WO2013141325A1 - Pellicle, pellicle frame, and method for manufacturing pellicle - Google Patents

Pellicle, pellicle frame, and method for manufacturing pellicle Download PDF

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Publication number
WO2013141325A1
WO2013141325A1 PCT/JP2013/058173 JP2013058173W WO2013141325A1 WO 2013141325 A1 WO2013141325 A1 WO 2013141325A1 JP 2013058173 W JP2013058173 W JP 2013058173W WO 2013141325 A1 WO2013141325 A1 WO 2013141325A1
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WO
WIPO (PCT)
Prior art keywords
pellicle
film
frame
pellicle frame
long side
Prior art date
Application number
PCT/JP2013/058173
Other languages
French (fr)
Japanese (ja)
Inventor
岩村　賢一郎
洋文 内村
雅弘 塚本
隆徳 廣瀬
政勝 平野
Original Assignee
旭化成イーマテリアルズ株式会社
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 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to CN201380015496.3A priority Critical patent/CN104204943B/en
Priority to JP2014506285A priority patent/JP5876927B2/en
Priority to KR1020167019157A priority patent/KR20160087927A/en
Priority to KR1020147025813A priority patent/KR101688713B1/en
Publication of WO2013141325A1 publication Critical patent/WO2013141325A1/en

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    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention foreign matter adheres to an exposure base such as a photomask or a reticle used in a lithography process when manufacturing a thin film transistor (TFT), a color filter (CF), or the like constituting an LSI or a liquid crystal display (LCD).
  • TFT thin film transistor
  • CF color filter
  • the present invention relates to a pellicle, a pellicle frame, and a method for manufacturing the pellicle that are used to prevent this.
  • a dust cover commonly called a pellicle
  • a pellicle is attached to the exposure substrate for the purpose of preventing foreign matter from adhering to the exposure substrate such as a photomask or reticle. Is done.
  • This pellicle is usually a transparent polymer material such as nitrocellulose, a cellulose derivative or a fluoropolymer having a thickness of 10 ⁇ m or less on the upper edge surface of a pellicle frame having a shape matched to the shape of the substrate for exposure and having a thickness of about several millimeters.
  • a film made of (hereinafter referred to as “pellicle film”) is spread and adhered, and an adhesive is applied to the lower edge surface of the pellicle frame, and a protective film is adhered to the surface of the adhesive with a predetermined adhesive force. It has been made.
  • the adhesive material is for fixing the pellicle to the exposure substrate, and the protective film protects the adhesive surface of the adhesive material in order to maintain the adhesive force of the adhesive material until the adhesive material is used. To do.
  • a pellicle frame applicable to a large photomask or reticle used in a photolithography process such as a large TFTLCD (Thin Film Transistor Liquid Crystal Display)
  • TFTLCD Thin Film Transistor Liquid Crystal Display
  • a rectangular shape having a long side and a short side is generally used.
  • the side of the frame is distorted inward due to the tension of the pellicle film, and the effective exposure area of the photomask or reticle may be reduced due to this distortion.
  • the phenomenon becomes more prominent as the stretched area of the pellicle film increases (the pecryl film increases).
  • Such a phenomenon has been solved by increasing the rigidity of the pellicle frame while maintaining the area inside the pellicle frame (hereinafter referred to as an effective area) as much as possible (for example, Patent Documents 1 to 4). 4).
  • the side of the frame is distorted inward due to the tension of the pellicle film.
  • the pellicle frame The amount of deformation was smaller than the amount of deformation due to the tension of the pellicle membrane, and a balance could be achieved.
  • the deformation amount of the pellicle frame becomes larger than the deformation amount due to the tension of the pellicle film. For this reason, when the pellicle film is cut, the pellicle frame is not simply distorted inward, but the pellicle frame is deformed up and down, and the corners of the pellicle frame are deformed. Further, since the rigidity of the pellicle frame is small, the force that balances with the tension of the pellicle film is small, so that the tension of the pellicle film cannot be maintained and film wrinkles are generated, and further, the film tension is weakened. Therefore, a new problem has occurred that the film swells during handling and is difficult to handle.
  • the present invention solves the above problems based on such knowledge.
  • the pellicle frame according to the present invention is a pellicle frame that is formed in a substantially rectangular frame shape by four sides to support the pellicle film, and the ratio of the long side width / long side length of the side is 0.3% or more and 2.2% or less, the ratio of the short side width / short side length of the side part is 0.3% or more and 3.8% or less, and at least a pair of side parts are outside the pellicle frame. Bulges.
  • the ratio of the long side width / long side length of the side portion is 0.3% or more and 2.2% or less, and the ratio of the short side width / short side length is 0.3%.
  • the long side length of the side portion may be 400 mm or more and 2000 mm or less, and the short side length of the side portion may be 200 mm or more and 1800 mm or less. If the area is the length of the long side at 20,000 cm 2 or more 30,000 2 or less is more than 1500 mm, in terms of wrinkle prevention with exposure area secured pellicle film, the long side width of the side portion is preferably more than 15mm below 8mm More preferably, it is 9 mm or more and 14.5 mm or less, further 10 mm or more and 14 mm or less, and the short side width of the side part is preferably 7 mm or more and 15 mm or less, more preferably 8 mm or more and 14.5 mm or less, and further 9 mm or more and 14 mm or less.
  • the long side width of the side part is preferably 5 mm or more and 11 mm or less, more preferably 6 mm or more and 11 mm or less. Furthermore, it is 7 mm or more and 10.5 mm or less, and the short side width of the side portion is 4 mm or more and 11 mm or less, preferably 5 mm or more and 10.5 mm or less, and further 6 mm or more and 10 mm or less.
  • the long side width of the side part is preferably 4 mm or more and 10 mm or less, more preferably 5 mm or more and 9 mm or less.
  • 0.5 mm or less, further 5.5 mm or more and 9 mm or less, and the short side width of the side portion is preferably 3 mm or more and 10 mm or less, more preferably 4 mm or more and 9 mm or less, and further preferably 5 mm or more and 8 mm or less.
  • the pair of long side portions of the side portion bulges outside the pellicle frame, and the bulge amount of the pair of long side portions is 3 mm or more and 20 mm or less. Is preferred.
  • the pellicle frame according to the present invention can be formed of a material having a Young's modulus of 1 GPa or more and 80 GPa.
  • the pellicle frame becomes a substantially rectangular shape when the pellicle film formed of a general material is attached to the pellicle frame. In the state, the restoring force of the pellicle frame and the film tension of the pellicle film can be appropriately balanced.
  • a pellicle according to the present invention is a pellicle having the above-described pellicle frame and a pellicle film that is stretched and supported by the pellicle frame, and at least a bulged side portion is elastically deformed toward the inside of the pellicle frame. In the state, the pellicle film is attached to the pellicle frame.
  • the effective exposure area can be made wider than before without changing the outer dimension of the pellicle, and the restoring force of the pellicle frame and the expansion tension of the pellicle film are balanced. Therefore, wrinkles can be prevented from occurring in the pellicle film.
  • the pellicle according to the present invention can be such that the bulged side portion is formed in a substantially linear shape by the balance between the restoring force of the side portion and the film tension of the pellicle membrane.
  • the balance between the restoring force of the side part and the film tension of the pellicle film forms the side part in a substantially linear shape, thereby securing the perforated exposure area and the restoring force of the pellicle frame and the pellicle film.
  • the film tension can be balanced appropriately.
  • the pellicle film is given a film tension having a magnitude that satisfies all of the following conditions A, B, and C.
  • the first reference point on the pellicle film is the center point of the inner edge of the long side part of the side part of the pellicle frame in plan view.
  • the sinking amount of the first reference point is 0.4 mm or more and 2.4 mm or less.
  • Condition B in a state where the pellicle is arranged so that the pellicle film is substantially horizontal, the second reference point on the pellicle film, which is a plan view from the center point of the inner edge of the short side part of the side part of the pellicle frame
  • the sinking amount of the second reference point is 0.3 mm or more and 2.3 mm or less.
  • Condition C The absolute value of the difference between the sinking amount of the first reference point and the sinking amount of the second reference point is 0.4 mm or less.
  • the pellicle film is effectively prevented from loosening. It is preferable that wrinkles occur in the pellicle film near the center and short sides, and it is preferable to suppress the pellicle film from being broken by slight vibrations because the film tension applied to the pellicle film is too strong. Therefore, it is preferable.
  • the film tension of the pellicle film is relatively strong along the diagonal line from the corner. Therefore, even when a thin pellicle frame is used, it is considered that the film tension of the pellicle film on the diagonal line can be maintained relatively strong.However, in contrast, the film of the pellicle film is near the center of the frame. Since the frame loses its tension and the sides are easily bent, the film tension of the pellicle film near the center of the frame decreases, so that when the pellicle film is attached to the pellicle frame, wrinkles are generated on the pellicle film. In the handling of the pellicle, wrinkles are likely to occur in the pellicle film.
  • the center of the long side and the short side of the pellicle frame The film tension of the pellicle film at the first reference point and the second reference point that are near the portion is increased, and the film tension of the pellicle film at the first reference point and the second reference point can be balanced.
  • the present inventors have found that the balance of the overall tension is improved and a pellicle capable of using a narrow pellicle frame can be manufactured.
  • a method for manufacturing a pellicle according to the present invention includes: (a) a step of attaching a pellicle film made of a polymer material formed on a substrate to a frame having an opening so as to cover the opening; ) A step of peeling the pellicle film attached to the frame from the substrate; and (c) a pellicle frame formed in a substantially rectangular frame shape by four sides, and at least a pair of sides is a pellicle frame.
  • the ratio of the long side width / long side length of the side part is 0.3% to 2.2%, and the short side width / short side length ratio of the side part is 0. 0%.
  • the substantially linear shape in the step (d) means a state in which the bulge P has approached the L straight line even slightly from the bulge P to the outside of FIG. Is preferred.
  • the pellicle after the step (e) has a substantially rectangular shape, which means that the shape is rectangular so as not to hinder the attachment to the exposure apparatus.
  • the ratio of the long side width / long side length in the step (c) is 0.3% or more and 2.2% or less, and the short side width of the side portion. / Since a pellicle frame having a short side length ratio of 0.3% or more and 3.8% or less is prepared, a pellicle having a wider effective exposure area than the conventional one can be obtained.
  • the at least one pair of sides is elastically deformed so that the at least one pair of sides is substantially linear, and in step (e), a pellicle film is attached to the pellicle frame in this state. Therefore, the restoring force of the pellicle frame and the spreading tension of the pellicle film can be balanced. As a result, wrinkles can be suppressed from occurring in the pellicle film.
  • the present invention can expand the effective exposure area without any problem even if a thin pellicle frame that was not expected to be used in the market is used, and there is no film wrinkle. Even if it is thin, sufficient film tension can be secured, and furthermore, a pellicle that does not have a problem in handling and a method for manufacturing such a pellicle can be provided.
  • the pellicle 1 includes, for example, a pellicle frame 10 that has a rectangular frame shape and has an opening F, and a pellicle film 11 that is attached to the upper surface of the pellicle frame 10 so as to cover the opening F and is stretched and supported on the pellicle frame 10.
  • the adhesive 12 applied to the lower surface of the pellicle frame 10 and the protective film 13 covering the surface of the adhesive 12 are provided.
  • the pellicle film 11 is made of a transparent polymer film such as nitrocellulose, cellulose derivative, cycloolefin resin, or fluorine polymer.
  • the film thickness is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 2 ⁇ m or more and 8 ⁇ m or less. More preferably, it is 2.5 ⁇ m or more and 7 ⁇ m or less.
  • the opening area of the opening F of the pellicle frame 10 is, for example, 1000 cm 2 or more, and the pellicle 1 in the present embodiment is a so-called large pellicle.
  • the opening area of the opening F of the pellicle frame 10 is 1000 cm 2 or more, if the film tension is weak during handling in the pellicle manufacturing process, film wrinkles may occur due to the weight of the pellicle frame or it may come off from the handling jig. However, by using this embodiment, the possibility of drastic film wrinkling during handling and removal from the handling jig is suppressed. Particularly pellicle area 3,000 cm 2, and more is exhibited in the case of a large-sized pellicle exceeding 6,000 2.
  • the rigidity of the pellicle frame 10 is lost due to the film tension of the pellicle film 11, and the pellicle film 11 is greatly deformed. Therefore, stress is applied to the pellicle frame 10 first, and the pellicle film 11 is attached to the pellicle frame 10 having this stress, so that the film tension of the pellicle film 11 and the stress of the pellicle frame 10 are balanced. It is important to make it. As will be described later, before the pellicle film 11 is attached to the pellicle frame 10, the pellicle film 11 is attached to the frame. To further increase the film tension of the pellicle film 11, the film tension in the frame is increased. It can also be left. By doing so, a pellicle that has film tension and can secure an effective exposure area can be manufactured.
  • the pellicle 1 is manufactured using the frame 20 shown in FIG.
  • the frame body 20 is formed in a substantially rectangular frame shape, and has four side portions including a pair of opposed long side portions 20a and a pair of opposed short side portions 20b.
  • the frame 20 has, for example, four sides that are linear as shown in FIG. 3A, and a pair of long sides 20a that protrude outward from the frame 20 as shown in FIG. A curved and bulging drum shape, or a curved and bulging drum shape such that the paired short side portions 20b are convex outward of the frame body 20 as shown in FIG.
  • a pair of long side portions 20a and a pair of short side portions 20b that are all side portions as shown in D) are formed in a drum-like shape that is curved and bulged so as to protrude outward from the frame body 20. Can do.
  • the shape that protrudes outward it may be a drum shape from one corner to the adjacent corner, and only the vicinity of the center of the long side 20a and the pair of short sides 20b is gently convex. It may be.
  • FIG. 4 is an explanatory diagram showing an outline of an example of a method for manufacturing the pellicle 1.
  • a frame 20 having an opening G is prepared.
  • the vicinity of the center of the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 is pressed inward using a jig or the like. Accordingly, an external force is applied from the outside to the inside, and the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 are elastically deformed toward the inside.
  • a substrate 30 on which the pellicle film 11 is formed by a film forming technique such as CVD or sputtering is prepared. Then, the pellicle film 11 formed on the substrate 30 is attached to the frame 20 in a state where the pair of long side portions 20a and the pair of short side portions 20b are elastically deformed inward. . At this time, adhesion between the pellicle film 11 and the frame body 20 is performed by an adhesive applied on the frame body 20. Thereafter, the external force that has elastically deformed the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 is removed. In FIG.
  • the amount of deformation inward of the frame body 20 is drawn large, but the actual pushing amount of the frame body 20 is an elastic deformation region of the frame body material. It can be pressed with any force.
  • the side is pressed by pressing from the outside.
  • the portion may be elastically deformed so as to be substantially linear.
  • the material of the frame member 20 for example, aluminum, an aluminum alloy (5000 series, 6000 series, 7000 series, etc.) or the like of metal, ceramics (SiC, A1N, A1 2 0 3 , etc.), ceramics and metal composites (Al -SiC, Al-A1N, AL-A1 2 0 3 etc.), resin, etc., among which aluminum and its alloys can be mentioned, more specifically, aluminum and magnesium alloys, aluminum and magnesium and silicon Alloys that cause elastic deformation such as alloys of aluminum, zinc, and magnesium are preferred.
  • the pellicle film 11 to which the frame body 20 is attached is peeled from the substrate 30.
  • the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 are restored to their original shapes by elastic restoring force (expansion force). Displaces outward to return.
  • a tensile force toward the outer side of the four sides acts on the pellicle film 11, and the film tension increases.
  • a pellicle frame 10 is prepared.
  • An adhesive is applied to the upper surface of the pellicle frame 10.
  • the pellicle film 11 with the frame 20 attached is attached to the upper surface of the pellicle frame 10 so as to cover the opening F.
  • the pellicle film 11 is attached to the pellicle frame 10 in a state where the film tension is maintained. Thereafter, an excess portion of the pellicle film 11 including the frame body 20 is removed.
  • the film tension of the pellicle film 11 made of a polymer material can be improved without causing a temperature change, the physical properties of the pellicle film 11 can be prevented from changing, and exposure using the pellicle 1 can be performed. Processing can be performed appropriately.
  • it is not necessary to use materials that can withstand temperature changes such as the pellicle frame 10, the adhesive 12, and the pellicle film 11, and the degree of freedom in selecting the material is increased. Further, there is no need for expensive equipment for imparting temperature changes or performing air conditioning accompanying temperature changes, and the control process is facilitated.
  • the adhesive 12 and the like are not deteriorated by heat, the flatness and dimensional accuracy of the pellicle 1 are ensured, and highly accurate exposure processing can be performed.
  • the pellicle 1 described in the present embodiment is a large pellicle with an opening area F of the pellicle frame 10 of 1000 cm 2 or more.
  • the film tension can be improved, Deflection due to its own weight can be suppressed. Therefore, even with a large pellicle, highly accurate exposure processing can be realized. Further, the swelling of the pellicle film 11 caused by the surrounding atmosphere involved when being mounted on the exposure substrate can be suppressed. Thereby, the waiting time until the swelling of the pellicle film 11 returns is reduced, and the manufacturing time can be shortened.
  • the frame 20 when the frame 20 has an initial shape that is curved and bulged so that at least one side of the frame 20 protrudes outward, the frame A large amount of deformation toward the inside of the 20 side portions can be ensured, and accordingly, a large amount of deformation can be secured when returning to the original state by an elastic restoring force (expansion force). Therefore, the pellicle film 11 can be pulled more strongly, and the film tension can be further increased.
  • the film tension can be increased only in the direction in which the tension in the long side direction or the short side direction of the pellicle film 11 is desired to be expressed.
  • the pellicle film 11 is rectangular, a strong tension is applied in the long side direction.
  • the tension balance in the four directions can be equalized.
  • the rigidity of the pellicle frame 10 is high, it is preferable that an arbitrary side portion of the frame body 20 is elastically deformed inward.
  • the range of high rigidity is the range of 90 to 450 Young's modulus. Specifically, they are fine ceramics (for example, alumina, silicon carbide, etc.), iron, SUS, titanium and the like.
  • the external force that deforms the pair of long sides 20a and the pair of short sides 20b of the frame 20 is applied to the pellicle film 11 from the substrate 30 after the pellicle film 11 is attached to the frame 20.
  • 11 may be removed before the pellicle film 11 is detached from the substrate 30 and before the pellicle film 11 is attached to the pellicle frame 10. Further, the external force may be removed after the pellicle film 11 is attached to the pellicle frame 10.
  • the frame 20 is elastically deformed when the pellicle film 11 is attached, but the pellicle frame 10 may be elastically deformed.
  • FIG. 5 shows the shape of the pellicle frame 10 used in this example.
  • the pellicle frame 10 is formed in a substantially rectangular frame shape, and has four sides including a pair of opposed long sides 10 a and a pair of opposed short sides 10 b. Yes.
  • the pellicle frame 10 is formed in a drum-like shape, for example, as shown in FIG. 5B, in which a pair of long side portions 10a are curved and bulged so as to protrude outward from the pellicle frame 10.
  • the material of the pellicle frame 10 may be anything as long as the Young's modulus is 1 GPa or more and 80 GPa or less.
  • this Young's modulus is less than 1 GPa, there is a problem that the tension of the film is too strong and the restoring force of the frame cannot be used.
  • the Young's modulus is larger than 80 GPa, there is a problem that it is difficult to elastically deform due to high rigidity and a high restoring force cannot be expected. For this reason, there exists an advantage that the moderate restoring force which balances a film
  • any material generally used for a pellicle frame such as aluminum, an alloy thereof, ceramics, or resin may be used.
  • the material of the pellicle frame 10 is preferably lightweight and rigid considering the increase in its own weight due to an increase in size, and is preferably aluminum or an alloy thereof.
  • the thickness of the pellicle frame 10 is 2.5 mm or more and 10 mm or less, preferably 3.0 mm or more and 8 mm or less, more preferably 4.0 mm or more and 7. 0 mm or less. This is because when the thickness is within this range, even if the foreign matter adheres to the pellicle film 11, the foreign matter and the pattern of the exposure base are not drawn as substantially the same image. This is because the transmittance of the glass is not substantially lowered.
  • the width of the pellicle frame 10 (the width of the long side portion 10a and the short side portion 10b) is such that the ratio of the long side width / the long side length is 0.3% or more and 2.2% or less.
  • 5% or more and 2.2% or less more preferably 0.55% or more and 2.1% or less, and further preferably 0.6% or more and 2.0% or less.
  • Another preferable example is 0.4% or more and 2.1% or less, more preferably 0.5% or more and 2.0% or less, and further preferably 0.9% or less, and further preferably Is 0.8% or less.
  • the ratio of short side width / short side length is 0.3% to 3.8%, preferably 0.5% to 3.8%, preferably 0.55% to 3. 5% or less, more preferably 0.6% or more and 3.0% or less, and other preferable examples of the ratio are 0.3% or more and 2.2% or less, and more preferably 0.4% or less.
  • the long side length means the outer dimension of the long side portion 10a in the pellicle frame 10
  • the short side length means the outer dimension of the short side portion 10b in the pellicle frame 10.
  • the long side length of the pellicle frame 10 is, for example, 400 mm or more and 2000 mm or less, preferably 700 mm or more and 1800 mm or less, more preferably 900 mm or more and 1600 mm or less, and particularly preferably 1200 mm or more and 1400 mm or less.
  • the short side length is, for example, 200 mm or more and 1800 mm or less, preferably 500 mm or more and 1600 mm or less, and further 700 mm or more and 1200 mm or less.
  • the long side width of the pellicle frame 10 can be, for example, 5 mm or more and 15 mm or less
  • the short side width of the pellicle frame 10 is, for example, 4 mm or more. It can be 15 mm or less.
  • FIG. 6 is an explanatory diagram showing an outline of a method for manufacturing the pellicle 1 of this example.
  • a pellicle frame 10 is prepared.
  • An adhesive is applied to the upper surface of the pellicle frame 10.
  • FIG. 6B the vicinity of the center of the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 is suppressed using a jig or the like. Thereby, an external force is applied from the outside to the inside, and the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 are elastically deformed inward.
  • the pellicle film 11 attached to the frame body 20 is attached to the upper surface of the pellicle frame 10 so as to cover the opening F.
  • the pellicle film 11 is formed on the substrate 30 first and then attached to the frame 20 as in the above-described embodiment, and then the substrate 30 is removed.
  • FIG. 6 the amount of deformation toward the inside of the pellicle frame 10 is drawn large for the sake of explanation, but the actual amount of push-in of the pellicle frame 10 is depressed by an arbitrary force as long as it is an elastic deformation region of the frame material. be able to. Further, as shown in FIGS.
  • the pellicle frame 10 in the case of the pellicle frame 10 that is curved and bulged so that the side is convex outward, the side is pressed by pressing from the outside.
  • the portion may be elastically deformed so as to be substantially linear.
  • the external force applied to the pellicle frame 10 is removed.
  • the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 are displaced outward so as to return to the original shape by an elastic restoring force (expansion force).
  • an elastic restoring force expansion force
  • a tensile force directed toward the outer side of the four sides acts on the pellicle film 11 to increase the film tension.
  • the excess portion of the pellicle film 11 is removed.
  • a pellicle When a pellicle is manufactured using a narrow pellicle frame, if the film tension of the pellicle film is weak, wrinkles may occur in the pellicle film during manufacturing or handling of the pellicle.
  • the pellicle When a pellicle in such a state is attached to a mask and used, the pellicle will bend and come into contact with a foreign substance inspection device, etc., or when handling a mask with a pellicle, there is a high possibility that the pellicle film will come into contact with the case.
  • the optical path of the exposure light at the time may be bent, and there is a possibility that normal exposure cannot be performed.
