ m, more preferably 30 ⁇ m to 200 ⁇ m.
  • the material for the protective film include polyester.
  • a release agent may be coated on the surface of the protective film that contacts the adhesive layer.
  • the mold release agent include silicone mold release agents and fluorine mold release agents.
  • the pellicle of the present disclosure may be included in an exposure original plate.
  • the exposure original plate includes an original plate and a pellicle.
  • the original version is the original version of the circuit pattern.
  • the original plate has a pattern.
  • the pellicle is attached to the patterned surface of the original plate.
  • the original plate does not need to have a support substrate, a reflective layer, and an absorber layer laminated in this order.
  • a desired image is formed on a sensitive substrate (eg, a semiconductor substrate with a photoresist film) by the absorption layer partially absorbing the light (eg, EUV).
  • the reflective layer include a multilayer film of molybdenum (Mo) and silicon (Si).
  • the material of the absorber layer may be a highly absorbent material such as EUV. Examples of materials with high absorption properties for EUV and the like include chromium (Cr), tantalum nitride, and the like.
  • the pellicle of the present disclosure may be included in an exposure apparatus.
  • the exposure apparatus includes a light source, the above-described exposure master, and an optical system.
  • a light source emits exposure light.
  • the optical system guides the exposure light emitted from the light source to the exposure master.
  • the exposure master is arranged so that the exposure light emitted from the light source passes through the pellicle film and is irradiated onto the master.
  • exposure equipment can also prevent resolution defects caused by foreign particles even when using EUV, which tends to cause resolution defects due to foreign particles. Reduced pattern exposure can be performed.
  • the exposure light is preferably EUV. Because EUV has a short wavelength, it is easily absorbed by gases such as oxygen or nitrogen. Therefore, exposure with EUV light is performed in a vacuum environment.
  • FIG. 4 is a cross-sectional view of a pellicle according to a second embodiment of the present disclosure.
  • a pellicle 1 according to a second embodiment of the present disclosure is used by being attached to the surface of an original, as shown in FIG. 4.
  • the pellicle 1 according to the second embodiment of the present disclosure includes a pellicle frame 10A, a pellicle membrane 20, and an adhesive layer 21.
  • the pellicle membrane 20 is supported by the pellicle frame 10A via a known adhesive layer 21.
  • the surface direction D1 of the pellicle film 20 will be referred to as the "surface direction D1"
  • the direction D2 perpendicular to the surface direction of the pellicle film 20 will be referred to as the "thickness direction D2”.
  • the pellicle frame 10A is a rectangular cylindrical object.
  • the pellicle frame 10A has an exposure through hole THA.
  • the exposure through hole THA extends linearly through the pellicle frame 10A along the thickness direction D2 at the center of the pellicle frame 10A in the surface direction D1.
  • the pellicle frame 10A is an assembled product and includes a soft frame member 11A and a hard frame member 12A.
  • the soft frame member 11A and the hard frame member 12A are stacked in the thickness direction D2 of the pellicle frame 10A.
  • the Young's modulus of the hard frame member 12A is higher than the apparent Young's modulus of the soft frame member 11A.
  • the Young's modulus of the rigid frame member 12A is 25 GPa or more.
  • the soft frame member 11A is a rectangular cylindrical member like the pellicle frame 10A.
  • the soft frame member 11A has a through hole TH11.
  • the through hole TH11 constitutes a part of the exposure through hole THA of the pellicle frame 10A.
  • the soft frame member 11A is formed by stacking six adhesive layers 111 and five base material layers 112 alternately in the thickness direction D2 so that the adhesive layers 111 are arranged at both ends.
  • the soft frame member 11A includes four ventilation paths THB and four ventilation filters 113.
  • One air passage THB is formed on each of the four side surfaces of the pellicle frame 10A.
  • the air passage THB extends non-linearly from the inner wall surface S10A of the pellicle frame 10A to the outer wall surface S10B in the surface direction D1.
  • One ventilation filter 113 is arranged in one ventilation path THB.
  • the ventilation filter 113 is fixed within the soft frame member 11A and covers the ventilation path THB. Specifically, in the second embodiment, the ventilation filter 113 is fixed by contacting the same surface of one adhesive layer 111 exposed in the ventilation path THB.
  • the ventilation filter 113 is, for example, a HEPA ventilation filter.
  • the rigid frame member 12A is a rectangular cylindrical member like the pellicle frame 10A.