  • the film tension of the pellicle film 11 in the vicinity of the center portion of the frame body 20 is reduced so that the pellicle film 11 is attached to the pellicle frame 10
  • wrinkles are likely to occur in the pellicle film 11 and wrinkles are likely to occur in the pellicle film 11 when the pellicle 1 is handled. Therefore, if the sinking amount at the first reference point and the sinking amount at the second reference point are within the range defined by the following conditions A to C as described below, the long side and the short side of the pellicle frame 10 are reduced.
  • the film tension of the pellicle film 11 at the first reference point and the second reference point in the vicinity of the central portion on the side is increased, and the film tension of the pellicle film 11 at the first reference point and the second reference point is balanced. Therefore, the present inventors have found that the balance of tension of the entire pellicle film 11 is improved, and the pellicle 1 capable of using the narrow pellicle frame 10 can be manufactured.
  • the pellicle film 11 is given a film tension having a magnitude that satisfies all of the following conditions A, B, and C.
  • Condition A In a state where the pellicle 1 is arranged so that the pellicle film 11 is substantially horizontal, it is the first reference point on the pellicle film 11 and the inner edge of the long side portion 10a of the side portion of the pellicle frame 10 in plan view Of the first reference point when a weight of 10.6 g is placed on the first reference point 30 mm away in the direction orthogonal to the inner edge of the long side portion 10a from the center point (hereinafter referred to as “long side side”) Is sometimes 0.4 mm or more and 2.4 mm or less, preferably 0.5 mm or more and 2.0 mm or less, more preferably 0.8 mm or more and 1.9 mm or less.
  • Condition B a second reference point on the pellicle film 11 in a state where the pellicle film 1 is arranged so that the pellicle film 11 is substantially horizontal, and the inner edge of the short side portion 10b of the side portion of the pellicle frame 10 in plan view Of the second reference point when a weight of 10.6 g is placed on the second reference point 30 mm away from the central point in the direction orthogonal to the short side portion 10b (hereinafter referred to as “film on the short side side”). Is sometimes 0.3 mm or more and 2.3 mm or less, preferably 0.4 mm or more and 1.9 mm or less, more preferably 0.7 mm or more and 1.7 mm or less.
  • the absolute value of the difference between the sinking amount at the first reference point and the sinking amount at the second reference point (that is, the difference between the film sinking amount on the long side and the film sinking amount on the short side) is 0 0.4 mm or less, preferably 0.3 mm or less, more preferably 0.25 mm or less.
  • the film tension applied to the pellicle film 11 satisfies the above conditions A, B and C, film wrinkles are less likely to occur in the pellicle film 11 after the pellicle film 11 is attached to the pellicle frame 10. is there.
  • the pellicle film 11 comes into contact with the mask when the pellicle 1 is handled, or when the pellicle film 11 attached to the pellicle 1 receives an external pressure such as wind pressure. This is because the pellicle film 11 is prevented from contacting the mask.
  • the inventors of the present application in the pellicle using a narrow pellicle frame, the difference between the film sinking amount on the short side and the film sinking amount on the long side is compared with the difference in the conventional pellicle, I found it very small. Therefore, unlike the case of the conventional pellicle, since the balance of the film tension is maintained throughout the rectangular pellicle film 11, the product can be used as a pellicle even if the width of the side of the pellicle frame is narrow.
  • FIG. 7 is a schematic perspective view for explaining a method of measuring the film sinking amount on the long side and the film sinking amount on the short side.
  • FIG. 8 shows the film sinking amount on the long side and the short side. It is typical sectional drawing for demonstrating the measuring method of the film sinking amount.
  • 8A shows a longitudinal section of the pellicle 1 at the center point in the length direction of the long side portion 10a of the pellicle frame 10
  • FIG. 8B shows the length of the short side portion 10b of the pellicle frame 10.
  • a longitudinal section of the pellicle 1 at the center point in the vertical direction is shown.
  • a pellicle storage container tray was used as the pellicle mounting table 50.
  • the pellicle 1 with the adhesive 12 and the protective film 13 (not shown in FIG. 7) is placed on the pellicle on the frame so that the pellicle film 11 is substantially horizontal. Place on the mounting table 50. Then, the two first reference points 111 in the pellicle film 11 are lightly marked so as not to break the pellicle film 11.
  • the first reference point 111 is the inner edge of the long side portion 10a from the center point 10ac of the long side portion 10a of the side portion of the pellicle frame 10 in plan view (as viewed from the thickness direction of the pellicle film 11). It is a point 30 mm away in the direction orthogonal to.
  • a 10.6 g weight 55 is placed on one of the first reference points 111, and the amount of sinking 111D of the pellicle film 11 (the amount of film sinking on the long side 111D) relative to the position before placing the weight is laser-displaced. Measure with a meter. More specifically, a weight 55 having a hole shape such as a donut shape is prepared, and the weight 55 is placed on one first reference point such that the center of gravity of the weight 55 is positioned on the first reference point 111. The laser deformation sensor 57 is controlled so as to be positioned above the weight 55 by the stand 61.
  • the first reference point 111 is irradiated with laser light from the sensor 57 through the hole in the center of the weight 55, and the size of the film sinking amount 111D on the long side of the pellicle film 11 is measured.
  • the controller 63 transmits a control signal to the sensor 57, and the position of the sensor 57, the timing of laser irradiation, and the like are controlled by this control signal.
  • the measurement data of the sensor 57 is transmitted to the computer 65 via the controller 63.
  • the computer 65 controls the controller 63 and calculates the value of the film sinking amount 111D on the long side from the measurement data transmitted through the controller 63. Similarly, the amount of film sink on the long side is also measured for the other first reference point 111.
  • the average value of the long-side film sinking amount for one first reference point 111 and the long-side film sinking amount for the other first reference point 111 is calculated, and the average value is calculated as the long-side film sinking amount. The amount of film sinking on the side.
  • the pellicle 1 with the adhesive 12 and the protective film 13 (not shown in FIG. 7) is placed on the frame so that the pellicle film 11 is substantially horizontal.
  • the pellicle mounting table 50 is left still.
  • the two second reference points 112 in the pellicle film 11 are lightly marked so as not to break the pellicle film 11.
  • the second reference point 112 is a plan view (as viewed from the thickness direction of the pellicle film 11) from the center point 10bc of the inner edge of the short side portion 10b of the side portion of the pellicle frame 10 to the inner edge of the short side portion 10b. It is a point 30 mm away in the direction orthogonal to.
  • a 10.6 g weight 55 is placed on one of the first reference points 112, and the amount of sinking 112D of the pellicle film 11 (the amount of film sinking 112D on the long side) relative to before placing the weight is laser-displaced. Measure with a meter. More specifically, the weight 55 is placed on one second reference point 112 so that the center of gravity of the weight 55 is positioned on one second reference point 112, and the laser deformation sensor 57 is weighted by the stand 61. It controls so that it may be located above 55.
  • the second reference point 112 is irradiated with laser light from the sensor 57 through the hole in the center of the weight 55, and the size of the film sinking amount 112D on the long side of the pellicle film 11 is measured.
  • the controller 63 transmits a control signal to the sensor 57, and the position of the sensor 57, the timing of laser irradiation, and the like are controlled by this control signal.
  • the measurement data of the sensor 57 is transmitted to the computer 65 via the controller 63.
  • the computer 65 controls the controller 63 and calculates the value of the film sinking amount 112D on the long side from the measurement data transmitted through the controller 63.
  • the film sink amount on the long side is measured.
  • an average value of the film sink amount on the short side for one second reference point 112 and the film sink amount on the short side for the other second reference point 112 is calculated, and the average value is calculated as the short side The amount of film sinking on the side.
  • the film tension of the pellicle film 11 made of a polymer material can be improved without causing a temperature change, the physical properties of the pellicle film 11 can be prevented from changing, and exposure using the pellicle 1 can be performed. Processing can be performed appropriately.
  • it is not necessary to use materials that can withstand temperature changes such as the pellicle frame 10, the adhesive 12, and the pellicle film 11, and the degree of freedom in selecting the material is increased. Further, there is no need for expensive equipment for imparting temperature changes or performing air conditioning accompanying temperature changes, and the control process is facilitated.
  • the adhesive 12 and the like are not deteriorated by heat, the flatness and dimensional accuracy of the pellicle 1 are ensured, and highly accurate exposure processing can be performed.
  • the film tension can be improved, it is possible to suppress the bending due to the weight of the pellicle film 11 that becomes conspicuous when the pellicle 1 is enlarged. Therefore, even with a large pellicle, highly accurate exposure processing can be realized. Further, the swelling of the pellicle film 11 caused by the surrounding atmosphere involved when being mounted on the exposure substrate can be suppressed. Thereby, the waiting time until the swelling of the pellicle film 11 returns is reduced, and the manufacturing time can be shortened.
  • all of the pair of long sides 10a and the pair of short sides 10b of the pellicle frame 10 are elastically deformed inward, but at least one of the four sides is inward. It may be deformed. Then, by selecting the side part to be deformed inside the pellicle frame 10, the film tension can be increased only in the direction in which the tension in the long side direction or the short side direction of the pellicle film 11 is desired to be expressed. When 11 is rectangular, it is possible to equalize the tension balance in the four directions, such as applying a strong tension in the long side direction.
  • the pellicle frame 10 when the pellicle frame 10 has an initial shape curved and bulged so that at least one side protrudes outward, the pellicle frame A large amount of deformation toward the inside of the 10 side portions can be ensured, and accordingly, a large amount of deformation can be secured when returning to the original state by the elastic restoring force (expansion force). Therefore, the pellicle film 11 can be pulled more strongly, and the film tension can be further increased.
  • the pellicle frame 10 is bulged to the outside by pressing down the curved and bulged portion so as to protrude outward.
  • the pressing can be performed with any force within the elastic deformation region of the frame, and the amount of bulging that protrudes outward from the pellicle frame 10 and the amount of pressing into the pellicle frame 10 are balanced.
  • the pair of long side portions 10a and the pair of short side portions 10b are preferably adjusted to be substantially linear after the pellicle 1 is molded.
  • the frame 20 and the pellicle frame 10 have a bulging amount that protrudes outward from the sides in the initial shape of at least a pair of sides.
  • the pair of side portions may be on either the long side or the short side, but it is preferable to form a bulging amount that protrudes outward on the long side.
  • the bulging amount on the long side is preferably 3 mm or more and 20 mm or less, more preferably 3.5 mm or more and 20 mm or less, still more preferably 3.8 mm or more and 18 mm or less, and further preferably 4.0 mm or more and 15 mm or less.
  • the bulging amount that protrudes outward from the side portion in the initial shape on the short side side is 2.8 mm to 15 mm, more preferably 2.9 mm to 12 mm, and still more preferably 3.0 mm to 9 mm.
  • the bulging amount on the long side is 2.5 mm to 20 mm and short.
  • the bulge amount on the side is preferably 0.5 mm or more and 15 mm or less
  • the bulge amount on the long side is 3.0 mm or more and 18 mm or less
  • the bulge amount on the short side is 1.0 mm or more and 12 mm or less.
  • the bulging amount on the long side is 3.5 mm or more and 15 mm or less
  • the bulging amount on the short side is more preferably 1.5 mm or more and 9 mm or less.
  • this bulge amount S is obtained when the straight line connecting the vertices C of the outer edges at the corners of each side of the pellicle frame 10 or the frame 20 is used as the virtual reference line L. The distance between the reference line L and the point P farthest from the reference line on the outer edge of the side.
  • the initial shape may be any shape as long as it has an outwardly convex bulge amount, but preferably has a bulge amount near the center as shown in FIG. It may be gradually convex outward from the vertex C, or may have a certain straight line from the vertex C and then convex outward.
  • the radius of curvature R of the outer edge of the corner of the pellicle frame 10 is preferably 1 mm or more and 5 mm or less, and more preferably 2 mm or more and 5 mm or less.
  • the radius of curvature R of the inner edge of the corner is preferably 1 mm or more and 3 mm or less, and most preferably 2 mm. This is because even if the pellicle frame 10 is narrow, if the curvature radius of the outer edge and the inner edge of the corner of the pellicle frame 10 is within the above range, stress can be prevented from concentrating on the corner. However, the corner can have a sufficient area.
  • the rigidity of the corner portion can be maintained, and the shape of the corner portion can be maintained even when the pellicle frame 10 has a restoring force. Therefore, the shape of the pellicle frame 10 is changed from a rectangular shape to a parallelogram shape. This is because it is difficult to be distorted into other shapes such as the above, and wrinkles can be prevented from occurring in the pellicle film due to the deformation of the shape.
  • a film adhesive or a mask adhesive when applied to the pellicle frame 10, the amount of application to the corners of the pellicle frame 10 tends to increase, but the curvature radius of the outer edge and inner edge of the pellicle frame 10 is increased. Is within the above range, it is difficult to cause adhesive sag and the like, and therefore it is preferable that a film adhesive or a mask adhesive can be uniformly applied to the pellicle frame 10.
  • the surface of the pellicle frame can be subjected to blackening treatment such as black chrome plating, black alumite, or black paint.
  • ⁇ Handling grooves can be provided on the frame, and there are cases where the grooves are provided along the entire length of a pair of short sides, or where grooves are partially provided on the four sides.
  • This groove is provided with a C surface, and C0.1 to 0.5 may be provided for deburring and the like.
  • a C surface is provided at the angle formed by the outer surface and the inner surface.
  • the C-plane having an angle with the outer side has C0.1 to 0.5
  • the C-plane having the angle with the inner side has C0.5 to 2.5. It is preferable that the C surface of the outer surface is within the above range because when cutting an excess film, the cutter, jigs, etc. are smooth and the film does not break due to the occurrence of burrs.
  • the C surface of the inner surface is within the above range because the film adhesive is difficult to sag.
  • a 5000 series aluminum alloy is generally used in many cases, and an aluminum alloy will be described as an example.
  • a pellicle frame is formed with an aluminum alloy, then anodized, fine pores generated by this treatment are sealed with a blackening agent, and a sealing treatment is applied to close the fine pores. Black anodized.
  • a general method is observed with an electron microscope, generation of fine cracks (microcracks) is confirmed.
  • micro-cracks have a problem that even if the pattern becomes finer and the wiring width is further narrowed, a very small foreign matter falling into the cracks also becomes a problem. Therefore, it is preferable to take the following method as a method for preventing the occurrence of such microcracks.
  • the surface of the pellicle frame is anodized.
  • This alumite treatment is performed in a sulfuric acid concentration of 10 to 20%, a current density of 1 to 2 A / dm 2 , an electrolyte temperature of 15 to 30 ° C., and an energization time of 10 to 30 minutes.
  • a large number of microscopic holes are regularly formed on the surface of the alloy.
  • a blackening process is performed using the holes. Since the blackening process is performed in order to prevent reflection of light from the frame, it is not limited to black, but also includes dark colors such as brown and dark blue that are close to black.
  • Examples of the blackening treatment include dyeing and electrolytic coloring.
  • Dyeing is a method of obtaining a color tone by adsorbing the dye in this hole by immersing it in a solution in which a black dye is dissolved
  • electrolytic coloring is a method in which a metallic element is electrically deposited in this hole to change the color tone. How to get.
  • the dyeing is performed at a dye concentration of 3 to 10 g / L and a dyeing solution temperature of 50 to 65 ° C.
  • a sealing process is performed to close the hole.
  • a sealing process for example, boiling water to which 6 to 12 g / L of a hard wall 3 (trade name) sealing aid, which is called a low-temperature sealing agent, is used is used.
  • the temperature of the sealing is slightly lower than 100 ° C., for example, 70 to 95 ° C., more preferably 80 ° C. If the sealing treatment is performed at ⁇ 90 ° C., a pellicle frame having a very uniform surface property and substantially free of microcracks can be produced.
  • the judgment of the presence or absence of a microcrack draws a 10 cm (actual dimension 0.1 mm) straight line in the photograph which expanded the frame body surface 1000 times with the electron microscope, and calculates the number of cracks which cross the straight line.
  • the width of the crack those that can be observed in the electron micrograph, that is, those having a crack width of 0.1 ⁇ m or more are counted. It is judged that cracks exist with higher density as this value increases.
  • a minute hole that penetrates the inside and outside of the pellicle frame body is made so that the pressure difference between the inside and outside of the space formed by the pellicle and photomask is eliminated, preventing swelling and dents in the film. I can do it.
  • the pellicle frame according to the present embodiment can have both appropriate rigidity and flexibility by satisfying the above requirements, so there is no distortion of the frame due to stretching of the pellicle film, and the pellicle can be used alone. It is possible to follow the bending of the mask itself in the handling after the pasting to the mask as well as the bending in the case of handling. As a result, the pellicle is not wrinkled and can follow the bending of the mask, so that an excellent effect is obtained that no air path is generated.
  • the pellicle film 11 is attached to the pellicle frame 10 having the opening F so as to cover the opening surface F.
  • the tension of the attached pellicle film 11 is 1.8 gf / mm or more. 6 gf / mm or less, preferably 1.9 gf / mm or more and 5 gf / mm or less, more preferably 2.0 gf / mm or more and 4.5 gf / mm or less.
  • the tension of the pellicle film 11 By adjusting the tension of the pellicle film 11 to be equal to or higher than the lower limit in the above range, the generation of wrinkles on the pellicle film 11 during the handling of the pellicle 1 is suppressed, and the handling property of the pellicle 1 is improved. Further, by adjusting the tension of the pellicle film 11 to be equal to or lower than the upper limit in the above range, cracks and breakage of the pellicle film 11 can be effectively suppressed.
  • the film adhesive for adhering the pellicle film and the pellicle frame is appropriately selected depending on the material of the pellicle film and the material of the pellicle frame.
  • an epoxy, acrylic, silicone or fluorine adhesive is used.
  • a curing method of the adhesive a curing method (thermal curing, photocuring, anaerobic curing, etc.) suitable for each adhesive is adopted. From the viewpoint of dust generation, cost, and workability, an acrylic ultraviolet curable adhesive is preferable.
  • the mask adhesive for attaching the pellicle frame to the photomask is a hot-melt type (rubber-based or acrylic-based) that has adhesive force on itself, and a tape-based (base material) with adhesive material applied to both sides of the base material.
  • a hot-melt type rubber-based or acrylic-based
  • base material with adhesive material applied to both sides of the base material.
  • Acrylic, PVC, etc. sheets or rubber, polyolefin, urethane, etc. foams can be applied, and rubber, acrylic, silicone, etc. adhesive materials are used as adhesives)
  • the adhesive material may be transparent, but may be black from the viewpoint of foreign matter inspection.
  • a relatively soft hot-melt material or foam is suitable as the mask adhesive material in order to uniformly apply the pellicle to the photomask with a low load.
  • foam dust generation from the foam can be prevented by covering the cross section with an acrylic or vinyl acetate adhesive material or a non-adhesive material.
  • the thickness of the mask adhesive is usually 0.2 mm or more, but preferably 1 mm or more for uniform sticking to the photomask.
  • a polyester film that has been subjected to a release treatment with silicone or fluorine is used.
  • Example 1 The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood. (Example) Example 1
  • a material having an aluminum alloy, a thickness of 8 mm, a width of a long side portion and a short side portion of 20 mm, and an internal size of 1600 mm ⁇ 1600 mm was prepared.
  • the frame has a shape that is curved and bulged so that the vicinity of the center of each side is convex outward, and the amount of bulging outward of the initial shape is 3.3 mm.
  • the material is aluminum alloy
  • the thickness is 5.0 mm
  • the width of the long side and the short side is 9 mm
  • the inside dimension is 1350 mm ⁇ 1140 mm
  • the vicinity of the center of each side is the outside
  • a shape having a long side portion of 9.0 mm and a short side portion side of 7.5 mm was prepared.
  • the large pellicle was manufactured as follows. Cellulose ester formed on the substrate on the frame while pressing the vicinity of the center of each side inward using a jig so that each side of the frame for the large pellicle is substantially linear Then, the pellicle film was peeled off from the substrate. After peeling from the substrate, the external force by the jig was released. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge of the pellicle frame for a large pellicle. Apply an acrylic film adhesive to the upper edge of the pellicle frame, and use a jig to hold the center of each side inward so that each side of the pellicle frame is substantially straight. A pellicle film was adhered to the frame 10, and then the excess film was excised.
  • the handling of the pellicle frame was carried out by gripping a part of each of the pair of short sides with a handling jig. Then, handling properties were evaluated in a series of handling steps from after the pellicle membrane was spread and adhered to the pellicle frame to storage in the storage container. The evaluation results are shown in FIG. In the notation of the evaluation results, “ ⁇ ” indicates that the tool has not fallen from the jig once in the handling process, and “x” indicates that the tool has fallen from the jig even once. (Example 2)
  • a material having an aluminum alloy, a thickness of 8 mm, a width of a long side and a short side of 20 mm, and an internal size of 1600 mm ⁇ 1600 mm was prepared.
  • the frame used was an initial shape with straight sides.
  • the material is an aluminum alloy
  • the thickness is 5.0 mm
  • the width of the long side and the short side is 9 mm
  • the inside dimension is 1350 mm ⁇ 1140 mm
  • the vicinity of the center of each side is outside
  • a shape bulging so as to be convex and having an initial bulging amount of 8.0 mm on the long side and 6.5 mm on the short side was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the center of the long side is directed inward with a jig so that the amount of bulging out of the long side of the pellicle frame is 5 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
  • Example 3 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. (Example 3)
  • the inner dimension is 1200 mm ⁇ 760 mm
  • the thickness is 5 mm
  • the long side width is 9 mm
  • the short side width is 5 mm
  • the long side width of the initial shape is 5 mm
  • the excess membrane was excised.
  • Example 2 the same as Example 2.
  • Example 4 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. (Example 4)
  • a material having an aluminum alloy, a thickness of 8 mm, a width of a long side and a short side of 20 mm, and an internal size of 1600 mm ⁇ 1600 mm was prepared.
  • the frame used was an initial shape with straight sides.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R5, the inner corner R2, the long side width is 6 mm
  • the short side width is 12 mm
  • the inner dimension is 1336mm x 1128mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 13.0mm on the long side and the short side A 1.5 mm side was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame and pressed by a jig toward the inner side of the bulge of the long side of the pellicle frame by 1.2 mm (a straight line of 1.2 mmL from P in FIG. 9). The pellicle film was adhered to the pellicle frame while fixing the bulging portion with a jig (fixing the jig with P in the figure), and then the excess film was cut off.
  • Example 5 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 4, the film sinking amount on the long side of the pellicle film was 2.23 mm, and the film sinking amount on the short side was 2.06 mm. (Example 5)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R2
  • the long side width is 7 mm
  • the short side width is 6 mm
  • the inner dimension is 1348mm x 1126mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 9.0mm on the long side and the short side
  • the side of 8.0mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 1.2 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
  • Example 6 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 5, the film sink amount on the long side of the pellicle film was 2.15 mm, and the film sink amount on the short side was 1.89 mm. (Example 6)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R3, the inner corner R2
  • the long side width is 9 mm
  • the short side width is 9 mm
  • the inner dimension is 1342mm x 1122mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side
  • the side of 4.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and the short side of the pellicle frame is pressed inward by 4.6mm from the bulging part while the long side does nothing Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
  • Example 6 the film sink amount on the long side of the pellicle film was 1.41 mm, and the film sink amount on the short side was 1.51 mm. (Example 7)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the frame used was an initial shape with straight sides.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R5, the inner corner R2,
  • the long side width is 12 mm
  • the short side width is 4 mm
  • the inner dimension is 1352mm x 1116mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward.
  • the bulging amount to the outside of the initial shape is 3.0mm on the long side and the short side.