  • the rigid frame member 12A has a through hole TH12.
  • the through hole TH12 constitutes a part of the exposure through hole THA of the pellicle frame 10A.
  • the thickness of the pellicle 1 is, for example, 2.375 mm.
  • the length L10 of one side of the pellicle frame 10A is, for example, 150 mm.
  • the width W10 of one side of the pellicle frame 10A is, for example, 4.0 mm.
  • the thickness of the soft frame member 11A is, for example, 1.650 mm.
  • the single layer thickness of the adhesive layer 111 is, for example, 0.236 mm.
  • the material of the adhesive layer 111 is, for example, acrylic resin (Young's modulus: 0.045 MPa).
  • the single layer thickness of the base material layer 112 is, for example, 0.236 mm.
  • the material of the base material layer 112 is, for example, polyethylene terephthalate resin (Young's modulus: 4 GPa).
  • the thickness of the rigid frame member 12A is, for example, 0.725 mm.
  • the pellicle 1 is suitably used for EUV exposure.
  • EUB exposure is performed in a vacuum atmosphere because EUV light is also easily absorbed by gases such as oxygen or nitrogen.
  • FIG. 5 is a cross-sectional view of a pellicle frame according to a third embodiment of the present disclosure.
  • a pellicle frame 10B according to the third embodiment of the present disclosure is the same as the pellicle frame 10A according to the second embodiment, except that the method of fixing the ventilation filter 113 is different.
  • the pellicle frame 10B is an assembled product and includes a soft frame member 11B and a hard frame member 12A.
  • the soft frame member 11B and the hard frame member 12A are stacked in the thickness direction D2.
  • the Young's modulus of the hard frame member 12A is higher than the apparent Young's modulus of the soft frame member 11B.
  • the Young's modulus of the rigid frame member 12A is 25 GPa or more.
  • the soft frame member 11B is a rectangular cylindrical member like the pellicle frame 10A.
  • the soft frame member 11B is formed by stacking six adhesive layers 111 and five base material layers 112 alternately in the thickness direction D2 so that the adhesive layers 111 are arranged at both ends.
  • the soft frame member 11B includes four ventilation paths THB and four ventilation filters 113.
  • One ventilation filter 113 is arranged in one ventilation path THB.
  • the ventilation filter 113 is fixed within the soft frame member 11B and covers the ventilation path THB.
  • one of the plurality of adhesive layers 111 has an adhesive part 111a and an adhesive part 111b, which are obtained by dividing one adhesive layer 111 into two in the thickness direction D2.
  • the ventilation filter 113 is fixed by being sandwiched between the divided adjoining adhesive parts 111a and 111b.
  • the ventilation filter 113 is, for example, a HEPA ventilation filter.
  • FIG. 6 is a cross-sectional view of a pellicle frame according to a fourth embodiment of the present disclosure.
  • a pellicle frame 10C according to the fourth embodiment of the present disclosure is the same as the pellicle frame 10A according to the second embodiment, except that the method of fixing the ventilation filter 113 is different.
  • the pellicle frame 10C is an assembled product and includes a soft frame member 11C and a hard frame member 12A.
  • the soft frame member 11C and the hard frame member 12A are stacked in the thickness direction D2.
  • the Young's modulus of the hard frame member 12A is higher than the apparent Young's modulus of the soft frame member 11C.
  • the Young's modulus of the rigid frame member 12A is 25 GPa or more.
  • the soft frame member 11C is a rectangular cylindrical member like the pellicle frame 10A.
  • the soft frame member 11C is formed by stacking six adhesive layers 111 and five base material layers 112 alternately in the thickness direction D2 so that the adhesive layers 111 are arranged at both ends.
  • the soft frame member 11C includes four ventilation paths THB and four ventilation filters 113.
  • One ventilation filter 113 is arranged in one ventilation path THB.
  • the ventilation filter 113 is fixed within the soft frame member 11C and covers the ventilation path THB. Specifically, in the fourth embodiment, the ventilation filter 113 is fixed by being welded onto the same surface of one base material layer 112 exposed within the ventilation path THB.
  • the ventilation filter 113 is, for example, a HEPA ventilation filter.
  • FIG. 7 is a cross-sectional view of a pellicle frame according to a fifth embodiment of the present disclosure.
  • the pellicle frame 10D according to the fifth embodiment of the present disclosure is different from the pellicle frame 10A according to the second embodiment, except that the configurations of the hard frame member and the soft frame member and the method of fixing the ventilation filter 113 are different. It is similar to
  • the pellicle frame 10D is an assembled product and includes a soft frame member 11D and a hard frame member 12D.
  • the soft frame member 11D and the hard frame member 12D are stacked in the thickness direction D2.
  • the Young's modulus of the hard frame member 12D is higher than the apparent Young's modulus of the soft frame member 11D.
  • the Young's modulus of the rigid frame member 12D is 25 GPa or more.
  • the soft frame member 11D and the hard frame member 12D are rectangular cylindrical members like the pellicle frame 10A.
  • the flexible frame member 11D has four adhesive layers 111 and three base material layers 112 alternately laminated in the thickness direction D2 such that the adhesive layers 111 are arranged at both ends.
  • the hard frame member 12D is formed by laminating three hard layers 121 in the thickness direction D2.
  • the flexible frame member 11D includes four ventilation paths THB and four ventilation filters 113. One ventilation filter 113 is arranged in one ventilation path THB.
  • the ventilation filter 113 is fixed within the soft frame member 11D and covers the ventilation path THB. Specifically, in the fifth embodiment, the ventilation filter 113 is fixed by contacting the same surface of one adhesive layer 111 exposed in the ventilation path THB.
  • the ventilation filter 113 is, for example, a HEPA ventilation filter.
  • the method for manufacturing a pellicle according to the present disclosure includes the steps of preparing the rigid frame member, at least one base layer sheet, and a plurality of adhesive layers. a laminating step of forming a laminate by alternately laminating layers for exposure in the thickness direction, and punching through the laminate so that exposure through holes are formed along the thickness direction, and forming the soft frame member. and a connecting step of connecting the hard frame member to the soft frame member.
  • the base material layer sheet and the plurality of adhesive layer layers are alternately laminated in the thickness direction to form a laminate. By punching through the laminate, it is possible to manufacture a pellicle frame with suppressed opening misalignment even in multiple laminates.
  • the "adhesive layer layer” includes an adhesive layer sheet and an adhesive layer coating layer obtained by applying an adhesive layer adhesive.
  • the method for manufacturing a pellicle of the present disclosure has the above configuration, it is possible to obtain a pellicle in which distortion caused by the tension of the pellicle membrane is suppressed and distortion of the original plate caused by deformation of the pellicle frame can be suppressed.
  • the lamination process and the punching process are performed in this order.
  • the preparation process may be performed before the lamination process, after the lamination process and before the punching process, or after the punching process.
  • the connecting process is performed after the punching process and the preparation process.
  • the method for manufacturing a pellicle of the present disclosure preferably further includes at least one of a surface treatment step described below and an air passage processing step described below.
  • the method for manufacturing a pellicle according to the present disclosure includes the step of processing an air passage
  • the surface treatment step is performed after the punching step.
  • the ventilation path processing step is performed before the lamination step.
  • the filter fixing step is performed after the air passage processing step and before the lamination step.
  • the method for manufacturing a pellicle according to the present embodiment includes, in addition to a lamination process, a punching process, a preparation process, and a connection process, a surface treatment process, an air passage processing process, and a filter fixing process.
  • the ventilation path processing step, filter fixing step, lamination step, punching step, surface treatment step, preparation step, and connection step are performed in this order.
  • the adhesive layer layer is an adhesive layer sheet.
  • Air passage processing step The pellicle manufacturing method of this embodiment includes an air passage processing step. Thereby, a pellicle is obtained in which the soft frame member includes a ventilation passage.
  • the ventilation path processing step at least one raw sheet for base material layer and the plurality of unprocessed sheets for adhesive layer are processed so that a ventilation path is formed. Form a sheet for the adhesive layer.
  • the ventilation path processing step is performed before the lamination step.
  • the "unprocessed sheet for base layer” refers to a solid sheet that is a material for the base layer.
  • the "unprocessed adhesive layer sheet” refers to a solid sheet that is a material for the adhesive layer.
  • the “sheet for base material layer” refers to the material of the base material layer.
  • the sheet for the base material layer may be a sheet processed so that air passages are formed, or may be a solid sheet.
  • the “adhesive layer sheet” refers to the material of the adhesive layer.
  • the sheet for the adhesive layer may be a sheet processed to form a ventilation path, or may be a solid sheet.
  • the material of the unprocessed sheet for the base material layer is the same as the material of the base material layer.