  • the one whose side was 12.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. An acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the bulging portion of the long side portion of the pellicle frame is fixed with a jig, and the short side portion is 4.6 mm inside the bulging portion. The pellicle film was adhered to the pellicle frame while being pressed down with a jig, and then the excess film was excised.
  • Example 7 the film sink amount on the long side of the pellicle film was 1.54 mm, and the film sink amount on the short side was 1.45 mm. (Example 8)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R4, the inner corner R2
  • the long side width is 11 mm
  • the short side width is 7 mm
  • the inner dimension is 1346mm x 1118mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side
  • the side of 6.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 2.3 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
  • Example 9 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 8, the film sink amount on the long side of the pellicle film was 1.46 mm, and the film sink amount on the short side was 1.76 mm. Example 9
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is an aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R4, the inner corner R2
  • the long side width is 10 mm
  • the short side width is 11 mm
  • the inner dimension is 1338mm x 1120mm
  • the shape is curved and bulged so that the vicinity of the center of each side protrudes to the outside, the amount of bulging outward from the initial shape is 4.0mm on the long side, and the short side
  • the side of 4.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 1.2 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 2.3 mm from the part, and then the excess film was excised.
  • Example 10 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 9, the film sink amount on the long side of the pellicle film was 1.05 mm, and the film sink amount on the short side was 0.89 mm. (Example 10)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R5.5
  • the width of the long side is 11 mm
  • the width of the short side is 10mm
  • inner dimension is 1340mm x 1118mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward
  • the amount of bulging outward from the initial shape is 7.5mm on the long side
  • a side having a side of 3.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed with a jig from the bulging part of the long side part of the pellicle frame to the inner side by 4.6 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
  • Example 11 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 10, the film sink amount on the long side of the pellicle film was 1.00 mm, and the film sink amount on the short side was 0.95 mm. (Example 11)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R3, the inner corner R2
  • the long side width is 11 mm
  • the short side width is 5 mm
  • the inner dimension is 1350mm x 1118mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side
  • the one whose side was 14.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 2.3 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed with a jig toward the inside 7.0 mm from the part, and then the excess film was excised.
  • Example 11 the film sink amount on the long side of the pellicle film was 1.67 mm, and the film sink amount on the short side was 1.98 mm.
  • Example 1 Using the large pellicle frame used in Example 1, the pellicle film was adhered to the frame without pressing down the center of the long side of the large pellicle frame. Other than that was the same as Example 1. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
  • Example 2 Using the large pellicle frame used in Example 2, the pellicle film was adhered to the pellicle frame without pressing the long side of the large pellicle frame inward. Other than that was the same as Example 2. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
  • the frame for the large pellicle used in Example 3 with the bulging amount of the initial shape of the long side set to 0 mm is used, and the pellicle film is peeled without pressing down the long side of the pellicle frame for the large pellicle. Glued to the frame. Other than that was the same as Example 3. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
  • Example 4 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. (Comparative Example 4)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R9
  • the long side width is 9 mm
  • the short side width is 10 mm
  • the inner dimension is 1340mm x 1122mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 2.3mm on the long side and the short side
  • a 1.5 mm side was prepared. Then, the pellicle film was bonded to the pellicle frame without pressing down the long side and the short side of the pellicle frame for the large pellicle.
  • Example 5 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.78 mm, and the film sink amount on the short side was 2.37 mm. (Comparative Example 5)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R6, the inner corner R2,
  • the long side width is 4 mm
  • the short side width is 4 mm
  • the inner dimension is 1352mm x 1132mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 30.0mm on the long side and the short side
  • the one with a side of 22.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and it is pressed inward by 7.0mm from the bulge of the long side of the pellicle frame, while the short side also bulges. The pellicle film was adhered to the pellicle frame while being pressed with a jig toward the inside 7.0 mm from the part, and then the excess film was excised.
  • Example 6 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, the pellicle frame did not become substantially rectangular. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.78 mm, and the film sink amount on the short side was 2.37 mm. (Comparative Example 6)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R5, the inner corner R2,
  • the long side width is 9 mm
  • the short side width is 7 mm
  • the inner dimension is 1346mm x 1122mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 8.0mm on the long side and the short side
  • the side of 7.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the short side of the pellicle frame is pressed inward by 1.2mm from the bulging part, while the long side does nothing Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
  • Example 7 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, self-weight deflection occurred in the pellicle film during handling of the large pellicle. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.53 mm, and the film sink amount on the short side was 2.21 mm. (Comparative Example 7)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R6, the inner corner R2,
  • the long side width is 8 mm
  • the short side width is 7 mm
  • the inner dimension is 1346mm x 1124mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 9.0mm on the long side and the short side
  • the side of 8.0mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and the short side is left untouched with a jig from the bulge of the long side of the pellicle frame toward the inside by 2.3 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
  • Example 8 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, when handling a large pellicle, a jig hits the short side of the pellicle frame, and wrinkles were generated in the portion of the pellicle film adjacent to the portion hit by the jig. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 1.97 mm, and the film sink amount on the short side was 2.35 mm. (Comparative Example 8)
  • a frame similar to that of Example 4 was prepared as a frame for a large pellicle.
  • the material is aluminum alloy
  • the thickness is 5.5 mm
  • the corners are the outer corner R5, the inner corner R2,
  • the long side width is 8 mm
  • the short side width is 10 mm
  • the inner dimension is 1340mm x 1124mm
  • the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 15.0mm on the long side, short side
  • the side of 4.0 mm was prepared.
  • the large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the short side is left untouched with a jig from the bulging part of the long side of the pellicle frame to the inside of 7.0 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
  • Example 2 As in Example 1, the presence or absence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, wrinkles occurred in the pellicle film near the short side of the pellicle frame. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 1.35 mm, and the film sink amount on the short side was 1.8 mm.

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Abstract

A pellicle provided with a pellicle frame (10) formed in a substantially rectangular frame shape by a pair of long side parts (10a) and a pair of short side parts (10b), and a pellicle film (11) stretchingly supported by the pellicle frame (10). The ratio of the long-side width/long-side length ratio of the side part is 0.3% to 2.2% inclusive. The short-side width/short-side length ratio of the side part is 0.3% to 3.8% inclusive. At least one side part of the long side parts (10a) and short side parts (10b) bulge to the outer side of the pellicle frame (10). The bulging side part elastically deforms toward the inner side of the pellicle film (10). In this state, the pellicle film (11) is affixed to the pellicle frame (10).

Description

ペリクル及びペリクルフレーム並びにペリクルの製造方法Pellicle, pellicle frame, and method for manufacturing pellicle
　本発明は、ＬＳＩ、液晶ディスプレイ（ＬＣＤ）を構成する薄膜トランジスタ（ＴＦＴ）やカラーフィルター（ＣＦ）等を製造する際のリソグラフィー工程で使用されるフォトマスクやレティクルなどの露光用基盤に異物が付着することを防止するために用いられるペリクル及びペリクルフレーム並びにペリクルの製造方法に関する。 In the present invention, foreign matter adheres to an exposure base such as a photomask or a reticle used in a lithography process when manufacturing a thin film transistor (TFT), a color filter (CF), or the like constituting an LSI or a liquid crystal display (LCD). The present invention relates to a pellicle, a pellicle frame, and a method for manufacturing the pellicle that are used to prevent this.
　例えば半導体装置や液晶ディスプレイ等の回路パターン製造時のリソグラフィー工程において、フォトマスク或いはレティクルなどの露光用基盤に異物が付着することを防止する目的で、一般にペリクルと呼ばれる防塵カバーが露光用基盤に装着される。 For example, in a lithography process when manufacturing circuit patterns such as semiconductor devices and liquid crystal displays, a dust cover, commonly called a pellicle, is attached to the exposure substrate for the purpose of preventing foreign matter from adhering to the exposure substrate such as a photomask or reticle. Is done.
　このペリクルは、通常露光用基盤の形状に合わせた形状を有する厚さ数ミリ程度のペリクルフレームの上縁面に、厚さ１０μｍ以下のニトロセルロース或いはセルロース誘導体或いはフッ素ポリマーなどの透明な高分子材料からなる膜（以下、「ペリクル膜」という）を展張して接着し、かつ該ペリクルフレームの下縁面に粘着材を塗着すると共に、この粘着材表面に所定の接着力で保護フィルムを粘着させたものである。 This pellicle is usually a transparent polymer material such as nitrocellulose, a cellulose derivative or a fluoropolymer having a thickness of 10 μm or less on the upper edge surface of a pellicle frame having a shape matched to the shape of the substrate for exposure and having a thickness of about several millimeters. A film made of (hereinafter referred to as “pellicle film”) is spread and adhered, and an adhesive is applied to the lower edge surface of the pellicle frame, and a protective film is adhered to the surface of the adhesive with a predetermined adhesive force. It has been made.
　前記粘着材は、ペリクルを露光用基盤に固着するためのものであり、また、保護フィルムは、粘着材が使用されるまで粘着材の接着力を維持するために、粘着材の接着面を保護するものである。 The adhesive material is for fixing the pellicle to the exposure substrate, and the protective film protects the adhesive surface of the adhesive material in order to maintain the adhesive force of the adhesive material until the adhesive material is used. To do.
　ところで、ペリクルが装着された露光用基盤を有する露光装置において、高い寸法精度の露光処理を行うためには、光が通るペリクル膜が自重により撓むことを抑制する必要がある。特に、近年、液晶パネルの大型化や生産性向上のために露光用基盤のサイズが大型化し、それに併せてペリクル膜も５，０００ｃｍ２、１０，０００ｃｍ２、１５，０００ｃｍ２と年々大面積化しているため、その分撓み量が大きくなり、ペリクル膜の撓みが大きな問題となりつつある。 By the way, in an exposure apparatus having an exposure substrate on which a pellicle is mounted, in order to perform exposure processing with high dimensional accuracy, it is necessary to prevent the pellicle film through which light passes from being bent by its own weight. In particular, in recent years, the size of the exposure base for the size and improving productivity of the liquid crystal panel becomes large, the pellicle film is also 5,000 cm 2 in conjunction therewith, 10,000cm 2, 15,000cm 2 and year by year large area For this reason, the amount of bending is increased correspondingly, and the bending of the pellicle film is becoming a serious problem.
　大型のＴＦＴＬＣＤ(薄膜トランジスタ液晶ディスプレイ)等のフォトリソグラフィ工程で使用される大型のフォトマスクやレティクルに適用出来るペリクルの枠体としては、長辺と短辺を有する矩形状のものが一般である。この枠体にペリクル膜を貼り付けると、該ペリクル膜の張力により枠体の辺が内側に向かって歪みが生じ、この歪みによってフォトマスクやレティクルの有効露光領域が小さくなってしまう場合があり、ペリクル膜の展張面積が大きくなる（ペクリル膜が大きくなる）につれてその現象は顕著になる。このような現象に対してはペリクルの枠体の内側の面積(以下、有効面積と称する)を極力維持した状態で、ペリクル枠体の剛性を高めることで解決してきた（例えば、特許文献１～４参照）。 As a pellicle frame applicable to a large photomask or reticle used in a photolithography process such as a large TFTLCD (Thin Film Transistor Liquid Crystal Display), a rectangular shape having a long side and a short side is generally used. When a pellicle film is attached to this frame, the side of the frame is distorted inward due to the tension of the pellicle film, and the effective exposure area of the photomask or reticle may be reduced due to this distortion. The phenomenon becomes more prominent as the stretched area of the pellicle film increases (the pecryl film increases). Such a phenomenon has been solved by increasing the rigidity of the pellicle frame while maintaining the area inside the pellicle frame (hereinafter referred to as an effective area) as much as possible (for example, Patent Documents 1 to 4). 4).
　また近年、液晶では、大きな一枚のパネルからパソコンや携帯電話等の面積の小さな画面のパターンを複数とれるように、大きな一枚のパネルを多面撮りすることが検討されている。そのため、有効露光面積を従来よりも広くしたい要望がある。しかし、装置自体は従来のものを使用するため、ペリクルの外寸を変更せずに、有効露光面積を従来よりも広くするという新しい課題が発生している。 Also, in recent years, it has been studied to take a large panel of multiple images so that a plurality of small screen patterns such as a personal computer or a mobile phone can be taken from a large panel. Therefore, there is a demand for making the effective exposure area wider than before. However, since the conventional apparatus itself is used, there is a new problem that the effective exposure area is made wider than before without changing the outer dimension of the pellicle.
特開２００１－１０９１３５号公報JP 2001-109135 A 特開２００１－４２５０７号公報JP 2001-42507 A 特開２００２－２９６７６３号公報JP 2002-296863 A 特開２００６－５６５４４号公報JP 2006-56544 A
　ペリクルは、上述のようにペリクル膜を貼り付けると、該ペリクル膜の張力によりフレームの辺が内側に向かって歪みを生じるが、上述の文献等に記載された技術を用いることで、ペリクルフレームの変形量がペリクル膜の張力による変形量より小さくなってバランスをとることができていた。 When the pellicle film is attached as described above, the side of the frame is distorted inward due to the tension of the pellicle film. By using the technique described in the above-mentioned literature, the pellicle frame The amount of deformation was smaller than the amount of deformation due to the tension of the pellicle membrane, and a balance could be achieved.
　しかし、新しい課題に対応するべく、ペリクルフレーム幅を細くして、従来通りの作製を行うと、ペリクルフレームの変形量がペリクル膜の張力による変形量より大きくなってしまう。このため、ペリクル膜をカットした時に、ペリクルフレームが単に内側に向けて歪むだではなく、ペリクルフレームが上下に変形したり、ペリクルフレームの角部が変形したりする。また、ペリクルフレームの剛性が小さいことから、ペリクル膜の張力とつり合う力が小さくなるためペリクル膜の張力を維持することができずに膜シワが発生してしまい、更には、膜張力が弱くなるためハンドリング時に膜が膨らんでハンドリングしにくいといった新しい問題が発生した。 However, if the pellicle frame width is narrowed and the conventional fabrication is performed in order to cope with a new problem, the deformation amount of the pellicle frame becomes larger than the deformation amount due to the tension of the pellicle film. For this reason, when the pellicle film is cut, the pellicle frame is not simply distorted inward, but the pellicle frame is deformed up and down, and the corners of the pellicle frame are deformed. Further, since the rigidity of the pellicle frame is small, the force that balances with the tension of the pellicle film is small, so that the tension of the pellicle film cannot be maintained and film wrinkles are generated, and further, the film tension is weakened. Therefore, a new problem has occurred that the film swells during handling and is difficult to handle.
　特にペリクル面積が、３，０００ｃｍ２、更に６，０００ｃｍ２、更には８，０００ｃｍ２を越えるような最大では３０，０００ｃｍ２以内の大型ペリクルでは特に問題になる。 Particularly pellicle area, 3,000 cm 2, further 6,000 2, more particularly problematic in large pellicle within 30,000 2 the maximum that exceeds the 8,000cm 2.
　本発明は、従来市場で使用されるとは予想されていなかった細い幅のペリクルフレームを使用して露光に影響しないペリクル及びペリクルフレーム並びにペリクルの製造方法を提供することをその目的にする。 It is an object of the present invention to provide a pellicle, a pellicle frame, and a method for manufacturing the pellicle that do not affect exposure using a thin pellicle frame that has not been expected to be used in the market.
　本願発明者らが鋭意検討した結果、細い幅の少なくとも一対の辺部がペリクルフレームの外側に膨出した略矩形のペリクルフレームを枠体内側へ応力をかけて撓ませた状態にした上で、ペリクル膜を貼り付けて展張することで、驚くべきことに、膜張力とフレーム応力とが、フレームが略矩形となる状態でつり合うことを見出した。そして、これまで、フレームを枠体外部へ突出した太鼓状に切り出し、そこにペリクル膜を展張することで、フレームを略矩形の形状にバランスさせていたが、細い幅の略矩形のペリクルフレームを用いた場合、ペリクル膜展張後にフレームを略矩形形状とするためには、予めペリクルフレームを枠体内部へ応力をかけて撓ませた状態にすることが重要であることを見出した。 As a result of diligent study by the inventors of the present application, after making a substantially rectangular pellicle frame in which at least a pair of sides with a narrow width bulge outside the pellicle frame is bent by applying stress to the inside of the frame body, It has been surprisingly found that the film tension and the frame stress are balanced in a state where the frame is substantially rectangular by pasting and spreading the pellicle film. And until now, the frame was cut out in a drum shape protruding outside the frame body, and the pellicle film was stretched there to balance the frame into a substantially rectangular shape. When used, it has been found that in order to make the frame substantially rectangular after the pellicle film is stretched, it is important that the pellicle frame is bent in advance by applying stress to the inside of the frame.
　本発明は、このような知見に基づいて上記課題を解決するものである。 The present invention solves the above problems based on such knowledge.
　すなわち、本発明に係るペリクルフレームは、四つの辺部により略矩形の枠状に形成されてペリクル膜を展張支持するペリクルフレームであって、辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、辺部の短辺幅／短辺長の割合が０．３％以上３．８％以下であり、少なくとも一対の辺部がペリクルフレームの外側に膨出している。 That is, the pellicle frame according to the present invention is a pellicle frame that is formed in a substantially rectangular frame shape by four sides to support the pellicle film, and the ratio of the long side width / long side length of the side is 0.3% or more and 2.2% or less, the ratio of the short side width / short side length of the side part is 0.3% or more and 3.8% or less, and at least a pair of side parts are outside the pellicle frame. Bulges.
　本発明に係るペリクルフレームによれば、辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、短辺幅／短辺長の割合が０．３％以上３．８％以下と細くすることで、ペリクルの外寸を変更せずに、有効露光面積を従来よりも広くすることができる。しかも、このように辺部の幅を狭くしても、少なくとも一対の辺部がペリクルフレームの外側に膨出しているので、この膨出した辺部をペリクルフレームの内側に向けて弾性変形させた状態で、ペリクルフレームにペリクル膜を貼り付けることで、ペリクルフレームの復元力とペリクル膜の展張力とをつり合わせることができる。その結果、ペリクル膜にシワが生じるのを抑制することができる。 According to the pellicle frame of the present invention, the ratio of the long side width / long side length of the side portion is 0.3% or more and 2.2% or less, and the ratio of the short side width / short side length is 0.3%. By reducing the thickness of the pellicle to not less than% and not more than 3.8%, the effective exposure area can be made wider than before without changing the outer dimension of the pellicle. In addition, even if the width of the side portion is reduced in this way, at least a pair of the side portions bulge outside the pellicle frame, so that the bulged side portions are elastically deformed toward the inside of the pellicle frame. In this state, by attaching the pellicle film to the pellicle frame, the restoring force of the pellicle frame and the expansion tension of the pellicle film can be balanced. As a result, wrinkles can be suppressed from occurring in the pellicle film.
　また、本発明に係るペリクルフレームにおいては、辺部の長辺長が、４００ｍｍ以上、２０００ｍｍ以下であり、辺部の短辺長が、２００ｍｍ以上、１８００ｍｍ以下とすることができるが、特に、ペリクル面積が２０，０００ｃｍ２以上３０，０００ｃｍ２以下で長辺の長さが１５００ｍｍ以上の場合、ペリクル膜のシワ防止と露光面積確保の観点から、辺部の長辺幅は８ｍｍ以上１５ｍｍ以下が好ましく、より好ましくは９ｍｍ以上１４．５ｍｍ以下、更には１０ｍｍ以上１４ｍｍ以下であり、辺部の短辺幅は７ｍｍ以上１５ｍｍ以下が好ましく、より好ましくは８ｍｍ以上１４．５ｍｍ以下、更には９ｍｍ以上１４ｍｍ以下である。また、ペリクル面積１２，０００ｃｍ２以上２０，０００ｃｍ２以下で、長辺の長さが１２００ｍｍ以上１５００ｍｍ以下の場合、辺部の長辺幅は５ｍｍ以上１１ｍｍ以下が好ましく、より好ましくは６ｍｍ以上１１ｍｍ以下、更には７ｍｍ以上１０．５ｍｍ以下であり、辺部の短辺幅が、４ｍｍ以上１１ｍｍ以下、好ましくは５ｍｍ以上１０．５ｍｍ以下、更には６ｍｍ以上１０ｍｍ以下である。また、ペリクル面積５，０００ｃｍ２以上１２，０００ｃｍ２以下で、長辺の長さが７００ｍｍ以上１４００ｍｍ以下の場合、辺部の長辺幅が、４ｍｍ以上１０ｍｍ以下が好ましく、より好ましくは５ｍｍ以上９．５ｍｍ以下、更には５．５ｍｍ以上９ｍｍ以下であり、辺部の短辺幅は、３ｍｍ以上１０ｍｍ以下が好ましく、より好ましくは４ｍｍ以上９ｍｍ以下、更には５ｍｍ以上８ｍｍ以下である。 In the pellicle frame according to the present invention, the long side length of the side portion may be 400 mm or more and 2000 mm or less, and the short side length of the side portion may be 200 mm or more and 1800 mm or less. If the area is the length of the long side at 20,000 cm 2 or more 30,000 2 or less is more than 1500 mm, in terms of wrinkle prevention with exposure area secured pellicle film, the long side width of the side portion is preferably more than 15mm below 8mm More preferably, it is 9 mm or more and 14.5 mm or less, further 10 mm or more and 14 mm or less, and the short side width of the side part is preferably 7 mm or more and 15 mm or less, more preferably 8 mm or more and 14.5 mm or less, and further 9 mm or more and 14 mm or less. It is. When the pellicle area is 12,000 cm 2 or more and 20,000 cm 2 or less and the length of the long side is 1200 mm or more and 1500 mm or less, the long side width of the side part is preferably 5 mm or more and 11 mm or less, more preferably 6 mm or more and 11 mm or less. Furthermore, it is 7 mm or more and 10.5 mm or less, and the short side width of the side portion is 4 mm or more and 11 mm or less, preferably 5 mm or more and 10.5 mm or less, and further 6 mm or more and 10 mm or less. When the pellicle area is 5,000 cm 2 or more and 12,000 cm 2 or less and the length of the long side is 700 mm or more and 1400 mm or less, the long side width of the side part is preferably 4 mm or more and 10 mm or less, more preferably 5 mm or more and 9 mm or less. 0.5 mm or less, further 5.5 mm or more and 9 mm or less, and the short side width of the side portion is preferably 3 mm or more and 10 mm or less, more preferably 4 mm or more and 9 mm or less, and further preferably 5 mm or more and 8 mm or less.
　また、本発明に係るペリクルフレームにおいては、辺部の一対の長辺部がペリクルフレームの外側に膨出しており、この一対の長辺部の膨出量が、３ｍｍ以上、２０ｍｍ以下であることが好ましい。これにより、この膨出した辺部をペリクルフレームの内側に向けて弾性変形させた状態で、ペリクルフレームにペリクル膜を貼り付ける際に、ペリクルフレームの復元力とペリクル膜の展張力とをつり合わせることが容易となるため、ペリクル膜にシワが生じるのをより有効に抑制することができる。 Further, in the pellicle frame according to the present invention, the pair of long side portions of the side portion bulges outside the pellicle frame, and the bulge amount of the pair of long side portions is 3 mm or more and 20 mm or less. Is preferred. Thus, when the pellicle film is affixed to the pellicle frame with the bulged sides elastically deformed toward the inside of the pellicle frame, the restoring force of the pellicle frame and the expansion tension of the pellicle film are balanced. Therefore, the generation of wrinkles in the pellicle film can be more effectively suppressed.