  • the material of the raw sheet for the adhesive layer is the same as that of the adhesive layer.
  • the ventilation path is constructed by forming an opening in at least one raw sheet for the base material layer and a plurality of raw sheets for the adhesive layer, and laminating these sheets.
  • the number of unprocessed sheets for the base material layer and the unprocessed adhesive layer sheet to be processed is appropriately selected depending on the shape of the ventilation passage formed in the flexible frame member, etc.
  • each of the unprocessed sheet for the base material layer and the unprocessed sheet for the adhesive layer may be processed individually, or the unprocessed sheet for the adhesive layer may be processed on at least one main surface of the unprocessed sheet for the base material layer. Processing may be performed in a laminated state.
  • the processing method for the unprocessed sheet for the base material layer and the unprocessed sheet for the adhesive layer is not particularly limited and may be any known method, such as a method using a punching die, a method using laser irradiation, a method using a slitting machine. Examples include a method using a water jet, and a method using a water jet.
  • the pellicle manufacturing method of this embodiment includes a filter fixing process. Thereby, a pellicle is obtained in which the flexible frame member includes a ventilation passage and a ventilation filter.
  • the ventilation filter is fixed to at least one base layer sheet or a part of the plurality of adhesive layer sheets so that the ventilation filter is disposed in the ventilation path.
  • the filter fixing step is performed after the air passage processing step and before the lamination step.
  • the method for fixing the ventilation filter is not particularly limited, and examples include welding or gluing the ventilation filter to the base layer sheet so that the openings formed in the base layer sheet are covered with the ventilation filter, and adhesive bonding. Examples include a method of adhering the ventilation filter to the adhesive layer so that the opening formed in the layer sheet is covered with the ventilation filter, and a method of holding the ventilation filter sandwiched between adjacent base material layer sheets. .
  • the pellicle manufacturing method of this embodiment includes a lamination process. Thereby, a laminate is obtained.
  • At least one base layer sheet and a plurality of adhesive layer sheets are alternately laminated in the thickness direction to form a laminate.
  • the number of laminated sheets for base material layers is the same as the number of base material layers included in the flexible frame member.
  • the number of laminated adhesive layer sheets is the same as the number of adhesive layers included in the flexible frame member.
  • the lamination method for alternately laminating the base layer sheet and the adhesive layer sheet in the thickness direction is not particularly limited, and any known method may be used.
  • a lamination method when forming a 5-layer laminate for example, a 3-layer laminate is formed by placing an adhesive layer sheet on both main surfaces of a base layer sheet and sandwiching it between a pair of rolls.
  • a pair of laminates is made by laminating two types of laminates: a body and a two-layer laminate formed by placing an adhesive layer sheet on one main surface of a base layer sheet and sandwiching it between a pair of rolls.
  • the sheet for the base material layer is placed on both main surfaces of the sheet for the adhesive layer, and the sheet for the base material layer is placed between a pair of rolls to form a 3-layer laminate.
  • Examples include a method in which adhesive layer sheets are placed on both main surfaces of a laminate of layers and sandwiched between a pair of rolls to form a 5-layer laminate. If more than 5 layers are to be laminated, the desired number of layers is to form a 2-layer laminate by placing the base material layer sheet on one main surface of the adhesive layer sheet and sandwiching it between a pair of rolls. A pair of rolls is produced by laminating a 3-layer laminate formed by placing the base material layer sheet on both main surfaces of the adhesive layer sheet and sandwiching it between a pair of rolls. It can be formed by being sandwiched between the two.
  • the pellicle manufacturing method of this embodiment includes a punching process. Thereby, a soft frame member is obtained.
  • the soft frame member is formed by punching through the laminate so that exposure through holes are formed along the thickness direction.
  • the method of punching through the laminate is not particularly limited and may be any known method, such as a method using a punching die, a method using laser irradiation, a method using a slitting machine, a method using a water jet, etc. .
  • the pellicle manufacturing method of this embodiment includes a surface treatment step. As a result, a pellicle is obtained in which the surface of the adhesive layer satisfies any one of the above-mentioned conditions (A) to (C).
  • the surface treatment process includes a process of coating an inorganic layer on at least the inner wall surface of the adhesive layer (hereinafter referred to as “coating process”), and a process of performing plasma nitriding treatment on at least the inner wall surface of the adhesive layer (hereinafter referred to as “plasma nitriding treatment”). ), and a step of subjecting at least the inner wall surface of the adhesive layer to extreme ultraviolet irradiation treatment (hereinafter referred to as "EUV irradiation treatment step”).
  • coating process a process of coating an inorganic layer on at least the inner wall surface of the adhesive layer
  • plasma nitriding treatment a process of performing plasma nitriding treatment on at least the inner wall surface of the adhesive layer
  • EUV irradiation treatment step extreme ultraviolet irradiation treatment
  • an inorganic layer may be coated on the inner wall surface of the adhesive layer, and an inorganic layer may be coated on the inner wall surface and the outer wall surface of the adhesive layer.
  • an inorganic layer may be coated on the entire inner wall surface of the pellicle frame, or an inorganic layer may be coated on the entire inner wall surface and the entire outer wall surface of the pellicle frame.
  • the method of coating the inorganic layer on at least the inner wall surface of the adhesive layer is not particularly limited, and examples thereof include vapor deposition, sputtering, and the like.
  • Plasma nitriding process In the plasma nitriding process, plasma nitriding may be performed on the inner wall surface of the adhesive layer, and plasma nitriding may be performed on the inner wall surface and outer wall surface of the adhesive layer. At this time, the plasma nitriding treatment may be performed on the entire inner wall surface of the pellicle frame, or the plasma nitriding treatment may be performed on the entire inner wall surface and the entire outer wall surface of the pellicle frame.
  • the plasma nitriding treatment is performed, for example, using a plasma processing apparatus (a research and development sputtering apparatus "CFS-4EP-LL” manufactured by Shibaura Mechatronics Co., Ltd., type: load-lock type) under the following processing conditions.
  • a plasma processing apparatus a research and development sputtering apparatus "CFS-4EP-LL” manufactured by Shibaura Mechatronics Co., Ltd., type: load-lock type
  • EUV irradiation treatment step the inner wall surface of the adhesive layer may be subjected to EUV irradiation treatment, and the inner wall surface and outer wall surface of the adhesive layer may be subjected to EUV irradiation treatment.
  • the entire inner wall surface of the pellicle frame may be subjected to EUV irradiation treatment, or the entire inner wall surface and outer wall surface of the pellicle frame may be subjected to EUV irradiation treatment.
  • EUV irradiation treatment can be performed using, for example, an EUV irradiation device (facility name: New Subaru Synchrotron Radiation Facility, beam line: "BL-9C_H-ch", operation: University of Hyogo Advanced Industrial Science and Technology Research), quadrupole mass spectrometer. : "M-200” manufactured by Canon Anelva Co., Ltd.) under the following processing conditions.
  • an EUV irradiation device facility name: New Subaru Synchrotron Radiation Facility, beam line: "BL-9C_H-ch", operation: University of Hyogo Advanced Industrial Science and Technology Research
  • quadrupole mass spectrometer “M-200” manufactured by Canon Anelva Co., Ltd.
  • the pellicle manufacturing method of this embodiment includes a preparation process. Thereby, a rigid frame member is obtained.
  • a rigid frame member is prepared.
  • the hard frame member prepared in the preparation step may have a pellicle membrane stretched over the hard frame member, or may not have a pellicle membrane stretched over the hard frame member.
  • methods for preparing a rigid frame member without a pellicle membrane stretched thereon include a method of obtaining a commercially available product by transfer, a method of obtaining a rigid frame member by a cutting method, and the like. In the cutting method, a raw material plate, which is a material for the rigid frame member, is carved out into a rigid frame member by a known method.
  • methods for preparing a rigid frame member with a pellicle membrane stretched thereon include a method of obtaining a commercially available product by transfer.
  • the pellicle manufacturing method of the present embodiment may include a stretching step when a rigid frame member on which a pellicle membrane is not stretched is prepared in the preparation step. As a result, the pellicle membrane is stretched over the rigid frame member. In other words, the pellicle membrane is supported by the rigid frame member.
  • the tensioning process may be performed after the preparation process is performed, and may be performed before the connection process or after the connection process is performed.
  • the pellicle membrane is stretched on the rigid frame member.
  • the method for tensioning the pellicle membrane on the rigid frame member is not particularly limited, and examples thereof include a method using an adhesive or a method not using an adhesive.
  • a known adhesive is applied to a hard frame member to obtain a coating film, and the resulting coating film is brought into contact with a pellicle membrane and heated. As a result, the coating film comes into close contact with the pellicle film and the hard frame member, and the pellicle frame and the hard frame member are integrated.