　また、本発明に係るペリクルフレームは、ヤング率が１ＧＰａ以上８０ＧＰａの材質により形成されるものとすることができる。このように、ヤング率が１ＧＰａ以上８０ＧＰａの材質によりペリクルフレームを形成することで、一般的な素材で製膜されたペリクル膜をペリクルフレームに貼り付けた際に、ペリクルフレームが略矩形状になる状態において、ペリクルフレームの復元力とペリクル膜の膜張力とを適切につり合わせることができる。 Also, the pellicle frame according to the present invention can be formed of a material having a Young's modulus of 1 GPa or more and 80 GPa. Thus, by forming the pellicle frame with a material having a Young's modulus of 1 GPa or more and 80 GPa, the pellicle frame becomes a substantially rectangular shape when the pellicle film formed of a general material is attached to the pellicle frame. In the state, the restoring force of the pellicle frame and the film tension of the pellicle film can be appropriately balanced.
　本発明に係るペリクルは、上記のペリクルフレームと、ペリクルフレームに展張支持されるペリクル膜と、を有するペリクルであって、少なくとも膨出された辺部がペリクルフレームの内側に向けて弾性変形された状態で、ペリクル膜がペリクルフレームに貼り付けられている。 A pellicle according to the present invention is a pellicle having the above-described pellicle frame and a pellicle film that is stretched and supported by the pellicle frame, and at least a bulged side portion is elastically deformed toward the inside of the pellicle frame. In the state, the pellicle film is attached to the pellicle frame.
　本発明に係るペリクルによれば、ペリクルの外寸を変更せずに、有効露光面積を従来よりも広くすることができ、しかも、ペリクルフレームの復元力とペリクル膜の展張力とをつり合わせることができるため、ペリクル膜にシワが生じるのを抑制することができる。 According to the pellicle of the present invention, the effective exposure area can be made wider than before without changing the outer dimension of the pellicle, and the restoring force of the pellicle frame and the expansion tension of the pellicle film are balanced. Therefore, wrinkles can be prevented from occurring in the pellicle film.
　また、本発明に係るペリクルは、膨出された辺部が、当該辺部の復元力とペリクル膜の膜張力とのつり合いにより、略直線状に形成されているものとすることができる。このように、辺部の復元力とペリクル膜の膜張力とのつり合いにより、辺部を略直線状に形成することで、有孔露光面積を確保しつつ、ペリクルフレームの復元力とペリクル膜の膜張力とを適切につり合わせることができる。 In addition, the pellicle according to the present invention can be such that the bulged side portion is formed in a substantially linear shape by the balance between the restoring force of the side portion and the film tension of the pellicle membrane. In this way, the balance between the restoring force of the side part and the film tension of the pellicle film forms the side part in a substantially linear shape, thereby securing the perforated exposure area and the restoring force of the pellicle frame and the pellicle film. The film tension can be balanced appropriately.
　また、本発明に係るペリクルにおいては、ペリクル膜には、以下の条件Ａ、条件Ｂ及び条件Ｃを全て満たすような大きさの膜張力が付与されていることが好ましい。 Further, in the pellicle according to the present invention, it is preferable that the pellicle film is given a film tension having a magnitude that satisfies all of the following conditions A, B, and C.
　条件Ａ：ペリクル膜が略水平となるようにペリクルを配置した状態において、ペリクル膜上の第１基準点であって、平面視でペリクルフレームの辺部の長辺部の内縁の中央点から当該長辺部の内縁と直交する方向に３０ｍｍ離れた第１基準点上に１０．６ｇの重りを載せた場合の当該第１基準点の沈み量が０．４ｍｍ以上、２．４ｍｍ以下である。 Condition A: In a state where the pellicle is arranged so that the pellicle film is substantially horizontal, the first reference point on the pellicle film is the center point of the inner edge of the long side part of the side part of the pellicle frame in plan view. When a 10.6 g weight is placed on the first reference point 30 mm away in the direction orthogonal to the inner edge of the long side, the sinking amount of the first reference point is 0.4 mm or more and 2.4 mm or less.
　条件Ｂ：ペリクル膜が略水平となるようにペリクルを配置した状態において、ペリクル膜上の第２基準点であって、平面視でペリクルフレームの辺部の短辺部の内縁の中央点から当該短辺部と直交する方向に３０ｍｍ離れた第２基準点上に１０．６ｇの重りを載せた場合の当該第２基準点の沈み量が０．３ｍｍ以上、２．３ｍｍ以下である。 Condition B: in a state where the pellicle is arranged so that the pellicle film is substantially horizontal, the second reference point on the pellicle film, which is a plan view from the center point of the inner edge of the short side part of the side part of the pellicle frame When a 10.6 g weight is placed on the second reference point 30 mm away in the direction orthogonal to the short side, the sinking amount of the second reference point is 0.3 mm or more and 2.3 mm or less.
　条件Ｃ：第１基準点の上記沈み量と第２基準点の上記沈み量との差の絶対値が０．４ｍｍ以下である。 Condition C: The absolute value of the difference between the sinking amount of the first reference point and the sinking amount of the second reference point is 0.4 mm or less.
　このように条件Ａ、条件Ｂ及び条件Ｃを満たすような大きさの膜張力をペリクル膜に付与することにより、有効露光面積を広く確保しながら、より有効にペリクル膜にシワが生じるのを抑制することができる。 In this way, by providing the pellicle film with a film tension having such a size as to satisfy the conditions A, B, and C, it is possible to suppress wrinkles on the pellicle film more effectively while ensuring a wide effective exposure area. can do.
　第１基準点での上記沈み量と第２基準点での上記沈み量が上記条件Ａ～条件Ｃで規定される範囲内にあると、ペリクル膜が緩むことが有効に抑制されるため長辺部及び短辺部付近でペリクル膜にシワが生じることが有効に抑制されるために好ましく、また、ペリクル膜に付与された膜張力が強すぎて少しの振動等でペリクル膜が破れることが抑制されるため好ましい。 If the sinking amount at the first reference point and the sinking amount at the second reference point are within the range defined by the conditions A to C, the pellicle film is effectively prevented from loosening. It is preferable that wrinkles occur in the pellicle film near the center and short sides, and it is preferable to suppress the pellicle film from being broken by slight vibrations because the film tension applied to the pellicle film is too strong. Therefore, it is preferable.
　ペリクルフレームは角部の剛性が相対的に強いため、角部からの対角線上に沿ってペリクル膜の膜張力は相対的に強くなると想定される。よって、細幅のペリクルフレームを用いた場合でも、対角線上のペリクル膜の膜張力は比較的強く維持できると考えられる、しかし、それとは対照的に、枠体の中央部付近はペリクル膜の膜張力に枠体が負けて辺が撓みやすくなるため、枠体の中央部分付近のペリクル膜の膜張力が小さくなることでペリクル膜をペリクルフレームに貼り付けた場合にペリクル膜にシワが発生したり、ペリクルのハンドリング時にペリクル膜にシワが発生したりしやすくなる。そのため、第１基準点での上記沈み量と第２基準点での上記沈み量が上記条件Ａ～条件Ｃで規定される範囲内にあると、ペリクルフレームの長辺側と短辺側の中央部分近傍である第１基準点及び第２基準点におけるペリクル膜の膜張力が強くなると共に、第１基準点及び第２基準点におけるペリクル膜の膜張力のバランスをとることができるため、ペリクル膜全体の張力のバランスがよくなり、細幅のペリクルフレームを用いることが可能なペリクルを作製することが可能となることを本発明者らは見出した。 Since the pellicle frame has relatively strong corner rigidity, it is assumed that the film tension of the pellicle film is relatively strong along the diagonal line from the corner. Therefore, even when a thin pellicle frame is used, it is considered that the film tension of the pellicle film on the diagonal line can be maintained relatively strong.However, in contrast, the film of the pellicle film is near the center of the frame. Since the frame loses its tension and the sides are easily bent, the film tension of the pellicle film near the center of the frame decreases, so that when the pellicle film is attached to the pellicle frame, wrinkles are generated on the pellicle film. In the handling of the pellicle, wrinkles are likely to occur in the pellicle film. Therefore, if the sinking amount at the first reference point and the sinking amount at the second reference point are within the range defined by the conditions A to C, the center of the long side and the short side of the pellicle frame The film tension of the pellicle film at the first reference point and the second reference point that are near the portion is increased, and the film tension of the pellicle film at the first reference point and the second reference point can be balanced. The present inventors have found that the balance of the overall tension is improved and a pellicle capable of using a narrow pellicle frame can be manufactured.
　本発明に係るペリクルの製造方法は、（ａ）基板上に成膜された高分子材料からなるペリクル膜を、開口部を有する枠体に当該開口部を覆うように貼り付ける工程と、（ｂ）枠体に貼り付けられたペリクル膜を、基板から剥離する工程と、（ｃ）四つの辺部により略矩形の枠状に形成されたペリクルフレームであって、少なくとも一対の辺部がペリクルフレームの外側に膨出しており、辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、辺部の短辺幅／短辺長の割合が０．３％以上３．８％以下である、ペリクルフレームを用意する工程と、（ｄ）ペリクルフレームの上記少なくとも一対の辺部に外力を付与することにより、当該少なくとも一対の辺部が略直線状になるように当該少なくとも一対の辺部を弾性変形させる工程と、（ｅ）工程（ｄ）の後に、上記少なくとも一対の辺部が略直線状になるように弾性変形している状態のペリクルフレームに、当該ペリクルフレームの開口部を覆うように枠体に貼り付けられたペリクル膜を貼り付ける工程と、（ｆ）工程（ｅ）の後に、上記少なくとも一対の辺部に付与している上記外力を取り除くことにより、ペリクル膜をペリクルフレームによって展張支持する工程と、（ｇ）工程（ｅ）の後に、ペリクル膜の余剰部分及び枠体を除去する工程と、を備える。なお、工程（ｄ）における略直線状にとは、図９の外側に膨出Ｐから少しでもＬ直線に近づいた状態をいい、具体的には、Ｐから０．５ｍｍ以上Ｌ直線に近づくことが好ましい。一方で、工程（ｅ）を経た後のペリクルは略矩形形状であるが、この形状は露光装置への取り付けに支障が無い程度に矩形形状であることをいう。 A method for manufacturing a pellicle according to the present invention includes: (a) a step of attaching a pellicle film made of a polymer material formed on a substrate to a frame having an opening so as to cover the opening; ) A step of peeling the pellicle film attached to the frame from the substrate; and (c) a pellicle frame formed in a substantially rectangular frame shape by four sides, and at least a pair of sides is a pellicle frame. The ratio of the long side width / long side length of the side part is 0.3% to 2.2%, and the short side width / short side length ratio of the side part is 0. 0%. A step of preparing a pellicle frame that is not less than 3% and not more than 3.8%, and (d) applying at least one external force to the at least one pair of sides of the pellicle frame so that the at least one pair of sides is substantially linear. Elastically deforming the at least one pair of sides so that (E) After step (d), the frame body is so formed as to cover the opening of the pellicle frame on the pellicle frame that is elastically deformed so that the at least one pair of sides are substantially linear. A step of affixing the pellicle film affixed to the substrate, and (f) after the step (e), the pellicle film is stretched and supported by the pellicle frame by removing the external force applied to the at least one pair of sides. And (g) after the step (e), a step of removing an excess portion of the pellicle film and a frame body. In addition, the substantially linear shape in the step (d) means a state in which the bulge P has approached the L straight line even slightly from the bulge P to the outside of FIG. Is preferred. On the other hand, the pellicle after the step (e) has a substantially rectangular shape, which means that the shape is rectangular so as not to hinder the attachment to the exposure apparatus.
　本発明に係るペリクルの製造方法によれば、工程（ｃ）において辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、辺部の短辺幅／短辺長の割合が０．３％以上３．８％以下であるペリクルフレームを用意しているため、有効露光面積が従来よりも広くなったペリクルを得ることができる。その上、工程（ｄ）において上記少なくとも一対の辺部が略直線状になるように上記少なくとも一対の辺部を弾性変形させ、工程（ｅ）において、この状態のペリクルフレームにペリクル膜を貼り付けるため、ペリクルフレームの復元力とペリクル膜の展張力とをつり合わせることができる。その結果、ペリクル膜にシワが生じるのを抑制することができる。 According to the pellicle manufacturing method of the present invention, the ratio of the long side width / long side length in the step (c) is 0.3% or more and 2.2% or less, and the short side width of the side portion. / Since a pellicle frame having a short side length ratio of 0.3% or more and 3.8% or less is prepared, a pellicle having a wider effective exposure area than the conventional one can be obtained. In addition, in step (d), the at least one pair of sides is elastically deformed so that the at least one pair of sides is substantially linear, and in step (e), a pellicle film is attached to the pellicle frame in this state. Therefore, the restoring force of the pellicle frame and the spreading tension of the pellicle film can be balanced. As a result, wrinkles can be suppressed from occurring in the pellicle film.
　本発明は、従来市場で使用されるとは予想されていなかった細い幅のペリクルフレームを使用しても、露光に問題なく、有効露光面積を拡大させることができ、また、膜シワもなく、細くても十分な膜張力を確保でき、更に、ハンドリングでも問題がないペリクル、及び、そのようなペリクルの製造方法を提供することができる。 The present invention can expand the effective exposure area without any problem even if a thin pellicle frame that was not expected to be used in the market is used, and there is no film wrinkle. Even if it is thin, sufficient film tension can be secured, and furthermore, a pellicle that does not have a problem in handling and a method for manufacturing such a pellicle can be provided.
ペリクルの斜視図である。It is a perspective view of a pellicle. ペリクルの縦断面図である。It is a longitudinal cross-sectional view of a pellicle. 枠体の形の説明図である。It is explanatory drawing of the shape of a frame. ペリクルの製造プロセスを示す説明図である。It is explanatory drawing which shows the manufacturing process of a pellicle. ペリクルフレームの形の説明図である。It is explanatory drawing of the shape of a pellicle frame. ペリクルの他の製造プロセスを示す説明図である。It is explanatory drawing which shows the other manufacturing process of a pellicle. 長辺側の膜沈み量と短辺側の膜沈み量の測定方法を説明するための模式的な斜視図である。It is a typical perspective view for demonstrating the measuring method of the film sink amount of a long side and the film sink amount of a short side. 長辺側の膜沈み量と短辺側の膜沈み量の測定方法を説明するための模式的な断面図である。It is typical sectional drawing for demonstrating the measuring method of the film sink amount of a long side and the film sink amount of a short side. 膨出量の定義を示す説明図である。It is explanatory drawing which shows the definition of the bulging amount. 実施例及び比較例の評価結果を示す図である。It is a figure which shows the evaluation result of an Example and a comparative example.
　本発明の実施形態を説明する。なお、以下に説明する実施形態は本発明の構成の例であり、本発明は以下の実施形態に制限されるものではない。また、本明細書及び図面において、実質的に同一の機能構成を有する構成要素については、同一の符号を付することにより重複説明を省略する。 Embodiments of the present invention will be described. The embodiments described below are examples of the configuration of the present invention, and the present invention is not limited to the following embodiments. Further, in the present specification and the drawings, the same reference numerals are given to constituent elements having substantially the same functional configuration, and redundant description is omitted.
　図１及び図２にペリクル１を示す。ペリクル１は、例えば矩形の枠状で開口部Ｆを有するペリクルフレーム１０と、ペリクルフレーム１０の上面にその開口部Ｆを覆うように貼り付けられてペリクルフレーム１０に展張支持されたペリクル膜１１と、ペリクルフレーム１０の下面に塗布された粘着剤１２及びその粘着剤１２の表面を覆う保護フィルム１３を有している。 1 and 2 show the pellicle 1. The pellicle 1 includes, for example, a pellicle frame 10 that has a rectangular frame shape and has an opening F, and a pellicle film 11 that is attached to the upper surface of the pellicle frame 10 so as to cover the opening F and is stretched and supported on the pellicle frame 10. The adhesive 12 applied to the lower surface of the pellicle frame 10 and the protective film 13 covering the surface of the adhesive 12 are provided.
　ペリクル膜１１は、ニトロセルロースやセルロース誘導体、シクロオレフィン系樹脂、フッ素系高分子など透明な高分子膜で構成されており、膜厚は、１μｍ以上１０μｍ以下が好ましく、より好ましくは２μｍ以上８μｍ以下、更に好ましくは２．５μｍ以上７μｍ以下である。また、ペリクルフレーム１０の開口部Ｆの開口面積は、例えば１０００ｃｍ２以上であり、本実施形態におけるペリクル１は、いわゆる大型ペリクルである。ペリクルフレーム１０の開口部Ｆの開口面積が１０００ｃｍ２以上である場合、ペリクル製造工程内のハンドリング時に膜張力が弱いとペリクルフレームの自重により膜シワが発生したり、ハンドリング治具から外れる可能性があるが、本実施形態を用いることで、劇的にハンドリング時の膜シワの発生やハンドリング治具から外れるといった可能性が抑止される。特にペリクル面積が３，０００ｃｍ２、更には６，０００ｃｍ２を越えるような大型ペリクルの場合に発揮される。 The pellicle film 11 is made of a transparent polymer film such as nitrocellulose, cellulose derivative, cycloolefin resin, or fluorine polymer. The film thickness is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less. More preferably, it is 2.5 μm or more and 7 μm or less. Further, the opening area of the opening F of the pellicle frame 10 is, for example, 1000 cm 2 or more, and the pellicle 1 in the present embodiment is a so-called large pellicle. When the opening area of the opening F of the pellicle frame 10 is 1000 cm 2 or more, if the film tension is weak during handling in the pellicle manufacturing process, film wrinkles may occur due to the weight of the pellicle frame or it may come off from the handling jig. However, by using this embodiment, the possibility of drastic film wrinkling during handling and removal from the handling jig is suppressed. Particularly pellicle area 3,000 cm 2, and more is exhibited in the case of a large-sized pellicle exceeding 6,000 2.
　ところで、細いペリクルフレーム１０にペリクル膜１１を展張させたペリクル１を作製すると、ペリクル膜１１の膜張力にペリクルフレーム１０の剛性が負けて大きく変形する。そこで、先にペリクルフレーム１０に応力を持たせておき、この応力を持たせたペリクルフレーム１０にペリクル膜１１を貼り付けて、ペリクル膜１１の膜張力とペリクルフレーム１０の応力とを釣合わせるようにすることが重要である。後述するように、ペリクル膜１１をペリクルフレーム１０貼り付ける前にペリクル膜１１を枠体に貼り付けるが、更にペリクル膜１１の膜張力を上げるためには、この枠体での膜張力を上げておくこともできる。そうすることで、膜張力もあり、有効露光面積も確保できるペリクルが作製可能になる。 Incidentally, when the pellicle 1 in which the pellicle film 11 is stretched on the thin pellicle frame 10 is manufactured, the rigidity of the pellicle frame 10 is lost due to the film tension of the pellicle film 11, and the pellicle film 11 is greatly deformed. Therefore, stress is applied to the pellicle frame 10 first, and the pellicle film 11 is attached to the pellicle frame 10 having this stress, so that the film tension of the pellicle film 11 and the stress of the pellicle frame 10 are balanced. It is important to make it. As will be described later, before the pellicle film 11 is attached to the pellicle frame 10, the pellicle film 11 is attached to the frame. To further increase the film tension of the pellicle film 11, the film tension in the frame is increased. It can also be left. By doing so, a pellicle that has film tension and can secure an effective exposure area can be manufactured.
　まずは枠体での膜張力を上げる方法を述べる。ペリクル１の製造は、図３に示す枠体２０を用いて行われる。枠体２０は、略矩形の枠状に形成されており、対向する一対の長辺部２０ａと対向する一対の短辺部２０ｂとからなる４辺部を有している。この枠体２０は、例えば図３の（Ａ）のように４辺部が直線状のもの、（Ｂ）のように対となる長辺部２０ａが枠体２０の外側に凸となるように湾曲膨出した太鼓状に形成されたもの、（Ｃ）のように対となる短辺部２０ｂが枠体２０の外側に凸となるように湾曲膨出した太鼓状に形成されたもの、（Ｄ）のように全ての辺部である一対の長辺部２０ａ及び一対の短辺部２０ｂが枠体２０の外側に凸となるように湾曲膨出した太鼓状に形成されたものを用いることができる。外側に凸となる形状としては、１つの角部から隣接する角部に亘って太鼓状になっていてもよく、長辺部２０ａ及び一対の短辺部２０ｂの中央付近のみがなだらかに凸形状になっていてもよい。 First, a method for increasing the film tension in the frame will be described. The pellicle 1 is manufactured using the frame 20 shown in FIG. The frame body 20 is formed in a substantially rectangular frame shape, and has four side portions including a pair of opposed long side portions 20a and a pair of opposed short side portions 20b. The frame 20 has, for example, four sides that are linear as shown in FIG. 3A, and a pair of long sides 20a that protrude outward from the frame 20 as shown in FIG. A curved and bulging drum shape, or a curved and bulging drum shape such that the paired short side portions 20b are convex outward of the frame body 20 as shown in FIG. A pair of long side portions 20a and a pair of short side portions 20b that are all side portions as shown in D) are formed in a drum-like shape that is curved and bulged so as to protrude outward from the frame body 20. Can do. As the shape that protrudes outward, it may be a drum shape from one corner to the adjacent corner, and only the vicinity of the center of the long side 20a and the pair of short sides 20b is gently convex. It may be.
　図４は、ペリクル１の製造方法の一例の概略を示す説明図である。図４の（Ａ）に示すように、先ず開口部Ｇを有する枠体２０を用意する。次に図４の（Ｂ）に示すように、枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂの中央付近を、治具などを用いて内側に押さえ込む。これにより、外側から内側に外力が付与されて、枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂが内側に向けて弾性変形する。 FIG. 4 is an explanatory diagram showing an outline of an example of a method for manufacturing the pellicle 1. As shown in FIG. 4A, first, a frame 20 having an opening G is prepared. Next, as shown in FIG. 4B, the vicinity of the center of the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 is pressed inward using a jig or the like. Accordingly, an external force is applied from the outside to the inside, and the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 are elastically deformed toward the inside.
　また、ＣＶＤ、スパッタリングなどの成膜技術によりペリクル膜１１が成膜された基板３０を用意する。そして、一対の長辺部２０ａ及び一対の短辺部２０ｂが内側に弾性変形した状態の枠体２０に、その開口部Ｇを覆うように、基板３０に成膜されたペリクル膜１１を貼り付ける。このときのペリクル膜１１と枠体２０との接着は、枠体２０上に塗布された接着材により行われる。その後、枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂを弾性変形させていた外力を取り除く。なお、図４の（Ｂ）では、説明のために枠体２０の内側への変形量を大きく描いているが、実際の枠体２０の押し込み量は、枠体材の弾性変形領域であれば任意の力で押さえ込むことができる。また、図３の（Ｂ）、（Ｃ）、（Ｄ）に示したように、辺部が外側に凸となるように湾曲膨出した枠体２０の場合には、外側から押さえ込むことにより辺部が略直線状になるよう弾性変形させてもよい。 Further, a substrate 30 on which the pellicle film 11 is formed by a film forming technique such as CVD or sputtering is prepared. Then, the pellicle film 11 formed on the substrate 30 is attached to the frame 20 in a state where the pair of long side portions 20a and the pair of short side portions 20b are elastically deformed inward. . At this time, adhesion between the pellicle film 11 and the frame body 20 is performed by an adhesive applied on the frame body 20. Thereafter, the external force that has elastically deformed the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 is removed. In FIG. 4B, for the sake of explanation, the amount of deformation inward of the frame body 20 is drawn large, but the actual pushing amount of the frame body 20 is an elastic deformation region of the frame body material. It can be pressed with any force. In addition, as shown in FIGS. 3B, 3C, and 3D, in the case of the frame body 20 that is curved and bulged so that the side portion protrudes outward, the side is pressed by pressing from the outside. The portion may be elastically deformed so as to be substantially linear.