  • the method of applying the adhesive is not particularly limited, and examples include a method using a dispenser.
  • the pellicle membrane is brought into contact with the rigid frame member and pressurized together. As a result, the pellicle membrane is brought into close contact with and integrated with the rigid frame member. Pressure may be applied with a coating provided between the hard frame member and the pellicle film so that the hard frame member and the pellicle film can be easily chemically bonded to each other.
  • connection process The pellicle manufacturing method of this embodiment includes a connection process. As a result, a pellicle frame in which the hard frame member and the soft frame member are integrated is obtained.
  • the hard frame member is connected to the soft frame member.
  • connection adhesive layer an adhesive layer that is integrally arranged in the thickness direction of the soft frame member.
  • connection adhesive layer heat the connection adhesive layer.
  • the adhesive layer for connection comes into close contact with the hard frame member, and the hard frame member and the soft frame member are integrated.
  • Example 1 [1.1] Lamination process A styrene-butadiene adhesive was prepared as an adhesive for the adhesive layer. A polyethylene terephthalate resin sheet (thickness: 0.55 mm) was prepared as a base layer sheet. The adhesive for the adhesive layer was applied onto both main surfaces of the sheet for the base material layer using a roll coater to form a coating layer for the adhesive layer on both the main surfaces of the sheet for the base material layer. As a result, one base material layer sheet and two adhesive layer layers are laminated alternately in the thickness direction to form a three-layer laminate of adhesive layer layer/base material sheet/adhesive layer layer. did. The single layer thickness of the base material layer was 0.55 mm. The single layer thickness of the adhesive layer was 0.55 mm.
  • a silicon rectangular pellicle frame (height: 0.725 mm, length of one side (long side): 151 mm, width of one side (long side): 4 0 mm, length of one side (short side): 119 mm, width of one side (short side): 4.0 mm) was prepared.
  • connection process Lift the hard frame member by suction under reduced pressure, position it so that the outer periphery of the hard frame member and the outer periphery of the soft frame member match, and apply 0.6N to the adhesive layer of the soft frame member at room temperature.
  • the hard frame member and the soft frame member were integrated by pressing with a load of . As a result, a pellicle frame was obtained.
  • the height of the pellicle frame was 2.375 mm.
  • the apparent Young's modulus of the soft frame member the apparent Young's modulus of the pellicle frame, and the bending rigidity of the pellicle frame are calculated using the following parameters as equations (iv), (v), and (vi). Calculated from. The calculation results are shown in Table 1.
  • Example 2 to Example 15 A pellicle was obtained in the same manner as in Example 1, except that the total number of layers, the single layer thickness of the base material layer, and the single layer thickness of the adhesive layer were changed as shown in Table 1. The rate etc. were calculated. The calculation results are shown in Table 1.
  • a three-layer laminate of adhesive layer layer/substrate sheet/adhesive layer layer and a two-layer laminate of adhesive layer layer/substrate sheet were prepared.
  • a pellicle frame was produced by laminating a three-layer laminate and a two-layer laminate so that the total number of layers was as shown in 1.
  • Example 7 a pellicle frame was produced by laminating a two-layer laminate, a two-layer laminate, a two-layer laminate, a two-layer laminate, and a three-layer laminate in this order.
  • Reference example 1 As shown in FIG. 8, a pellicle frame made of anodized aluminum (external dimensions: 150 mm x 122 mm, height H91: 3.5 mm, width W: 2.0 mm) was prepared as the hard frame member 91. A prepared styrene-butadiene resin adhesive was applied onto the original plate side end surface of the hard frame member 91 using a dispenser. After disposing a protective film thereon, hot pressing was performed at 100° C., and after heating, a flattening treatment was performed to form a soft frame member 92 with a flat surface shape. As a result, a pellicle frame 90 was obtained. The thickness H92 of the soft frame member 92 was 0.5 mm.
  • the Young's modulus of the rigid frame member, etc. were calculated in the same manner as in Example 1.
  • the apparent Young's modulus of the pellicle frame 90 of Reference Example 1 was 693 GPa (6.93 ⁇ 10 11 Pa).
  • the bending rigidity of the pellicle frame 90 of Reference Example 1 was 51.9 ⁇ 10 ⁇ 2 Pa ⁇ m 4 .
  • the amount of distortion of the original plate when the pellicle 9 of Reference Example 1 was attached to the original plate was not within an allowable range.
  • the “total number of layers” indicates the total number of base material layers and the number of adhesive layers included in the flexible frame member.
  • Total thickness ratio of adhesive layers refers to the ratio of the total thickness of adhesive layers included in the flexible frame member to the total thickness of the base material layers included in the flexible frame member.
  • Single layer thickness of adhesive layer refers to the thickness of each adhesive layer included in the flexible frame member.
  • Single layer thickness of base material layer refers to the thickness of one base material layer included in the flexible frame member.
  • Youngng's modulus ratio of the base material layer refers to the ratio of the Young's modulus of the base material layer included in the flexible frame member to the Young's modulus of the adhesive layer included in the flexible frame member.
  • the pellicle frames of Examples 1 to 15 include a hard frame member and a soft frame member connected to the hard frame member.
  • the flexible frame member is made up of a base layer and an adhesive layer that are alternately laminated in the thickness direction so that the adhesive layer is disposed at both ends.
  • the Young's modulus of the hard frame member was higher than the apparent Young's modulus of the soft frame member.
  • the Young's modulus of the rigid frame member was 185 GPa, which was 25 GPa or more. Therefore, the bending rigidity of the soft frame members of Examples 1 to 15 is 5.38 ⁇ 10 ⁇ 2 Pa ⁇ m 4 or less, and the bending rigidity of the pellicle frame of Reference Example 1 (51.9 ⁇ 10 ⁇ 2 The value was lower than that of Pa ⁇ m 4 ).
  • the bending rigidity of the soft frame members of Examples 1 to 15 can reduce the amount of distortion of the original when the pellicle is attached to the original.
  • the pellicle frame of the present disclosure can suppress distortion of the original plate caused by deformation of the pellicle frame.
  • the Young's modulus of the rigid frame members of Examples 1 to 15 was 185 GPa.
  • the rigid frame members of Examples 1 to 15 are sufficiently hard.
  • the pellicle frames of Examples 1 to 15 were not easily distorted inside the pellicle frame due to the tension of the pellicle membrane. From the above, it was found that the pellicle frames of Examples 1 to 15 were able to suppress distortion caused by the tension of the pellicle membrane, and also suppressed distortion of the original plate caused by deformation of the pellicle frame.

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Abstract

Le but de la présente invention est de fournir : un cadre de pellicule dans lequel un gauchissement provoqué par une tension dans un film de pellicule est supprimé, et qui peut supprimer le gauchissement d'une plaque originale provoqué par la déformation du cadre de pellicule ; une pellicule ; et un procédé de production de pellicule.　Un cadre de pellicule comprend : un élément de cadre dur (12A) servant à supporter un film de pellicule ; et un élément de cadre mou (11X) destiné à être relié à une plaque originale à motif. L'élément de cadre mou (11X) est relié à l'élément de cadre dur (12A). L'élément de cadre mou (11X) est obtenu en stratifiant des couches de matériau de base (112) et des couches adhésives (111) en alternance dans le sens de l'épaisseur orthogonal à la direction plane du film de pellicule, de telle sorte qu'une couche adhésive (111) est disposée à chaque extrémité. Le module de Young de l'élément de cadre dur (12A) est supérieur au module de Young apparent de l'élément de cadre mou (11X). Le module de Young de l'élément de cadre dur (12A) est d'au moins 25 GPa.
PCT/JP2023/008184 2022-03-22 2023-03-03 Cadre de pellicule, pellicule, plaque originale pour exposition, dispositif d'exposition et procédé de production de pellicule Ceased WO2023181869A1 (fr)

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CN202380027548.2A CN118974649A (zh) 2022-03-22 2023-03-03 防护膜组件框、防护膜组件、曝光原版、曝光装置和防护膜组件的制造方法
JP2024509928A JPWO2023181869A1 (fr) 2022-03-22 2023-03-03
KR1020247030047A KR20240141326A (ko) 2022-03-22 2023-03-03 펠리클 프레임, 펠리클, 노광 원판, 노광 장치 및 펠리클의 제조 방법

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2025203872A1 (fr) * 2024-03-28 2025-10-02 株式会社巴川コーポレーション Cadre pour pellicule
US12474632B2 (en) * 2020-04-23 2025-11-18 Asml Netherlands B.V. Pellicle frame for EUV lithography

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