　枠体２０の材質としては、例えば、アルミニウム、アルミニウム合金（５０００系、６０００系、７０００系等）等の金属、セラミックス（ＳｉＣ、Ａ１Ｎ、Ａ１２０３等）、セラミックスと金属の複合材料（Ａｌ－ＳｉＣ、Ａｌ－Ａ１Ｎ、ＡＬ－Ａ１２０３等）、樹脂等があげられ、中でもアルミニウムやその合金を挙げることができ、より具体的には、アルミニウムとマグネシウムの合金、アルミニウムとマグネシウムそしてケイ素の合金、アルミニウムと亜鉛そしてマグネシウムの合金など、弾性変形をおこさせるものが好ましい。 The material of the frame member 20, for example, aluminum, an aluminum alloy (5000 series, 6000 series, 7000 series, etc.) or the like of metal, ceramics (SiC, A1N, A1 2 0 3 , etc.), ceramics and metal composites (Al -SiC, Al-A1N, AL-A1 2 0 3 etc.), resin, etc., among which aluminum and its alloys can be mentioned, more specifically, aluminum and magnesium alloys, aluminum and magnesium and silicon Alloys that cause elastic deformation such as alloys of aluminum, zinc, and magnesium are preferred.
　次に図４の（Ｃ）に示すように、枠体２０が貼り付けられたペリクル膜１１を基板３０から剥離する。このとき、枠体２０の弾性変形を維持していた力を取り除くことにより、枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂが弾性復元力（膨張力）により元の形に戻ろうとして外側に変位する。これにより、ペリクル膜１１には４辺の外側方向に向かう引張力が作用し、膜張力が上がる。 Next, as shown in FIG. 4C, the pellicle film 11 to which the frame body 20 is attached is peeled from the substrate 30. At this time, by removing the force that maintained the elastic deformation of the frame body 20, the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 are restored to their original shapes by elastic restoring force (expansion force). Displaces outward to return. As a result, a tensile force toward the outer side of the four sides acts on the pellicle film 11, and the film tension increases.
　次に図４の（Ｄ）に示すように、ペリクルフレーム１０を用意する。ペリクルフレーム１０の上面には、接着剤が塗布されている。次に、図４の（Ｅ）に示すように、ペリクルフレーム１０の上面に、その開口部Ｆを覆うように、枠体２０が貼り付けられたペリクル膜１１を貼り付ける。これにより、ペリクル膜１１は、膜張力が維持された状態で、ペリクルフレーム１０に貼り付けられる。その後、枠体２０を含むペリクル膜１１の余剰部分を除去する。 Next, as shown in FIG. 4D, a pellicle frame 10 is prepared. An adhesive is applied to the upper surface of the pellicle frame 10. Next, as shown in FIG. 4E, the pellicle film 11 with the frame 20 attached is attached to the upper surface of the pellicle frame 10 so as to cover the opening F. As a result, the pellicle film 11 is attached to the pellicle frame 10 in a state where the film tension is maintained. Thereafter, an excess portion of the pellicle film 11 including the frame body 20 is removed.
　本実施形態によれば、温度変化を与えることなく、高分子材料からなるペリクル膜１１の膜張力を向上できるので、ペリクル膜１１の物性が変動することを防止でき、当該ペリクル１を利用した露光処理を適正に行うことができる。また、ペリクルフレーム１０や粘着剤１２、ペリクル膜１１などの材質に温度変化に耐え得るものを用いる必要がなく、材質の選択の自由度が広がる。また、温度変化の付与や、温度変化に伴う空調を行う高価な設備が必要なく、その制御プロセスが容易になる。さらに、高温若しくは低温に曝されないため、熱による粘着剤１２等の劣化がなく、ペリクル１の平坦性や寸法精度が確保され、精度の高い露光処理を行うことができる。 According to the present embodiment, since the film tension of the pellicle film 11 made of a polymer material can be improved without causing a temperature change, the physical properties of the pellicle film 11 can be prevented from changing, and exposure using the pellicle 1 can be performed. Processing can be performed appropriately. In addition, it is not necessary to use materials that can withstand temperature changes such as the pellicle frame 10, the adhesive 12, and the pellicle film 11, and the degree of freedom in selecting the material is increased. Further, there is no need for expensive equipment for imparting temperature changes or performing air conditioning accompanying temperature changes, and the control process is facilitated. Furthermore, since it is not exposed to high or low temperatures, the adhesive 12 and the like are not deteriorated by heat, the flatness and dimensional accuracy of the pellicle 1 are ensured, and highly accurate exposure processing can be performed.
　また、本実施形態で記載したペリクル１は、ペリクルフレーム１０の開口部Ｆの開口面積が１０００ｃｍ２以上の大型ペリクルであるが、膜張力を向上できるので、大型化によって顕著になるペリクル膜１１の自重による撓みを抑制できる。よって、大型ペリクルであっても、精度の高い露光処理を実現できる。また、露光用基盤への装着時に周囲雰囲気を巻き込んで生じるペリクル膜１１の膨らみも抑制できる。これにより、そのペリクル膜１１の膨らみが戻るまでの待ち時間が減り、製造時間を短縮できる。 The pellicle 1 described in the present embodiment is a large pellicle with an opening area F of the pellicle frame 10 of 1000 cm 2 or more. However, since the film tension can be improved, Deflection due to its own weight can be suppressed. Therefore, even with a large pellicle, highly accurate exposure processing can be realized. Further, the swelling of the pellicle film 11 caused by the surrounding atmosphere involved when being mounted on the exposure substrate can be suppressed. Thereby, the waiting time until the swelling of the pellicle film 11 returns is reduced, and the manufacturing time can be shortened.
　さらに、図３（Ｂ）～（Ｄ）に示したように、枠体２０の少なくとも１辺部が外側に凸となるように湾曲膨出した初期形状を有している場合には、枠体２０の辺部の内側への変形量を大きく確保でき、その分、弾性復元力（膨張力）により元に戻る際の変形量も大きく確保できる。よって、ペリクル膜１１をより強く引っ張ることができ、膜張力をさらに上げることができる。 Furthermore, as shown in FIGS. 3B to 3D, when the frame 20 has an initial shape that is curved and bulged so that at least one side of the frame 20 protrudes outward, the frame A large amount of deformation toward the inside of the 20 side portions can be ensured, and accordingly, a large amount of deformation can be secured when returning to the original state by an elastic restoring force (expansion force). Therefore, the pellicle film 11 can be pulled more strongly, and the film tension can be further increased.
　なお、本実施形態では、ペリクル膜１１を貼り付ける際に枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂの全てを内側に弾性変形させてもよく、４辺部のうちの任意の辺部を内側に弾性変形させてもよい。これにより、ペリクル膜１１の長辺方向、若しくは短辺方向の張力を発現させたい方向のみに膜張力を増加させることができ、ペリクル膜１１が長方形の場合などは長辺方向に強い張力を与えるなど、４方向の張力バランスの均等化を図ることができる。特に、ペリクルフレーム１０の剛性が高い場合には、枠体２０の任意の辺部を内側に弾性変形させておくことが好ましい。ここで、高い剛性の範囲はヤング率が９０～４５０の範囲である。具体的には、ファインセラミック（例えば、アルミナ、炭化ケイ素など）、鉄、ＳＵＳ、チタン等である。 In the present embodiment, when the pellicle film 11 is attached, all of the pair of long side portions 20a and the pair of short side portions 20b of the frame body 20 may be elastically deformed inward. Any side may be elastically deformed inward. Thus, the film tension can be increased only in the direction in which the tension in the long side direction or the short side direction of the pellicle film 11 is desired to be expressed. When the pellicle film 11 is rectangular, a strong tension is applied in the long side direction. For example, the tension balance in the four directions can be equalized. In particular, when the rigidity of the pellicle frame 10 is high, it is preferable that an arbitrary side portion of the frame body 20 is elastically deformed inward. Here, the range of high rigidity is the range of 90 to 450 Young's modulus. Specifically, they are fine ceramics (for example, alumina, silicon carbide, etc.), iron, SUS, titanium and the like.
　また、本実施形態では、枠体２０の一対の長辺部２０ａ及び一対の短辺部２０ｂを変形させる外力を、枠体２０にペリクル膜１１を貼り付けた後であって基板３０からペリクル膜１１を離脱させる前に除去していたが、基板３０からペリクル膜１１を離脱させた後であってペリクル膜１１をペリクルフレーム１０に貼り付ける前に除去してもよい。また、当該外力の除去を、ペリクル膜１１をペリクルフレーム１０に貼り付けた後に行ってもよい。 In the present embodiment, the external force that deforms the pair of long sides 20a and the pair of short sides 20b of the frame 20 is applied to the pellicle film 11 from the substrate 30 after the pellicle film 11 is attached to the frame 20. 11 may be removed before the pellicle film 11 is detached from the substrate 30 and before the pellicle film 11 is attached to the pellicle frame 10. Further, the external force may be removed after the pellicle film 11 is attached to the pellicle frame 10.
　上記実施形態では、ペリクル膜１１を貼り付ける際に枠体２０を弾性変形させていたが、ペリクルフレーム１０を弾性変形させてもよい。 In the above embodiment, the frame 20 is elastically deformed when the pellicle film 11 is attached, but the pellicle frame 10 may be elastically deformed.
　図５は、この例で用いられるペリクルフレーム１０の形状を示す。図５に示すように、ペリクルフレーム１０は、略矩形の枠状に形成されており、対向する一対の長辺部１０ａと対向する一対の短辺部１０ｂとからなる４辺部を有している。このペリクルフレーム１０は、例えば図５の（Ｂ）のように対となる長辺部１０ａがペリクルフレーム１０の外側に凸となるように湾曲膨出した太鼓状に形成されたもの、（Ｃ）のように対となる短辺部１０ｂがペリクルフレーム１０の外側に凸となるように湾曲膨出した太鼓状に形成されたもの、（Ｄ）のように全ての辺部であるの一対の長辺部１０ａ及び一対の短辺部１０ｂがペリクルフレーム１０の外側に凸となるように湾曲膨出した太鼓状に形成されたものを用いることができる。 FIG. 5 shows the shape of the pellicle frame 10 used in this example. As shown in FIG. 5, the pellicle frame 10 is formed in a substantially rectangular frame shape, and has four sides including a pair of opposed long sides 10 a and a pair of opposed short sides 10 b. Yes. The pellicle frame 10 is formed in a drum-like shape, for example, as shown in FIG. 5B, in which a pair of long side portions 10a are curved and bulged so as to protrude outward from the pellicle frame 10. A pair of short sides 10b formed in a drum-like shape that is curved and bulged so as to protrude outward from the pellicle frame 10, and a pair of long sides that are all sides as shown in (D) It is possible to use a drum-like shape in which the side portion 10 a and the pair of short side portions 10 b are curved and bulged so as to protrude outward from the pellicle frame 10.
　ペリクルフレーム１０の材質は、ヤング率が１ＧＰａ以上８０ＧＰａ以下のものであれば何でもよい。このヤング率を１ＧＰａよりも小さくすると、膜の張力の方が強すぎて、フレームの復元力を利用することができないというという問題がある。一方、このヤング率を８０ＧＰａよりも大きくすると、剛性が高いため弾性変形させることが困難になり、また高い復元力を望めないという問題がある。このため、このヤング率を１ＧＰａ以上８０ＧＰａ以下とすることで、膜張力とつりあう適度な復元力を利用できるという利点がある。例えば、アルミニウムやその合金、あるいはセラミックス、樹脂等といったペリクルフレームに一般的に用いられるものであればよい。ペリクルフレーム１０の材質は、大型化による自重の増加を考慮すれば、軽量で、かつ、剛性を有するものが好ましく、アルミニウムやその合金が好ましい。 The material of the pellicle frame 10 may be anything as long as the Young's modulus is 1 GPa or more and 80 GPa or less. When this Young's modulus is less than 1 GPa, there is a problem that the tension of the film is too strong and the restoring force of the frame cannot be used. On the other hand, when the Young's modulus is larger than 80 GPa, there is a problem that it is difficult to elastically deform due to high rigidity and a high restoring force cannot be expected. For this reason, there exists an advantage that the moderate restoring force which balances a film | membrane tension can be utilized by making this Young's modulus 1 GPa or more and 80 GPa or less. For example, any material generally used for a pellicle frame such as aluminum, an alloy thereof, ceramics, or resin may be used. The material of the pellicle frame 10 is preferably lightweight and rigid considering the increase in its own weight due to an increase in size, and is preferably aluminum or an alloy thereof.
　ペリクルフレーム１０の厚み（長辺部１０ａ及び短辺部１０ｂの厚み）は、２．５ｍｍ以上１０ｍｍ以下であり、好ましくは、３．０ｍｍ以上８ｍｍ以下であり、更に好ましくは４．０ｍｍ以上７．０ｍｍ以下である。何故なら、当該厚みがこの範囲にあると、異物がペリクル膜１１に付着した場合であっても、この異物と露光用基盤のパターンとが実質的に同じ像として描写されない上に、ペリクル膜１１の透過率を実質的に低下させないためである。また、ペリクルフレーム１０の幅（長辺部１０ａ及び短辺部１０ｂの幅）は、長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、好ましくは０．５％以上２．２％以下であり、更に好ましくは、０．５５％以上２．１％以下であり、更に好ましくは０．６％以上２．０％以下であることが好ましく、当該割合の他の好ましい例は、０．４％以上２．１％以下であり、更に好ましくは、０．５％以上２．０％以下であり、更に好ましくは、０．９％以下であり、更に好ましくは、０．８％以下である。また、短辺幅／短辺長の割合は、０．３％以上３．８％以下であり、好ましくは０．５％以上３．８％以下であり、好ましくは０．５５％以上３．５％以下であり、更に好ましくは、０．６％以上３．０％以下であり、当該割合の他の好ましい例は０．３％以上２．２％以下であり、更に好ましくは０．４％以上２．１％以下であり、更に好ましくは０．５％以上２．０％以下であり、更に好ましくは１．０％以下であり、更に好ましくは、０．９％以下である。 The thickness of the pellicle frame 10 (thickness of the long side portion 10a and the short side portion 10b) is 2.5 mm or more and 10 mm or less, preferably 3.0 mm or more and 8 mm or less, more preferably 4.0 mm or more and 7. 0 mm or less. This is because when the thickness is within this range, even if the foreign matter adheres to the pellicle film 11, the foreign matter and the pattern of the exposure base are not drawn as substantially the same image. This is because the transmittance of the glass is not substantially lowered. The width of the pellicle frame 10 (the width of the long side portion 10a and the short side portion 10b) is such that the ratio of the long side width / the long side length is 0.3% or more and 2.2% or less. 5% or more and 2.2% or less, more preferably 0.55% or more and 2.1% or less, and further preferably 0.6% or more and 2.0% or less. Another preferable example is 0.4% or more and 2.1% or less, more preferably 0.5% or more and 2.0% or less, and further preferably 0.9% or less, and further preferably Is 0.8% or less. The ratio of short side width / short side length is 0.3% to 3.8%, preferably 0.5% to 3.8%, preferably 0.55% to 3. 5% or less, more preferably 0.6% or more and 3.0% or less, and other preferable examples of the ratio are 0.3% or more and 2.2% or less, and more preferably 0.4% or less. % Or more and 2.1% or less, more preferably 0.5% or more and 2.0% or less, further preferably 1.0% or less, and further preferably 0.9% or less.
　なお、長辺長とは、ペリクルフレーム１０における長辺部１０ａの外寸を意味し、短辺長とは、ペリクルフレーム１０における短辺部１０ｂの外寸を意味する。 The long side length means the outer dimension of the long side portion 10a in the pellicle frame 10, and the short side length means the outer dimension of the short side portion 10b in the pellicle frame 10.
　ペリクルフレーム１０の長辺長は、例えば４００ｍｍ以上、２０００ｍｍ以下、好ましくは、７００ｍｍ以上、１８００ｍｍ以下、更に好ましくは、９００ｍｍ以上、１６００ｍｍ以下、特に好ましくは、１２００ｍｍ以上、１４００ｍｍ以下であり、ペリクルフレーム１０の短辺長は、例えば２００ｍｍ以上、１８００ｍｍ以下、好ましくは、５００ｍｍ以上、１６００ｍｍ以下、更には、７００ｍｍ以上、１２００ｍｍ以下である。 The long side length of the pellicle frame 10 is, for example, 400 mm or more and 2000 mm or less, preferably 700 mm or more and 1800 mm or less, more preferably 900 mm or more and 1600 mm or less, and particularly preferably 1200 mm or more and 1400 mm or less. The short side length is, for example, 200 mm or more and 1800 mm or less, preferably 500 mm or more and 1600 mm or less, and further 700 mm or more and 1200 mm or less.
　ペリクルフレーム１０の長辺幅（長辺部１０ａの幅）は、例えば５ｍｍ以上、１５ｍｍ以下とすることができ、ペリクルフレーム１０の短辺幅（短辺部１０ｂの幅）は、例えば４ｍｍ以上、１５ｍｍ以下とすることができる。 The long side width of the pellicle frame 10 (width of the long side portion 10a) can be, for example, 5 mm or more and 15 mm or less, and the short side width of the pellicle frame 10 (width of the short side portion 10b) is, for example, 4 mm or more. It can be 15 mm or less.
　図６は、この例のペリクル１の製造方法の概略を示す説明図である。図６の（Ａ）に示すように、先ずペリクルフレーム１０を用意する。ペリクルフレーム１０の上面には、接着剤が塗布されている。次に図６の（Ｂ）に示すように、ペリクルフレーム１０の一対の長辺部１０ａ及び一対の短辺部１０ｂの中央付近を、治具などを用いて抑え込む。これにより、外側から内側に外力が付与されて、ペリクルフレーム１０の一対の長辺部１０ａ及び一対の短辺部１０ｂが内側に向けて弾性変形する。この状態で、ペリクルフレーム１０の上面に、その開口部Ｆを覆うように、枠体２０に貼り付けられたペリクル膜１１を貼り付ける。このペリクル膜１１は、上述の実施形態のように初めに基板３０上に成膜され、次に枠体２０に貼り付けられ、その後基板３０が取り外されたものである。なお、本実施形態では、上述の実施形態のように外力を付与して枠体２０を弾性変形させている必要はない。また、図６では、説明のためにペリクルフレーム１０の内側への変形量を大きく描いているが、実際のペリクルフレーム１０の押し込み量は、フレーム材の弾性変形領域であれば任意の力で押さえ込むことができる。また、図５の（Ｂ）、（Ｃ）、（Ｄ）に示したように、辺部が外側に凸となるように湾曲膨出したペリクルフレーム１０の場合には、外側から押さえ込むことにより辺部が略直線状になるように弾性変形させてもよい。 FIG. 6 is an explanatory diagram showing an outline of a method for manufacturing the pellicle 1 of this example. As shown in FIG. 6A, first, a pellicle frame 10 is prepared. An adhesive is applied to the upper surface of the pellicle frame 10. Next, as shown in FIG. 6B, the vicinity of the center of the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 is suppressed using a jig or the like. Thereby, an external force is applied from the outside to the inside, and the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 are elastically deformed inward. In this state, the pellicle film 11 attached to the frame body 20 is attached to the upper surface of the pellicle frame 10 so as to cover the opening F. The pellicle film 11 is formed on the substrate 30 first and then attached to the frame 20 as in the above-described embodiment, and then the substrate 30 is removed. In the present embodiment, it is not necessary to elastically deform the frame body 20 by applying an external force as in the above-described embodiment. Further, in FIG. 6, the amount of deformation toward the inside of the pellicle frame 10 is drawn large for the sake of explanation, but the actual amount of push-in of the pellicle frame 10 is depressed by an arbitrary force as long as it is an elastic deformation region of the frame material. be able to. Further, as shown in FIGS. 5B, 5C, and 5D, in the case of the pellicle frame 10 that is curved and bulged so that the side is convex outward, the side is pressed by pressing from the outside. The portion may be elastically deformed so as to be substantially linear.
　次に図６の（Ｃ）に示すように、ペリクルフレーム１０に付与されていた外力を取り除く。すると、ペリクルフレーム１０の一対の長辺部１０ａ及び一対の短辺部１０ｂが弾性復元力（膨張力）により元の形に戻ろうとして外側に変位する。これにより、ペリクル膜１１には、４辺の外側方向に向かう引張力が作用し、膜張力が上がる。その後、ペリクル膜１１の余剰部分を除去する。 Next, as shown in FIG. 6C, the external force applied to the pellicle frame 10 is removed. Then, the pair of long side portions 10a and the pair of short side portions 10b of the pellicle frame 10 are displaced outward so as to return to the original shape by an elastic restoring force (expansion force). As a result, a tensile force directed toward the outer side of the four sides acts on the pellicle film 11 to increase the film tension. Thereafter, the excess portion of the pellicle film 11 is removed.
　このように、ペリクルフレーム１０に対してペリクル膜１１に与える張力の方向と逆方向の力を加えることで、ペリクル膜１１の張力が上がる。なお、ペリクルフレーム１０を細くすると、その変形量が大きいため、膜も大きく変形しようとするが、実際には、膜は無限に変形できないため、上述したように、ペリクルフレーム１０の復元力（膨張力）によりペリクル膜１１の張力が上がる。 Thus, by applying a force in the direction opposite to the direction of tension applied to the pellicle film 11 to the pellicle frame 10, the tension of the pellicle film 11 is increased. Note that if the pellicle frame 10 is made thin, the amount of deformation is large, so the membrane tends to deform greatly. However, since the membrane cannot be deformed indefinitely, the restoring force (expansion) of the pellicle frame 10 as described above. Force) increases the tension of the pellicle film 11.
　細幅のペリクルフレームを用いてペリクルを作製した場合、ペリクル膜の膜張力が弱いとペリクルの作製時やハンドリング時等にペリクル膜にシワが生じる可能性がある。そのような状態のペリクルをマスクに貼り付けて使用すると、ペリクルが撓んで異物検査装置等に接触したり、ペリクル付マスクをハンドリングする時にペリクル膜がケースに接触する可能性が高くなったり、露光時における露光光の光路が屈曲して正常に露光できない可能性が生じたりするため、好ましくない。 When a pellicle is manufactured using a narrow pellicle frame, if the film tension of the pellicle film is weak, wrinkles may occur in the pellicle film during manufacturing or handling of the pellicle. When a pellicle in such a state is attached to a mask and used, the pellicle will bend and come into contact with a foreign substance inspection device, etc., or when handling a mask with a pellicle, there is a high possibility that the pellicle film will come into contact with the case. The optical path of the exposure light at the time may be bent, and there is a possibility that normal exposure cannot be performed.
　そのため、細幅のペリクルフレーム１０を用いてペリクル１を構成した場合のペリクル膜１１の膜張力をある程度の大きさに保つ必要がある。ところで、ペリクルフレーム１０は角部の剛性が相対的に強いため、角部からの対角線上に沿ってペリクル膜１１の膜張力は相対的に強くなると想定される。よって、細幅のペリクルフレーム１０を用いた場合でも、対角線上のペリクル膜１１の膜張力は比較的強く維持できると考えられる、しかし、それとは対照的に、枠体２０の中央部付近はペリクル膜１１の膜張力に枠体２０が負けて辺が撓みやすくなるため、枠体２０の中央部分付近のペリクル膜１１の膜張力が小さくなることでペリクル膜１１をペリクルフレーム１０に貼り付けた場合にペリクル膜１１にシワが発生したり、ペリクル１のハンドリング時にペリクル膜１１にシワが発生したりしやすくなる。そのため、下記のように第１基準点での沈み量と第２基準点での沈み量が下記の条件Ａ～条件Ｃで規定される範囲内にあると、ペリクルフレーム１０の長辺側と短辺側の中央部分近傍である第１基準点及び第２基準点におけるペリクル膜１１の膜張力が強くなると共に、第１基準点及び第２基準点におけるペリクル膜１１の膜張力のバランスをとることができるため、ペリクル膜１１全体の張力のバランスがよくなり、細幅のペリクルフレーム１０を用いることが可能なペリクル１を作製することが可能となることを本発明者らは見出した。 Therefore, it is necessary to maintain the film tension of the pellicle film 11 at a certain level when the pellicle 1 is configured using the narrow pellicle frame 10. Incidentally, since the pellicle frame 10 has relatively strong corners, it is assumed that the film tension of the pellicle film 11 is relatively strong along the diagonal line from the corners. Therefore, even when the narrow pellicle frame 10 is used, it is considered that the film tension of the pellicle film 11 on the diagonal line can be maintained relatively strong, but in contrast, the vicinity of the center portion of the frame body 20 is near the pellicle. When the frame body 20 is defeated by the film tension of the film 11 and the sides are easily bent, the film tension of the pellicle film 11 in the vicinity of the center portion of the frame body 20 is reduced so that the pellicle film 11 is attached to the pellicle frame 10 In addition, wrinkles are likely to occur in the pellicle film 11 and wrinkles are likely to occur in the pellicle film 11 when the pellicle 1 is handled. Therefore, if the sinking amount at the first reference point and the sinking amount at the second reference point are within the range defined by the following conditions A to C as described below, the long side and the short side of the pellicle frame 10 are reduced. The film tension of the pellicle film 11 at the first reference point and the second reference point in the vicinity of the central portion on the side is increased, and the film tension of the pellicle film 11 at the first reference point and the second reference point is balanced. Therefore, the present inventors have found that the balance of tension of the entire pellicle film 11 is improved, and the pellicle 1 capable of using the narrow pellicle frame 10 can be manufactured.
　即ち、ペリクル膜１１には、以下の条件Ａ、条件Ｂ及び条件Ｃを全て満たすような大きさの膜張力が付与されていることが好ましい。 That is, it is preferable that the pellicle film 11 is given a film tension having a magnitude that satisfies all of the following conditions A, B, and C.
　条件Ａ：ペリクル膜１１が略水平となるようにペリクル１を配置した状態において、ペリクル膜１１上の第１基準点であって、平面視でペリクルフレーム１０の辺部の長辺部１０ａの内縁の中央点から当該長辺部１０ａの内縁と直交する方向に３０ｍｍ離れた第１基準点上に１０．６ｇの重りを載せた場合の当該第１基準点の沈み量（以下、「長辺側の膜沈み量」という場合がある）が０．４ｍｍ以上、２．４ｍｍ以下、好ましくは０．５ｍｍ以上、２．０ｍｍ以下、より好ましくは０．８ｍｍ以上、１．９ｍｍ以下である。 Condition A: In a state where the pellicle 1 is arranged so that the pellicle film 11 is substantially horizontal, it is the first reference point on the pellicle film 11 and the inner edge of the long side portion 10a of the side portion of the pellicle frame 10 in plan view Of the first reference point when a weight of 10.6 g is placed on the first reference point 30 mm away in the direction orthogonal to the inner edge of the long side portion 10a from the center point (hereinafter referred to as “long side side”) Is sometimes 0.4 mm or more and 2.4 mm or less, preferably 0.5 mm or more and 2.0 mm or less, more preferably 0.8 mm or more and 1.9 mm or less.
　条件Ｂ：ペリクル膜１１が略水平となるようにペリクル１を配置した状態において、ペリクル膜１１上の第２基準点であって、平面視でペリクルフレーム１０の辺部の短辺部１０ｂの内縁の中央点から当該短辺部１０ｂと直交する方向に３０ｍｍ離れた第２基準点上に１０．６ｇの重りを載せた場合の当該第２基準点の沈み量（以下、「短辺側の膜沈み量」という場合がある）が０．３ｍｍ以上、２．３ｍｍ以下、好ましくは０．４ｍｍ以上、１．９ｍｍ以下、より好ましくは０．７ｍｍ以上、１．７ｍｍ以下である。 Condition B: a second reference point on the pellicle film 11 in a state where the pellicle film 1 is arranged so that the pellicle film 11 is substantially horizontal, and the inner edge of the short side portion 10b of the side portion of the pellicle frame 10 in plan view Of the second reference point when a weight of 10.6 g is placed on the second reference point 30 mm away from the central point in the direction orthogonal to the short side portion 10b (hereinafter referred to as “film on the short side side”). Is sometimes 0.3 mm or more and 2.3 mm or less, preferably 0.4 mm or more and 1.9 mm or less, more preferably 0.7 mm or more and 1.7 mm or less.
　条件Ｃ：第１基準点の上記沈み量と第２基準点の上記沈み量との差（即ち、長辺側の膜沈み量と短辺側の膜沈み量との差）の絶対値が０．４ｍｍ以下、好ましくは０．３ｍｍ以下、より好ましくは０．２５ｍｍ以下である。 Condition C: The absolute value of the difference between the sinking amount at the first reference point and the sinking amount at the second reference point (that is, the difference between the film sinking amount on the long side and the film sinking amount on the short side) is 0 0.4 mm or less, preferably 0.3 mm or less, more preferably 0.25 mm or less.
　ペリクル膜１１に付与されている膜張力が上記条件Ａ、条件Ｂ及び条件Ｃを満たしていると、ペリクル膜１１をペリクルフレーム１０に貼り付けた後にペリクル膜１１に膜シワが生じ難くなるためである。また、マスクにペリクル１を貼り付けた際に、ペリクル１のハンドリング時等にペリクル膜１１がマスクに接触したり、ペリクル１に貼り付けられたペリクル膜１１が、風圧等の外圧を受けた時にペリクル膜１１がマスクに接触したりすることが抑制されるためである。更には、本願発明者らは、細幅のペリクルフレームを用いたペリクルにおいては、短辺側の膜沈み量と長辺側の膜沈み量の差が、従来のペリクルにおける差と比較して、非常に小さいことを見出した。そのため従来のペリクルにおける場合とは異なり、矩形状のペリクル膜１１の全体で膜張力のバランスが保たれているため、ペリクルフレームの辺部の幅を細くてもペリクルとして使用可能な製品になる。 If the film tension applied to the pellicle film 11 satisfies the above conditions A, B and C, film wrinkles are less likely to occur in the pellicle film 11 after the pellicle film 11 is attached to the pellicle frame 10. is there. When the pellicle 1 is attached to the mask, the pellicle film 11 comes into contact with the mask when the pellicle 1 is handled, or when the pellicle film 11 attached to the pellicle 1 receives an external pressure such as wind pressure. This is because the pellicle film 11 is prevented from contacting the mask. Furthermore, the inventors of the present application, in the pellicle using a narrow pellicle frame, the difference between the film sinking amount on the short side and the film sinking amount on the long side is compared with the difference in the conventional pellicle, I found it very small. Therefore, unlike the case of the conventional pellicle, since the balance of the film tension is maintained throughout the rectangular pellicle film 11, the product can be used as a pellicle even if the width of the side of the pellicle frame is narrow.
　次に、長辺側の膜沈み量と短辺側の膜沈み量の測定方法について説明する。図７は、長辺側の膜沈み量と短辺側の膜沈み量の測定方法を説明するための模式的な斜視図であり、図８は、長辺側の膜沈み量と短辺側の膜沈み量の測定方法を説明するための模式的な断面図である。図８（Ａ）は、ペリクルフレーム１０の長辺部１０ａの長さ方向の中央点におけるペリクル１の縦断面を示しており、図８（Ｂ）は、ペリクルフレーム１０の短辺部１０ｂの長さ方向の中央点におけるペリクル１の縦断面を示している。また、ペリクル載置台５０として、ペリクル収納容器のトレイを使用した。 Next, a method for measuring the film sinking amount on the long side and the film sinking amount on the short side will be described. FIG. 7 is a schematic perspective view for explaining a method of measuring the film sinking amount on the long side and the film sinking amount on the short side. FIG. 8 shows the film sinking amount on the long side and the short side. It is typical sectional drawing for demonstrating the measuring method of the film sinking amount. 8A shows a longitudinal section of the pellicle 1 at the center point in the length direction of the long side portion 10a of the pellicle frame 10, and FIG. 8B shows the length of the short side portion 10b of the pellicle frame 10. A longitudinal section of the pellicle 1 at the center point in the vertical direction is shown. Further, as the pellicle mounting table 50, a pellicle storage container tray was used.
　長辺側の膜沈み量を測定する際は、まず、粘着剤１２及び保護フィルム１３（図７においては図示せず）付ペリクル１を、ペリクル膜１１が略水平となるように枠上のペリクル載置台５０に静置する。そして、ペリクル膜１１における２箇所の第１基準点１１１に、ペリクル膜１１を破かないように軽くマーキングする。ここで、第１基準点１１１は、平面視で（ペリクル膜１１の厚さ方向から見て）ペリクルフレーム１０の辺部の長辺部１０ａの内縁の中央点１０ａｃから当該長辺部１０ａの内縁と直交する方向に３０ｍｍ離れた点である。 When measuring the amount of film sink on the long side, first, the pellicle 1 with the adhesive 12 and the protective film 13 (not shown in FIG. 7) is placed on the pellicle on the frame so that the pellicle film 11 is substantially horizontal. Place on the mounting table 50. Then, the two first reference points 111 in the pellicle film 11 are lightly marked so as not to break the pellicle film 11. Here, the first reference point 111 is the inner edge of the long side portion 10a from the center point 10ac of the long side portion 10a of the side portion of the pellicle frame 10 in plan view (as viewed from the thickness direction of the pellicle film 11). It is a point 30 mm away in the direction orthogonal to.
　次に、一方の第１基準点１１１に１０．６ｇの重り５５を置いて、当該重りを置く前を基準としたペリクル膜１１の沈み量１１１Ｄ（長辺側の膜沈み量１１１Ｄ）をレーザー変位計によって測定する。より具体的には、ドーナツ形状等の孔を有する形状の重り５５を準備し、重り５５の重心点が一方の第１基準点１１１上に位置するように、重り５５を一方の第１基準点１１１上に載せ、レーザー変形のセンサー５７をスタンド６１によって重り５５の上方に位置するように制御する。そして、センサー５７から重り５５の中央部の孔を通して第１基準点１１１にレーザー光を照射して、ペリクル膜１１の長辺側の膜沈み量１１１Ｄの大きさを測定する。コントローラ６３は、センサー５７に制御信号を送信し、この制御信号によって、センサー５７の位置やレーザー照射のタイミング等が制御される。センサー５７の測定データは、コントローラ６３を介してコンピュータ６５に送信される。コンピュータ６５は、コントローラ６３を制御すると共に、コントローラ６３を介して送信された上記測定データから、長辺側の膜沈み量１１１Ｄの値を計算する。また、他方の第１基準点１１１についても同様に長辺側の膜沈み量を測定する。そして、一方の第１基準点１１１についての長辺側の膜沈み量と、他方の第１基準点１１１についての長辺側の膜沈み量との平均値を計算し、当該平均値を長辺側の膜沈み量とする。 Next, a 10.6 g weight 55 is placed on one of the first reference points 111, and the amount of sinking 111D of the pellicle film 11 (the amount of film sinking on the long side 111D) relative to the position before placing the weight is laser-displaced. Measure with a meter. More specifically, a weight 55 having a hole shape such as a donut shape is prepared, and the weight 55 is placed on one first reference point such that the center of gravity of the weight 55 is positioned on the first reference point 111. The laser deformation sensor 57 is controlled so as to be positioned above the weight 55 by the stand 61. Then, the first reference point 111 is irradiated with laser light from the sensor 57 through the hole in the center of the weight 55, and the size of the film sinking amount 111D on the long side of the pellicle film 11 is measured. The controller 63 transmits a control signal to the sensor 57, and the position of the sensor 57, the timing of laser irradiation, and the like are controlled by this control signal. The measurement data of the sensor 57 is transmitted to the computer 65 via the controller 63. The computer 65 controls the controller 63 and calculates the value of the film sinking amount 111D on the long side from the measurement data transmitted through the controller 63. Similarly, the amount of film sink on the long side is also measured for the other first reference point 111. Then, the average value of the long-side film sinking amount for one first reference point 111 and the long-side film sinking amount for the other first reference point 111 is calculated, and the average value is calculated as the long-side film sinking amount. The amount of film sinking on the side.
　短辺側の膜沈み量についても同様に測定を行う。即ち、短辺側の膜沈み量を測定する際は、まず、粘着剤１２及び保護フィルム１３（図７においては図示せず）付ペリクル１を、ペリクル膜１１が略水平となるように枠上のペリクル載置台５０に静置する。そして、ペリクル膜１１における２箇所の第２基準点１１２に、ペリクル膜１１を破かないように軽くマーキングする。ここで、第２基準点１１２は、平面視で（ペリクル膜１１の厚さ方向から見て）ペリクルフレーム１０の辺部の短辺部１０ｂの内縁の中央点１０ｂｃから当該短辺部１０ｂの内縁と直交する方向に３０ｍｍ離れた点である。 Measure the amount of film sinking on the short side in the same way. That is, when measuring the film sinking amount on the short side, first, the pellicle 1 with the adhesive 12 and the protective film 13 (not shown in FIG. 7) is placed on the frame so that the pellicle film 11 is substantially horizontal. The pellicle mounting table 50 is left still. Then, the two second reference points 112 in the pellicle film 11 are lightly marked so as not to break the pellicle film 11. Here, the second reference point 112 is a plan view (as viewed from the thickness direction of the pellicle film 11) from the center point 10bc of the inner edge of the short side portion 10b of the side portion of the pellicle frame 10 to the inner edge of the short side portion 10b. It is a point 30 mm away in the direction orthogonal to.
　次に、一方の第１基準点１１２に１０．６ｇの重り５５を置いて、当該重りを置く前を基準としたペリクル膜１１の沈み量１１２Ｄ（長辺側の膜沈み量１１２Ｄ）をレーザー変位計によって測定する。より具体的には、重り５５の重心点が一方の第２基準点１１２上に位置するように、重り５５を一方の第２基準点１１２上に載せ、レーザー変形のセンサー５７をスタンド６１によって重り５５の上方に位置するように制御する。そして、センサー５７から重り５５の中央部の孔を通して第２基準点１１２にレーザー光を照射して、ペリクル膜１１の長辺側の膜沈み量１１２Ｄの大きさを測定する。コントローラ６３は、センサー５７に制御信号を送信し、この制御信号によって、センサー５７の位置やレーザー照射のタイミング等が制御される。センサー５７の測定データは、コントローラ６３を介してコンピュータ６５に送信される。コンピュータ６５は、コントローラ６３を制御すると共に、コントローラ６３を介して送信された上記測定データから、長辺側の膜沈み量１１２Ｄの値を計算する。また、他方の第２基準点１１２についても同様に長辺側の膜沈み量を測定する。そして、一方の第２基準点１１２についての短辺側の膜沈み量と、他方の第２基準点１１２についての短辺側の膜沈み量との平均値を計算し、当該平均値を短辺側の膜沈み量とする。 Next, a 10.6 g weight 55 is placed on one of the first reference points 112, and the amount of sinking 112D of the pellicle film 11 (the amount of film sinking 112D on the long side) relative to before placing the weight is laser-displaced. Measure with a meter. More specifically, the weight 55 is placed on one second reference point 112 so that the center of gravity of the weight 55 is positioned on one second reference point 112, and the laser deformation sensor 57 is weighted by the stand 61. It controls so that it may be located above 55. Then, the second reference point 112 is irradiated with laser light from the sensor 57 through the hole in the center of the weight 55, and the size of the film sinking amount 112D on the long side of the pellicle film 11 is measured. The controller 63 transmits a control signal to the sensor 57, and the position of the sensor 57, the timing of laser irradiation, and the like are controlled by this control signal. The measurement data of the sensor 57 is transmitted to the computer 65 via the controller 63. The computer 65 controls the controller 63 and calculates the value of the film sinking amount 112D on the long side from the measurement data transmitted through the controller 63. Similarly, for the other second reference point 112, the film sink amount on the long side is measured. Then, an average value of the film sink amount on the short side for one second reference point 112 and the film sink amount on the short side for the other second reference point 112 is calculated, and the average value is calculated as the short side The amount of film sinking on the side.
　本実施形態によれば、温度変化を与えることなく、高分子材料からなるペリクル膜１１の膜張力を向上できるので、ペリクル膜１１の物性が変動することを防止でき、当該ペリクル１を利用した露光処理を適正に行うことができる。また、ペリクルフレーム１０や粘着剤１２、ペリクル膜１１などの材質に温度変化に耐え得るものを用いる必要がなく、材質の選択の自由度が広がる。また、温度変化の付与や、温度変化に伴う空調を行う高価な設備が必要なく、その制御プロセスが容易になる。さらに、高温若しくは低温に曝されないため、熱による粘着剤１２等の劣化がなく、ペリクル１の平坦性や寸法精度が確保され、精度の高い露光処理を行うことができる。 According to the present embodiment, since the film tension of the pellicle film 11 made of a polymer material can be improved without causing a temperature change, the physical properties of the pellicle film 11 can be prevented from changing, and exposure using the pellicle 1 can be performed. Processing can be performed appropriately. In addition, it is not necessary to use materials that can withstand temperature changes such as the pellicle frame 10, the adhesive 12, and the pellicle film 11, and the degree of freedom in selecting the material is increased. Further, there is no need for expensive equipment for imparting temperature changes or performing air conditioning accompanying temperature changes, and the control process is facilitated. Furthermore, since it is not exposed to high or low temperatures, the adhesive 12 and the like are not deteriorated by heat, the flatness and dimensional accuracy of the pellicle 1 are ensured, and highly accurate exposure processing can be performed.
　また、本実施形態によれば、膜張力を向上できるので、ペリクル１の大型化によって顕著になるペリクル膜１１の自重による撓みを抑制できる。よって、大型ペリクルであっても、精度の高い露光処理を実現できる。また、露光用基盤への装着時に周囲雰囲気を巻き込んで生じるペリクル膜１１の膨らみも抑制できる。これにより、そのペリクル膜１１の膨らみが戻るまでの待ち時間が減り、製造時間を短縮できる。 In addition, according to the present embodiment, since the film tension can be improved, it is possible to suppress the bending due to the weight of the pellicle film 11 that becomes conspicuous when the pellicle 1 is enlarged. Therefore, even with a large pellicle, highly accurate exposure processing can be realized. Further, the swelling of the pellicle film 11 caused by the surrounding atmosphere involved when being mounted on the exposure substrate can be suppressed. Thereby, the waiting time until the swelling of the pellicle film 11 returns is reduced, and the manufacturing time can be shortened.
　また、本実施形態では、ペリクルフレーム１０の一対の長辺部１０ａ及び一対の短辺部１０ｂの全てを内側に弾性変形させていたが、４辺部のうちの少なくも１辺部を内側に変形させてもよい。そして、ペリクルフレーム１０の内側に変形させる辺部を選択することにより、ペリクル膜１１の長辺方向、若しくは短辺方向の張力を発現させたい方向のみに膜張力を増加させることもでき、ペリクル膜１１が長方形の場合などは長辺方向に強い張力を与えるなど、４方向の張力バランスの均等化を図ることができる。 In the present embodiment, all of the pair of long sides 10a and the pair of short sides 10b of the pellicle frame 10 are elastically deformed inward, but at least one of the four sides is inward. It may be deformed. Then, by selecting the side part to be deformed inside the pellicle frame 10, the film tension can be increased only in the direction in which the tension in the long side direction or the short side direction of the pellicle film 11 is desired to be expressed. When 11 is rectangular, it is possible to equalize the tension balance in the four directions, such as applying a strong tension in the long side direction.
　さらに、図５の（Ｂ）～（Ｄ）に示したように、ペリクルフレーム１０の少なくとも１辺が外側に凸となるように湾曲膨出した初期形状を有している場合には、ペリクルフレーム１０の辺部の内側への変形量を大きく確保でき、その分、弾性復元力（膨張力）により元に戻る際の変形量も大きく確保できる。よって、ペリクル膜１１をより強く引っ張ることができ、膜張力をさらに上げることができる。 Further, as shown in FIGS. 5B to 5D, when the pellicle frame 10 has an initial shape curved and bulged so that at least one side protrudes outward, the pellicle frame A large amount of deformation toward the inside of the 10 side portions can be ensured, and accordingly, a large amount of deformation can be secured when returning to the original state by the elastic restoring force (expansion force). Therefore, the pellicle film 11 can be pulled more strongly, and the film tension can be further increased.
　また、図５の（Ｂ）～（Ｄ）に示したペリクルフレーム１０において、ペリクルフレーム１０の外側に凸となるように湾曲膨出した部分を押さえ込むことで、ペリクルフレーム１０の外側への膨出量とペリクルフレーム１０の内側への押さえ込み量を制御することにより、任意の膜張力を発現させることが可能である。そして、押さえ込みはフレームの弾性変形領域であれば任意の力で押さえることが可能であり、ペリクルフレーム１０の外側に凸となる膨出量とペリクルフレーム１０の内側への押さえ込み量とのバランスを取り、ペリクル１の成形後に一対の長辺部１０ａ及び一対の短辺部１０ｂが略直線状になるように調整することが好ましい。 Further, in the pellicle frame 10 shown in FIGS. 5 (B) to 5 (D), the pellicle frame 10 is bulged to the outside by pressing down the curved and bulged portion so as to protrude outward. By controlling the amount and the amount of pressing inside the pellicle frame 10, it is possible to develop an arbitrary film tension. The pressing can be performed with any force within the elastic deformation region of the frame, and the amount of bulging that protrudes outward from the pellicle frame 10 and the amount of pressing into the pellicle frame 10 are balanced. The pair of long side portions 10a and the pair of short side portions 10b are preferably adjusted to be substantially linear after the pellicle 1 is molded.
　以上の実施形態において、枠体２０及びペリクルフレーム１０の少なくとも一対の辺部の初期形状における辺部の外側に凸となる膨出量をもつ。更には、前記一対の辺部は長辺側、短辺側のどちらでもよいが、特に長辺側に外側に凸となる膨出量を形成することが好ましい。また、４辺全てに外側に凸となる膨出量を形成しても良い。長辺側の膨出量としては、３ｍｍ以上、２０ｍｍ以下が好ましく、３．５ｍｍ以上２０ｍｍ以下がより好ましく、更に好ましくは３．８ｍｍ以上１８ｍｍ以下、更に好ましくは４．０ｍｍ以上１５ｍｍ以下である。また短辺側の初期形状における辺部の外側に凸となる膨出量は、２．８ｍｍ以上１５ｍｍ以下、より好ましくは２．９ｍｍ以上１２ｍｍ以下、更に好ましくは３．０ｍｍ以上９ｍｍ以下である。特に、長辺と短辺のそれぞれの対を合わせて外側に凸となる膨出量をもたせる場合の膨出量としては、長辺側の膨出量が２．５ｍｍ以上２０ｍｍ以下であって短辺側の膨出量が０．５ｍｍ以上１５ｍｍ以下であることが好ましく、長辺側の膨出量が３．０ｍｍ以上１８ｍｍ以下であって短辺側の膨出量が１．０ｍｍ以上１２ｍｍ以下であることがよりに好ましく、長辺側の膨出量が３．５ｍｍ以上１５ｍｍ以下であって短辺側の膨出量が１．５ｍｍ以上９ｍｍ以下であることが更に好ましい。なお、図９に示すように、この膨出量Ｓは、ペリクルフレーム１０又は枠体２０の各辺部の角部における外縁の頂点Ｃ同士をつないだ直線を仮想の基準線Ｌとした際の、該辺の外縁上における前記基準線から最も離れた点Ｐと前記基準線Ｌとの距離とする。 In the above embodiment, the frame 20 and the pellicle frame 10 have a bulging amount that protrudes outward from the sides in the initial shape of at least a pair of sides. Furthermore, the pair of side portions may be on either the long side or the short side, but it is preferable to form a bulging amount that protrudes outward on the long side. Moreover, you may form the bulging amount which becomes convex outside on all four sides. The bulging amount on the long side is preferably 3 mm or more and 20 mm or less, more preferably 3.5 mm or more and 20 mm or less, still more preferably 3.8 mm or more and 18 mm or less, and further preferably 4.0 mm or more and 15 mm or less. In addition, the bulging amount that protrudes outward from the side portion in the initial shape on the short side side is 2.8 mm to 15 mm, more preferably 2.9 mm to 12 mm, and still more preferably 3.0 mm to 9 mm. In particular, as the bulging amount when the pair of the long side and the short side are combined to have a bulging amount that protrudes outward, the bulging amount on the long side is 2.5 mm to 20 mm and short. The bulge amount on the side is preferably 0.5 mm or more and 15 mm or less, the bulge amount on the long side is 3.0 mm or more and 18 mm or less, and the bulge amount on the short side is 1.0 mm or more and 12 mm or less. More preferably, the bulging amount on the long side is 3.5 mm or more and 15 mm or less, and the bulging amount on the short side is more preferably 1.5 mm or more and 9 mm or less. As shown in FIG. 9, this bulge amount S is obtained when the straight line connecting the vertices C of the outer edges at the corners of each side of the pellicle frame 10 or the frame 20 is used as the virtual reference line L. The distance between the reference line L and the point P farthest from the reference line on the outer edge of the side.
　初期形状としては、外側に凸となる膨出量をもてばどのような形状でもよいが、図９のように中央付近に膨出量をもつことが好ましい。頂点Ｃから徐々に外側に凸となってもよいし、頂点Ｃからある程度の直線を持ってから、外側に凸となってもよい。 The initial shape may be any shape as long as it has an outwardly convex bulge amount, but preferably has a bulge amount near the center as shown in FIG. It may be gradually convex outward from the vertex C, or may have a certain straight line from the vertex C and then convex outward.
　また、ペリクルフレーム１０の角部の外縁の曲率半径Ｒは、１ｍｍ以上、５ｍｍ以下であることが好ましく、２ｍｍ以上、５ｍｍ以下であることがより好ましい。当該角部の内縁の曲率半径Ｒは、１ｍｍ以上、３ｍｍ以下であることが好ましく、２ｍｍであることが最も好ましい。何故なら、ペリクルフレーム１０を細幅にした場合であっても、ペリクルフレーム１０の角部の外縁及び内縁の曲率半径が上記範囲内であれば、当該角部に応力が集中することを回避しつつ、当該角部に十分な面積を持たせることができる。その結果、当該角部の剛性を保つことができ、ペリクルフレーム１０に復元力を持たせた場合においても当該角部の形状を維持できるため、ペリクルフレーム１０の形状が、矩形形状から平行四辺形状等の他の形状に歪み難くなり、形状の変形に起因してペリクル膜にシワが生じることを抑制することができるからである。 Further, the radius of curvature R of the outer edge of the corner of the pellicle frame 10 is preferably 1 mm or more and 5 mm or less, and more preferably 2 mm or more and 5 mm or less. The radius of curvature R of the inner edge of the corner is preferably 1 mm or more and 3 mm or less, and most preferably 2 mm. This is because even if the pellicle frame 10 is narrow, if the curvature radius of the outer edge and the inner edge of the corner of the pellicle frame 10 is within the above range, stress can be prevented from concentrating on the corner. However, the corner can have a sufficient area. As a result, the rigidity of the corner portion can be maintained, and the shape of the corner portion can be maintained even when the pellicle frame 10 has a restoring force. Therefore, the shape of the pellicle frame 10 is changed from a rectangular shape to a parallelogram shape. This is because it is difficult to be distorted into other shapes such as the above, and wrinkles can be prevented from occurring in the pellicle film due to the deformation of the shape.
　また、ペリクルフレーム１０に膜接着剤又はマスク粘着材を塗布する場合においては、ペリクルフレーム１０の角部への塗布量が増える傾向にあるが、ペリクルフレーム１０の角部の外縁及び内縁の曲率半径が上記範囲内であれば接着剤ダレ等を生じ難くなるため、膜接着剤又はマスク粘着材をペリクルフレーム１０に均一に塗布でき好ましい。 Further, when a film adhesive or a mask adhesive is applied to the pellicle frame 10, the amount of application to the corners of the pellicle frame 10 tends to increase, but the curvature radius of the outer edge and inner edge of the pellicle frame 10 is increased. Is within the above range, it is difficult to cause adhesive sag and the like, and therefore it is preferable that a film adhesive or a mask adhesive can be uniformly applied to the pellicle frame 10.
　また、ペリクル枠体の表面に、黒色クロムメッキ、黒色アルマイト、黒色塗装等の黒色化処理を施すことも出来る。 Also, the surface of the pellicle frame can be subjected to blackening treatment such as black chrome plating, black alumite, or black paint.
　フレームにはハンドリング用の溝を設けることができ、１対の短辺の全長に沿って設ける場合や４辺に部分的に溝を設ける場合などがある。この溝には、Ｃ面が設けられておりバリ取り等のためにＣ０．１～０．５が設けられる場合がある。 ¡Handling grooves can be provided on the frame, and there are cases where the grooves are provided along the entire length of a pair of short sides, or where grooves are partially provided on the four sides. This groove is provided with a C surface, and C0.1 to 0.5 may be provided for deburring and the like.
　フレームの膜接着剤側において、外側面及び内側面とのなす角には、Ｃ面が設けられている。外側面とのなす角のＣ面は、Ｃ０．１～０．５あり、内側面とのなす角のＣ面は、Ｃ０．５～２．５が設けられている。外側面のＣ面が上記範囲内にあると、余剰分の膜をカッティングする場合にカッターや冶具等が滑らかにいきバリ等の発生で膜が破れない為好ましい。また、内側面のＣ面が上記範囲内にあると、膜接着剤が垂れにくいために好ましい。 On the film adhesive side of the frame, a C surface is provided at the angle formed by the outer surface and the inner surface. The C-plane having an angle with the outer side has C0.1 to 0.5, and the C-plane having the angle with the inner side has C0.5 to 2.5. It is preferable that the C surface of the outer surface is within the above range because when cutting an excess film, the cutter, jigs, etc. are smooth and the film does not break due to the occurrence of burrs. Moreover, it is preferable that the C surface of the inner surface is within the above range because the film adhesive is difficult to sag.
　この中で、黒色アルマイト処理についてさらに説明する。 In this, the black alumite treatment will be further described.
　ペリクル用の枠体（支持枠）としては一般に５０００系のアルミニウム合金を用いることが多いので、アルミニウム合金を例に挙げて説明する。 As the frame body (support frame) for the pellicle, a 5000 series aluminum alloy is generally used in many cases, and an aluminum alloy will be described as an example.
　一般的な黒色アルマイト処理は、アルミニウム合金でペリクル枠体を成形後、アルマイト処理し、この処理により発生した微細な孔を黒色化剤で封入処理し、そしてその微細孔をふさぐ封孔処理を施して黒色アルマイト処理がなされる。しかし、このようにして一般的な方法で作られた枠体の表面を、電子顕微鏡で観察すると、細かいひびわれ（マイクロクラック）の発生が確認される。このようなマイクロクラックはパターンの微細化が進展し、配線幅が一層狭くなると、該クラックに入り込んだ極小さい異物の落下も問題となる。そこで、このようなマイクロクラックの発生を防止する方法として以下のような方法をとることが好ましい。 In general black alumite treatment, a pellicle frame is formed with an aluminum alloy, then anodized, fine pores generated by this treatment are sealed with a blackening agent, and a sealing treatment is applied to close the fine pores. Black anodized. However, when the surface of the frame body thus made by a general method is observed with an electron microscope, generation of fine cracks (microcracks) is confirmed. Such micro-cracks have a problem that even if the pattern becomes finer and the wiring width is further narrowed, a very small foreign matter falling into the cracks also becomes a problem. Therefore, it is preferable to take the following method as a method for preventing the occurrence of such microcracks.
　先ず、ペリクル枠体の表面をアルマイト処理する。このアルマイト処理は、硫酸濃度１０～２０％、電流密度１～２Ａ／ｄｍ２、電解液温度１５～３０℃、通電時間１０～３０分の範囲で行われる。その際、合金の表面にはミクロな孔（直径５０～２００Å、ピッチ５００～１５００Å）が規則正しく多数形成される。その後、この孔を使って黒色化処理を行う。黒色化処理は枠からの光の反射を防止するために行うので黒色に限らず黒に近い、茶色や紺色等の濃い色も含むものである。黒色化処理には、染色、電解着色等が挙げられる。染色は、黒色の染料を溶解した液の中に浸漬することでこの孔に染料を吸着させ色調を得る方法であり、また、電解着色は、この孔に電気的に金属元素を析出させ色調を得る方法である。染色は例えば、染料濃度３～１０ｇ／Ｌ、染色液温度５０～６５℃にて行う。 First, the surface of the pellicle frame is anodized. This alumite treatment is performed in a sulfuric acid concentration of 10 to 20%, a current density of 1 to 2 A / dm 2 , an electrolyte temperature of 15 to 30 ° C., and an energization time of 10 to 30 minutes. At that time, a large number of microscopic holes (diameter 50 to 200 mm, pitch 500 to 1500 mm) are regularly formed on the surface of the alloy. Thereafter, a blackening process is performed using the holes. Since the blackening process is performed in order to prevent reflection of light from the frame, it is not limited to black, but also includes dark colors such as brown and dark blue that are close to black. Examples of the blackening treatment include dyeing and electrolytic coloring. Dyeing is a method of obtaining a color tone by adsorbing the dye in this hole by immersing it in a solution in which a black dye is dissolved, and electrolytic coloring is a method in which a metallic element is electrically deposited in this hole to change the color tone. How to get. For example, the dyeing is performed at a dye concentration of 3 to 10 g / L and a dyeing solution temperature of 50 to 65 ° C.
　続いて、この孔を塞ぐ封孔処理が施される。この処理には、例えば低温封孔剤とよばれる日華化学工業（株）製ハードウォール３（商品名）封孔助剤６～１２ｇ／Ｌを加えた煮沸水が使われる。 Subsequently, a sealing process is performed to close the hole. For this treatment, for example, boiling water to which 6 to 12 g / L of a hard wall 3 (trade name) sealing aid, which is called a low-temperature sealing agent, is used is used.
　この時の封孔によりアルマイト膜表面の微細な孔が埋められアルマイト膜は緻密になっていくのであるが、封孔の温度を１００℃より若干低い温度、例えば７０～９５℃、より好ましくは８０～９０℃で封孔処理を行えば、極めて均一な表面性を有し、実質的にマイクロクラックのないペリクル枠体を作ることができる。 Although the fine pores on the surface of the alumite film are filled by the sealing at this time and the alumite film becomes dense, the temperature of the sealing is slightly lower than 100 ° C., for example, 70 to 95 ° C., more preferably 80 ° C. If the sealing treatment is performed at ˜90 ° C., a pellicle frame having a very uniform surface property and substantially free of microcracks can be produced.
　尚、マイクロクラックの有無の判断は、枠体表面を電子顕微鏡にて１０００倍に拡大した写真において１０ｃｍ（実寸法０．１ｍｍ）の直線を引き、その直線に交差するクラック数を計算する。クラックの幅は、その電子顕微鏡写真で観察できるもの、即ちクラック幅０．１μｍ以上のものを計数する。この数値が多いほどクラックが高密度で存在すると判断する。 In addition, the judgment of the presence or absence of a microcrack draws a 10 cm (actual dimension 0.1 mm) straight line in the photograph which expanded the frame body surface 1000 times with the electron microscope, and calculates the number of cracks which cross the straight line. As for the width of the crack, those that can be observed in the electron micrograph, that is, those having a crack width of 0.1 μm or more are counted. It is judged that cracks exist with higher density as this value increases.
　必要に応じてペリクル枠体の内壁面又は全面に、異物を補足するための粘着材（アクリル系、酢酸ビニル系、シリコーン系、ゴム系等）やグリース（シリコーン系、フッ素系等）を塗布しても良い。 If necessary, apply adhesive (acrylic, vinyl acetate, silicone, rubber, etc.) or grease (silicone, fluorine, etc.) to capture foreign substances on the inner wall surface or the entire surface of the pellicle frame. May be.
　また、必要に応じてペリクル枠体の内部と外部を貫通する微細な穴を開けて、ペリクルとフォトマスクで形成された空間の内外の気圧差がなくなるようにすると、膜の膨らみや凹みを防止出来る。 In addition, if necessary, a minute hole that penetrates the inside and outside of the pellicle frame body is made so that the pressure difference between the inside and outside of the space formed by the pellicle and photomask is eliminated, preventing swelling and dents in the film. I can do it.
　また、この時、微細な穴の外側に異物除去フィルターを取り付けると、気圧調整が可能な上、ペリクルとフォトマスクで形成された空間の中に異物が侵入することを防げるので好ましい。 Also, at this time, it is preferable to attach a foreign matter removing filter outside the fine hole because the atmospheric pressure can be adjusted and foreign matter can be prevented from entering the space formed by the pellicle and the photomask.
　ペリクルとフォトマスクで形成された空間容積が大きい場合には、これらの穴やフィルターを複数個設けると、気圧変動による膜の膨らみや凹みの回復時間が短くなり、好ましい。 When the space volume formed by the pellicle and the photomask is large, it is preferable to provide a plurality of these holes and filters because the recovery time of the swelling and dent of the film due to atmospheric pressure fluctuation is shortened.
　本実施形態のペリクル枠体は、上記の要件を満足することで適度な剛性と柔軟性を兼ね備えることが可能となるため、ペリクル膜を展張することによる枠体の歪がなく、ペリクルを単独でハンドリングする場合の撓みはもちろん、その後の、マスクへの貼り付け後のハンドリングにおけるマスク自身の撓みにも追従することが可能である。その結果、ペリクルにシワが生じず、かつ、マスクの撓みにも追従できるので、エアパスが生じることもないといった優れた効果を奏するものである。 The pellicle frame according to the present embodiment can have both appropriate rigidity and flexibility by satisfying the above requirements, so there is no distortion of the frame due to stretching of the pellicle film, and the pellicle can be used alone. It is possible to follow the bending of the mask itself in the handling after the pasting to the mask as well as the bending in the case of handling. As a result, the pellicle is not wrinkled and can follow the bending of the mask, so that an excellent effect is obtained that no air path is generated.
　本実施形態に係るペリクル膜１１は、開口部Ｆを有するペリクルフレーム１０にその開口面Ｆを覆うように貼り付けられているが、張り付けられたペリクル膜１１の張力が、１．８ｇｆ／ｍｍ以上、６ｇｆ／ｍｍ以下であることが好ましいく、１．９ｇｆ／ｍｍ以上、５ｇｆ／ｍｍ以下であることがより好ましく、２．０ｇｆ／ｍｍ以上、４．５ｇｆ／ｍｍ以下であることが更に好ましい。 The pellicle film 11 according to this embodiment is attached to the pellicle frame 10 having the opening F so as to cover the opening surface F. The tension of the attached pellicle film 11 is 1.8 gf / mm or more. 6 gf / mm or less, preferably 1.9 gf / mm or more and 5 gf / mm or less, more preferably 2.0 gf / mm or more and 4.5 gf / mm or less.
　ペリクル膜１１の張力を上記範囲における下限値以上に調整することで、ペリクル１のハンドリング時にペリクル膜１１に膜シワが生じること等が抑制され、ペリクル１のハンドリング性が向上する。また、ペリクル膜１１の張力を上記範囲における上限値以下に調整することで、ペリクル膜１１の亀裂や破損を有効に抑制することができる。 By adjusting the tension of the pellicle film 11 to be equal to or higher than the lower limit in the above range, the generation of wrinkles on the pellicle film 11 during the handling of the pellicle 1 is suppressed, and the handling property of the pellicle 1 is improved. Further, by adjusting the tension of the pellicle film 11 to be equal to or lower than the upper limit in the above range, cracks and breakage of the pellicle film 11 can be effectively suppressed.
　ペリクル膜とペリクル枠体とを接着するための膜接着剤は、ペリクル膜の材質とペリクル枠体の材質によって適宜選択する。たとえば、エポキシ系、アクリル系、シリコーン系、フッ素系等の接着剤が使用される。 The film adhesive for adhering the pellicle film and the pellicle frame is appropriately selected depending on the material of the pellicle film and the material of the pellicle frame. For example, an epoxy, acrylic, silicone or fluorine adhesive is used.
　また、接着剤の硬化方法は夫々の接着剤に適した硬化方法（熱硬化、光硬化、嫌気性硬化等）が採用される。発塵性、コスト、作業性の面から、アクリル系の紫外線硬化型接着剤が好ましい。 Also, as the curing method of the adhesive, a curing method (thermal curing, photocuring, anaerobic curing, etc.) suitable for each adhesive is adopted. From the viewpoint of dust generation, cost, and workability, an acrylic ultraviolet curable adhesive is preferable.
　ペリクル枠体をフォトマスクに貼り付けるためのマスク粘着材には、それ自身に粘着力のあるホットメルト系（ゴム系、アクリル系）、基材の両面に粘着材を塗布したテープ系（基材としてアクリル系、PVC系等のシートあるいはゴム系、ポリオレフィン系、ウレタン系等のフォーム等が適用出来、粘着材としてゴム系、アクリル系、シリコーン系等の粘着材が適用される）等が使用される。また、粘着材は透明でも良いが、異物検査性の観点から、黒色でも良い。 The mask adhesive for attaching the pellicle frame to the photomask is a hot-melt type (rubber-based or acrylic-based) that has adhesive force on itself, and a tape-based (base material) with adhesive material applied to both sides of the base material. Acrylic, PVC, etc. sheets or rubber, polyolefin, urethane, etc. foams can be applied, and rubber, acrylic, silicone, etc. adhesive materials are used as adhesives) The The adhesive material may be transparent, but may be black from the viewpoint of foreign matter inspection.
　本実施形態に係る大型ペリクルでは、マスク粘着材として、ペリクルをフォトマスクに低荷重で均一に貼り付けるために、比較的柔らかいホットメルト材料やフォームが好適である。フォームの場合は、その断面にアクリル系や酢酸ビニル系の粘着性材料あるいは非粘着性材料で覆うことにより、フォームからの発塵を防ぐことが出来る。 In the large pellicle according to the present embodiment, a relatively soft hot-melt material or foam is suitable as the mask adhesive material in order to uniformly apply the pellicle to the photomask with a low load. In the case of foam, dust generation from the foam can be prevented by covering the cross section with an acrylic or vinyl acetate adhesive material or a non-adhesive material.
　マスク粘着材の厚さは通常０．２ｍｍ以上とされるが、フォトマスクへの均一な貼付のために、好ましくは１ｍｍ以上とされる。上記マスク粘着材の粘着面をフォトマスクに貼り付けるまでの間保護するために、シリコーンやフッ素で離型処理されたポリエステルフィルムが使用される。 The thickness of the mask adhesive is usually 0.2 mm or more, but preferably 1 mm or more for uniform sticking to the photomask. In order to protect the adhesive surface of the mask adhesive material until it is attached to the photomask, a polyester film that has been subjected to a release treatment with silicone or fluorine is used.
　以上、添付図面を参照しながら本発明の好適な実施の形態について説明したが、本発明はかかる例に限定されない。当業者であれば、特許請求の範囲に記載された思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。
（実施例）
（実施例１） The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various modifications or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood.
(Example)
Example 1
　大型ペリクル用の枠体として、材質がアルミニウム合金、厚みが８ｍｍ、長辺部及び短辺部の幅が２０ｍｍ、内寸が１６００ｍｍ×１６００ｍｍのものを用意した。当該枠体は、各辺部の中央付近を外側に凸となるように湾曲膨出した形状とし、初期形状の外側への膨出量を３．３ｍｍとした。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．０ｍｍ、長辺部及び短辺部の幅が９ｍｍ、内寸が１３５０ｍｍ×１１４０ｍｍで、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が９．０ｍｍ、短辺部側が７．５ｍｍのものを用意した。 As a frame for a large pellicle, a material having an aluminum alloy, a thickness of 8 mm, a width of a long side portion and a short side portion of 20 mm, and an internal size of 1600 mm × 1600 mm was prepared. The frame has a shape that is curved and bulged so that the vicinity of the center of each side is convex outward, and the amount of bulging outward of the initial shape is 3.3 mm. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.0 mm, the width of the long side and the short side is 9 mm, the inside dimension is 1350 mm × 1140 mm, and the vicinity of the center of each side is the outside As the amount of bulging to the outside of the initial shape, a shape having a long side portion of 9.0 mm and a short side portion side of 7.5 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体の各辺部が略直線状になるように治具を用いて各辺部の中央付近を内側に向けて押さえ込みながら、当該枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。基板から剥離後、治具による外力を開放した。大型ペリクル用のペリクルフレームの下縁面にスチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの各辺部が略直線状になるように冶具で各辺部の中央付近を内側に向けて押さえ込みながら、ペリクルフレーム１０にペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. Cellulose ester formed on the substrate on the frame while pressing the vicinity of the center of each side inward using a jig so that each side of the frame for the large pellicle is substantially linear Then, the pellicle film was peeled off from the substrate. After peeling from the substrate, the external force by the jig was released. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge of the pellicle frame for a large pellicle. Apply an acrylic film adhesive to the upper edge of the pellicle frame, and use a jig to hold the center of each side inward so that each side of the pellicle frame is substantially straight. A pellicle film was adhered to the frame 10, and then the excess film was excised.
　ここで、ペリクル膜をペリクル枠体に展張して接着された時に発生するシワの有無を評価した。評価結果を図１０に示す。評価結果の表記において、「○」は、膜に全くシワがない状態、「△」は、膜をよくみると少し波打っている状態、「×」は、膜に少しシワが入っている状態、を示している。 Here, the presence or absence of wrinkles generated when the pellicle film was spread and adhered to the pellicle frame was evaluated. The evaluation results are shown in FIG. In the evaluation result notation, “○” indicates that there is no wrinkle on the film, “△” indicates that the film is slightly wavy, and “×” indicates that the film is slightly wrinkled. , Shows.
　また、ペリクル枠体のハンドリングは、一対の短辺部の各々の一部をハンドリング治具にて把持することにより実施した。そして、ペリクル膜のペリクル枠体への展張・接着後から収納容器への保管までの一連のハンドリング工程において、ハンドリング性を評価した。評価結果を図１０に示す。評価結果の表記において、「○」は、一回もハンドリング工程で冶具から脱落しなかった、「×」は、一回でもハンドリング工程で冶具から脱落した、を示している。
（実施例２） The handling of the pellicle frame was carried out by gripping a part of each of the pair of short sides with a handling jig. Then, handling properties were evaluated in a series of handling steps from after the pellicle membrane was spread and adhered to the pellicle frame to storage in the storage container. The evaluation results are shown in FIG. In the notation of the evaluation results, “◯” indicates that the tool has not fallen from the jig once in the handling process, and “x” indicates that the tool has fallen from the jig even once.
(Example 2)
　大型ペリクル用の枠体として、材質がアルミニウム合金、厚みが８ｍｍ、長辺と短辺の幅が２０ｍｍ、内寸が１６００ｍｍ×１６００ｍｍのものを用意した。枠体は、各辺部が直線状の初期形状のものを用いた。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．０ｍｍ、長辺部及び短辺部の幅が９ｍｍ、内寸が１３５０ｍｍ×１１４０ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が８．０ｍｍ、短辺部側が６．５ｍｍのものを用意した。 As a frame for a large pellicle, a material having an aluminum alloy, a thickness of 8 mm, a width of a long side and a short side of 20 mm, and an internal size of 1600 mm × 1600 mm was prepared. The frame used was an initial shape with straight sides. Separately, as a pellicle frame for a large pellicle, the material is an aluminum alloy, the thickness is 5.0 mm, the width of the long side and the short side is 9 mm, the inside dimension is 1350 mm × 1140 mm, and the vicinity of the center of each side is outside A shape bulging so as to be convex and having an initial bulging amount of 8.0 mm on the long side and 6.5 mm on the short side was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の外側への膨出量が５ｍｍになるように治具で長辺部の中央を内側に向けて押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the center of the long side is directed inward with a jig so that the amount of bulging out of the long side of the pellicle frame is 5 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。
（実施例３） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG.
(Example 3)
　大型ペリクル用のペリクルフレームとして、内寸が１２００ｍｍ×７６０ｍｍ、厚さ５ｍｍ、長辺部の幅が９ｍｍ、短辺部の幅が５ｍｍ、長辺部の初期形状の外側への膨出量が５．５ｍｍのものを用い、長辺部の外側への膨出量が３ｍｍになるように長辺部の中央付近を治具で内側に向けて押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。それ以外は、実施例２と同様とした。 As a pellicle frame for a large pellicle, the inner dimension is 1200 mm × 760 mm, the thickness is 5 mm, the long side width is 9 mm, the short side width is 5 mm, and the long side width of the initial shape is 5 Using a 5 mm one, attach the pellicle film to the pellicle frame while pressing the center of the long side inward with a jig so that the amount of bulging to the outside of the long side is 3 mm. The excess membrane was excised. Other than that was the same as Example 2.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。
（実施例４） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG.
(Example 4)
　大型ペリクル用の枠体として、材質がアルミニウム合金、厚みが８ｍｍ、長辺と短辺の幅が２０ｍｍ、内寸が１６００ｍｍ×１６００ｍｍのものを用意した。枠体は、各辺部が直線状の初期形状のものを用いた。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ５、内側コーナーＲ２とし、長辺部の幅が６ｍｍ、短辺部の幅が１２ｍｍ、内寸が１３３６ｍｍ×１１２８ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が１３．０ｍｍ、短辺部側が１．５ｍｍのものを用意した。 As a frame for a large pellicle, a material having an aluminum alloy, a thickness of 8 mm, a width of a long side and a short side of 20 mm, and an internal size of 1600 mm × 1600 mm was prepared. The frame used was an initial shape with straight sides. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R5, the inner corner R2, the long side width is 6 mm, the short side width is 12 mm, The inner dimension is 1336mm x 1128mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 13.0mm on the long side and the short side A 1.5 mm side was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から１．２ｍｍ内側に向けて冶具で押さえ込み（図９のＰから１．２ｍｍＬ直線側に押えこむ状態）、短辺部は膨出部を冶具で固定しながら（図のＰで冶具を固定する）ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame and pressed by a jig toward the inner side of the bulge of the long side of the pellicle frame by 1.2 mm (a straight line of 1.2 mmL from P in FIG. 9). The pellicle film was adhered to the pellicle frame while fixing the bulging portion with a jig (fixing the jig with P in the figure), and then the excess film was cut off.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例４におけるペリクル膜の長辺側の膜沈み量は２．２３ｍｍ、短辺側の膜沈み量は２．０６ｍｍであった。
（実施例５） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 4, the film sinking amount on the long side of the pellicle film was 2.23 mm, and the film sinking amount on the short side was 2.06 mm.
(Example 5)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ２、内側コーナーＲ２とし、長辺部の幅が７ｍｍ、短辺部の幅が６ｍｍ、内寸が１３４８ｍｍ×１１２６ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が９．０ｍｍ、短辺部側が８．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R2, the inner corner R2, the long side width is 7 mm, the short side width is 6 mm, The inner dimension is 1348mm x 1126mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 9.0mm on the long side and the short side The side of 8.0mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 1.2 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例５におけるペリクル膜の長辺側の膜沈み量は２．１５ｍｍ、短辺側の膜沈み量は１．８９ｍｍであった。
（実施例６） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 5, the film sink amount on the long side of the pellicle film was 2.15 mm, and the film sink amount on the short side was 1.89 mm.
(Example 6)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ３、内側コーナーＲ２とし、長辺部の幅が９ｍｍ、短辺部の幅が９ｍｍ、内寸が１３４２ｍｍ×１１２２ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が５．０ｍｍ、短辺部側が４．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R3, the inner corner R2, the long side width is 9 mm, the short side width is 9 mm, The inner dimension is 1342mm x 1122mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side The side of 4.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの短辺部も膨出部から４．６ｍｍ内側に向けて冶具で押さえ込みながら、長辺部は何もしない状態で、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and the short side of the pellicle frame is pressed inward by 4.6mm from the bulging part while the long side does nothing Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例６におけるペリクル膜の長辺側の膜沈み量は１．４１ｍｍ、短辺側の膜沈み量は１．５１ｍｍであった。
（実施例７） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 6, the film sink amount on the long side of the pellicle film was 1.41 mm, and the film sink amount on the short side was 1.51 mm.
(Example 7)
　大型ペリクル用の枠体として実施例４と同様の枠体を用意した。枠体は、各辺部が直線状の初期形状のものを用いた。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ５、内側コーナーＲ２とし、長辺部の幅が１２ｍｍ、短辺部の幅が４ｍｍ、内寸が１３５２ｍｍ×１１１６ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が３．０ｍｍ、短辺部側が１２．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. The frame used was an initial shape with straight sides. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R5, the inner corner R2, the long side width is 12 mm, the short side width is 4 mm, The inner dimension is 1352mm x 1116mm, and the shape is curved and bulged so that the vicinity of the center of each side is convex outward. The bulging amount to the outside of the initial shape is 3.0mm on the long side and the short side. The one whose side was 12.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部を冶具で固定し、また、短辺部は膨出部から４．６ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. An acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the bulging portion of the long side portion of the pellicle frame is fixed with a jig, and the short side portion is 4.6 mm inside the bulging portion. The pellicle film was adhered to the pellicle frame while being pressed down with a jig, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例７におけるペリクル膜の長辺側の膜沈み量は１．５４ｍｍ、短辺側の膜沈み量は１．４５ｍｍであった。
（実施例８） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 7, the film sink amount on the long side of the pellicle film was 1.54 mm, and the film sink amount on the short side was 1.45 mm.
(Example 8)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ４、内側コーナーＲ２とし、長辺部の幅が１１ｍｍ、短辺部の幅が７ｍｍ、内寸が１３４６ｍｍ×１１１８ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が５．０ｍｍ、短辺部側が６．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R4, the inner corner R2, the long side width is 11 mm, the short side width is 7 mm, The inner dimension is 1346mm x 1118mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side The side of 6.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から２．３ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 2.3 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例８におけるペリクル膜の長辺側の膜沈み量は１．４６ｍｍ、短辺側の膜沈み量は１．７６ｍｍであった。
（実施例９） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 8, the film sink amount on the long side of the pellicle film was 1.46 mm, and the film sink amount on the short side was 1.76 mm.
Example 9
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ４、内側コーナーＲ２とし、長辺部の幅が１０ｍｍ、短辺部の幅が１１ｍｍ、内寸が１３３８ｍｍ×１１２０ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が４．０ｍｍ、短辺部側が４．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is an aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R4, the inner corner R2, the long side width is 10 mm, the short side width is 11 mm, The inner dimension is 1338mm x 1120mm, the shape is curved and bulged so that the vicinity of the center of each side protrudes to the outside, the amount of bulging outward from the initial shape is 4.0mm on the long side, and the short side The side of 4.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から２．３ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 1.2 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 2.3 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例９におけるペリクル膜の長辺側の膜沈み量は１．０５ｍｍ、短辺側の膜沈み量は０．８９ｍｍであった。
（実施例１０） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 9, the film sink amount on the long side of the pellicle film was 1.05 mm, and the film sink amount on the short side was 0.89 mm.
(Example 10)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ５．５、内側コーナーＲ２とし、長辺部の幅が１１ｍｍ、短辺部の幅が１０ｍｍ、内寸が１３４０ｍｍ×１１１８ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が７．５ｍｍ、短辺部側が３．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R5.5, the inner corner R2, the width of the long side is 11 mm, the width of the short side is 10mm, inner dimension is 1340mm x 1118mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, the amount of bulging outward from the initial shape is 7.5mm on the long side A side having a side of 3.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から４．６ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed with a jig from the bulging part of the long side part of the pellicle frame to the inner side by 4.6 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed by a jig toward the inside by 1.2 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例１０におけるペリクル膜の長辺側の膜沈み量は１．００ｍｍ、短辺側の膜沈み量は０．９５ｍｍであった。
（実施例１１） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 10, the film sink amount on the long side of the pellicle film was 1.00 mm, and the film sink amount on the short side was 0.95 mm.
(Example 11)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ３、内側コーナーＲ２とし、長辺部の幅が１１ｍｍ、短辺部の幅が５ｍｍ、内寸が１３５０ｍｍ×１１１８ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が５．０ｍｍ、短辺部側が１４．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R3, the inner corner R2, the long side width is 11 mm, the short side width is 5 mm, The inner dimension is 1350mm x 1118mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 5.0mm on the long side and the short side The one whose side was 14.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から２．３ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から７．０ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and it is pressed by a jig from the bulging part of the long side part of the pellicle frame to the inside by 2.3 mm, and the short side part also bulges. The pellicle film was adhered to the pellicle frame while being pressed with a jig toward the inside 7.0 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、実施例１１におけるペリクル膜の長辺側の膜沈み量は１．６７ｍｍ、短辺側の膜沈み量は１．９８ｍｍであった。
（比較例１） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Example 11, the film sink amount on the long side of the pellicle film was 1.67 mm, and the film sink amount on the short side was 1.98 mm.
(Comparative Example 1)
　実施例１で使用した大型ペリクル用の枠体を用い、大型ペリクル用の枠体の長辺部の中央を押さえ込まないでペリクル膜を枠体に接着した。それ以外は、実施例１と同様とした。その結果、ペリクルフレームのコーナー部付近に湾曲部が残る形状になり、角部が変形したため、外観に不具合が生じた。 Using the large pellicle frame used in Example 1, the pellicle film was adhered to the frame without pressing down the center of the long side of the large pellicle frame. Other than that was the same as Example 1. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。
（比較例２） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG.
(Comparative Example 2)
　実施例２で使用した大型ペリクル用の枠体を用い、大型ペリクル用のペリクルフレームの長辺部を内側に向けて押さえ込まないでペリクル膜をペリクルフレームに接着した。それ以外は、実施例２と同様とした。その結果、ペリクルフレームのコーナー部付近に湾曲部が残る形状になり、角部が変形したため、外観に不具合が生じた。 Using the large pellicle frame used in Example 2, the pellicle film was adhered to the pellicle frame without pressing the long side of the large pellicle frame inward. Other than that was the same as Example 2. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。
（比較例３） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG.
(Comparative Example 3)
　実施例３で使用した大型ペリクル用の枠体で、長辺部の初期形状の膨出量を０ｍｍにしたものを用い、大型ペリクル用のペリクルフレームの長辺部を押さえ込まないでペリクル膜をペリクルフレームに接着した。それ以外は、実施例３と同様とした。その結果、ペリクルフレームのコーナー部付近に湾曲部が残る形状になり、角部が変形したため、外観に不具合が生じた。 The frame for the large pellicle used in Example 3 with the bulging amount of the initial shape of the long side set to 0 mm is used, and the pellicle film is peeled without pressing down the long side of the pellicle frame for the large pellicle. Glued to the frame. Other than that was the same as Example 3. As a result, a curved portion remains in the vicinity of the corner portion of the pellicle frame, and the corner portion is deformed, resulting in a defect in appearance.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。
（比較例４） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG.
(Comparative Example 4)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ９、内側コーナーＲ２とし、長辺部の幅が９ｍｍ、短辺部の幅が１０ｍｍ、内寸が１３４０ｍｍ×１１２２ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が２．３ｍｍ、短辺部側が１．５ｍｍのものを用意した。そして、この大型ペリクル用のペリクルフレームの長辺部及び短辺部を押さえ込まないでペリクル膜をペリクルフレームに接着した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R9, the inner corner R2, the long side width is 9 mm, the short side width is 10 mm, The inner dimension is 1340mm x 1122mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 2.3mm on the long side and the short side A 1.5 mm side was prepared. Then, the pellicle film was bonded to the pellicle frame without pressing down the long side and the short side of the pellicle frame for the large pellicle.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。また、比較例４におけるペリクル膜の長辺側の膜沈み量は２．７８ｍｍ、短辺側の膜沈み量は２．３７ｍｍであった。
（比較例５） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.78 mm, and the film sink amount on the short side was 2.37 mm.
(Comparative Example 5)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ６、内側コーナーＲ２とし、長辺部の幅が４ｍｍ、短辺部の幅が４ｍｍ、内寸が１３５２ｍｍ×１１３２ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が３０．０ｍｍ、短辺部側が２２．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R6, the inner corner R2, the long side width is 4 mm, the short side width is 4 mm, The inner dimension is 1352mm x 1132mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 30.0mm on the long side and the short side The one with a side of 22.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から７．０ｍｍ内側に向けて冶具で押さえ込みながら、また、短辺部も膨出部から７．０ｍｍ内側に向けて冶具で押さえ込みながら、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and it is pressed inward by 7.0mm from the bulge of the long side of the pellicle frame, while the short side also bulges. The pellicle film was adhered to the pellicle frame while being pressed with a jig toward the inside 7.0 mm from the part, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。本比較例においては、ペリクルフレームが略四角形にはならなかった。
また、比較例４におけるペリクル膜の長辺側の膜沈み量は２．７８ｍｍ、短辺側の膜沈み量は２．３７ｍｍであった。
（比較例６） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, the pellicle frame did not become substantially rectangular.
In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.78 mm, and the film sink amount on the short side was 2.37 mm.
(Comparative Example 6)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ５、内側コーナーＲ２とし、長辺部の幅が９ｍｍ、短辺部の幅が７ｍｍ、内寸が１３４６ｍｍ×１１２２ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が８．０ｍｍ、短辺部側が７．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R5, the inner corner R2, the long side width is 9 mm, the short side width is 7 mm, The inner dimension is 1346mm x 1122mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 8.0mm on the long side and the short side The side of 7.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの短辺部も膨出部から１．２ｍｍ内側に向けて冶具で押さえ込みながら、長辺部は何もしない状態で、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the short side of the pellicle frame is pressed inward by 1.2mm from the bulging part, while the long side does nothing Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。本比較例においては、大型ペリクルのハンドリング時にペリクル膜に自重撓みが発生した。また、比較例４におけるペリクル膜の長辺側の膜沈み量は２．５３ｍｍ、短辺側の膜沈み量は２．２１ｍｍであった。
（比較例７〕 In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, self-weight deflection occurred in the pellicle film during handling of the large pellicle. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 2.53 mm, and the film sink amount on the short side was 2.21 mm.
(Comparative Example 7)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ６、内側コーナーＲ２とし、長辺部の幅が８ｍｍ、短辺部の幅が７ｍｍ、内寸が１３４６ｍｍ×１１２４ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が９．０ｍｍ、短辺部側が８．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R6, the inner corner R2, the long side width is 8 mm, the short side width is 7 mm, The inner dimension is 1346mm x 1124mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 9.0mm on the long side and the short side The side of 8.0mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から２．３ｍｍ内側に向けて冶具で押さえ込みながら、短辺部は何もしない状態で、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge of the pellicle frame, and the short side is left untouched with a jig from the bulge of the long side of the pellicle frame toward the inside by 2.3 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。本比較例においては、大型ペリクルのハンドリング時にペリクルフレームの短辺部にジグが当たり、ジグが当たった部分に隣接するペリクル膜の部分にシワが発生した。また、比較例４におけるペリクル膜の長辺側の膜沈み量は１．９７ｍｍ、短辺側の膜沈み量は２．３５ｍｍであった。
（比較例８） In the same manner as in Example 1, the presence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, when handling a large pellicle, a jig hits the short side of the pellicle frame, and wrinkles were generated in the portion of the pellicle film adjacent to the portion hit by the jig. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 1.97 mm, and the film sink amount on the short side was 2.35 mm.
(Comparative Example 8)
　大型ペリクル用の枠体として、実施例４と同様の枠体を用意した。別途、大型ペリクル用のペリクルフレームとして、材質がアルミニウム合金、厚さが５．５ｍｍ、角部は外側コーナーＲ５、内側コーナーＲ２とし、長辺部の幅が８ｍｍ、短辺部の幅が１０ｍｍ、内寸が１３４０ｍｍ×１１２４ｍｍ、各辺部の中央付近が外側に凸となるように湾曲膨出した形状で、初期形状の外側への膨出量として、長辺部側が１５．０ｍｍ、短辺部側が４．０ｍｍのものを用意した。 A frame similar to that of Example 4 was prepared as a frame for a large pellicle. Separately, as a pellicle frame for a large pellicle, the material is aluminum alloy, the thickness is 5.5 mm, the corners are the outer corner R5, the inner corner R2, the long side width is 8 mm, the short side width is 10 mm, The inner dimension is 1340mm x 1124mm, the shape is curved and bulged so that the vicinity of the center of each side is convex outward, and the bulging amount to the outside of the initial shape is 15.0mm on the long side, short side The side of 4.0 mm was prepared.
　大型ペリクルは、次のように製造した。大型ペリクル用の枠体に、基板上に成膜したセルロースエステルのペリクル膜に接着させ、その後基板からペリクル膜を剥離させた。大型ペリクル用のペリクルフレームの下縁面には、スチレンエチレンブチレンスチレン系のマスク粘着材を塗布した。ペリクルフレームの上縁面には、アクリル系の膜接着剤を塗布し、ペリクルフレームの長辺部の膨出部から７．０ｍｍ内側に向けて冶具で押さえ込みながら、短辺部は何もしない状態で、ペリクルフレームにペリクル膜を接着し、その後、余剰膜を切除した。 The large pellicle was manufactured as follows. A large pellicle frame was adhered to a cellulose ester pellicle film formed on the substrate, and then the pellicle film was peeled off from the substrate. A styrene ethylene butylene styrene mask adhesive was applied to the lower edge surface of the pellicle frame for a large pellicle. Acrylic film adhesive is applied to the upper edge surface of the pellicle frame, and the short side is left untouched with a jig from the bulging part of the long side of the pellicle frame to the inside of 7.0 mm. Then, the pellicle film was adhered to the pellicle frame, and then the excess film was excised.
　実施例１と同様に、シワの有無とハンドリング性を評価した。評価結果を図１０に示す。本比較例においては、ペリクルフレームの短辺部近傍のペリクル膜にシワが発生した。また、比較例４におけるペリクル膜の長辺側の膜沈み量は１．３５ｍｍ、短辺側の膜沈み量は１．８ｍｍであった。 As in Example 1, the presence or absence of wrinkles and handling properties were evaluated. The evaluation results are shown in FIG. In this comparative example, wrinkles occurred in the pellicle film near the short side of the pellicle frame. In Comparative Example 4, the film sink amount on the long side of the pellicle film was 1.35 mm, and the film sink amount on the short side was 1.8 mm.
　１…ペリクル、１０…ペリクルフレーム、１０ａ…長辺部、１０ｂ…短辺部、１１…ペリクル膜、１２…粘着剤、１３…保護フィルム、２０…枠体、２０ａ…長辺部、２０ｂ…短辺部、３０…基板、Ｆ…開口部、Ｇ…開口部、Ｓ…膨出量。 DESCRIPTION OF SYMBOLS 1 ... Pellicle, 10 ... Pellicle frame, 10a ... Long side part, 10b ... Short side part, 11 ... Pellicle film, 12 ... Adhesive, 13 ... Protective film, 20 ... Frame, 20a ... Long side part, 20b ... Short Side, 30 ... substrate, F ... opening, G ... opening, S ... bulge amount.

Claims (9)

  1. 　四つの辺部により略矩形の枠状に形成されてペリクル膜を展張支持するペリクルフレームであって、
    　前記辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、前記辺部の短辺幅／短辺長の割合が０．３％以上３．８％以下であり、
    　少なくとも一対の前記辺部が前記ペリクルフレームの外側に膨出している、ペリクルフレーム。     A pellicle frame that is formed into a substantially rectangular frame shape by four sides and supports the pellicle film in a stretched manner,
    The ratio of the long side width / long side length of the side part is 0.3% to 2.2%, and the ratio of the short side width / short side length of the side part is 0.3% to 3.8. % Or less,
    A pellicle frame in which at least a pair of the side portions bulge to the outside of the pellicle frame.
  2. 　前記辺部の前記長辺幅が、５ｍｍ以上、１５ｍｍ以下であり、前記辺部の前記短辺幅が、４ｍｍ以上、１５ｍｍ以下である、請求項１に記載のペリクルフレーム。 The pellicle frame according to claim 1, wherein the long side width of the side portion is 5 mm or more and 15 mm or less, and the short side width of the side portion is 4 mm or more and 15 mm or less.
  3. 　前記辺部の一対の長辺部が前記ペリクルフレームの外側に膨出しており、当該一対の長辺部の膨出量が、３ｍｍ以上、２０ｍｍ以下である、請求項１又は２に記載のペリクルフレーム。 The pellicle according to claim 1 or 2, wherein a pair of long side portions of the side portions bulge outside the pellicle frame, and a bulge amount of the pair of long side portions is 3 mm or more and 20 mm or less. flame.
  4. 　前記辺部の前記長辺長が、４００ｍｍ以上、２０００ｍｍ以下であり、前記辺部の前記短辺長が、２００ｍｍ以上、１８００ｍｍ以下である、請求項１～３のいずれか一項に記載のペリクルフレーム。 The pellicle according to any one of claims 1 to 3, wherein the long side length of the side portion is 400 mm or more and 2000 mm or less, and the short side length of the side portion is 200 mm or more and 1800 mm or less. flame.
  5. 　ヤング率が１ＧＰａ以上８０ＧＰａ以下の材質により形成される、請求項１～４のいずれか一項に記載のペリクルフレーム。 The pellicle frame according to any one of claims 1 to 4, wherein the pellicle frame is formed of a material having a Young's modulus of 1 GPa to 80 GPa.
  6. 　請求項１～５のいずれか一項に記載のペリクルフレームと、
    　前記ペリクルフレームに展張支持されるペリクル膜と、
    を有するペリクルであって、
    　少なくとも膨出された前記辺部が前記ペリクルフレームの内側に向けて弾性変形された状態で、前記ペリクル膜が前記ペリクルフレームに貼り付けられている、ペリクル。     A pellicle frame according to any one of claims 1 to 5,
    A pellicle membrane that is stretched and supported by the pellicle frame;
    A pellicle having
    A pellicle in which the pellicle film is attached to the pellicle frame in a state where at least the bulged side portion is elastically deformed toward the inside of the pellicle frame.
  7. 　膨出された前記辺部が、当該辺部の復元力と前記ペリクル膜の膜張力とのつり合いにより、略直線状に形成されている、請求項６に記載のペリクル。 7. The pellicle according to claim 6, wherein the bulged side portion is formed in a substantially linear shape by a balance between a restoring force of the side portion and a film tension of the pellicle membrane.
  8. 　上記ペリクル膜には、以下の条件Ａ、条件Ｂ及び条件Ｃを全て満たすような大きさの膜張力が付与されている、請求項６又は７に記載のペリクル。
    条件Ａ：前記ペリクル膜が略水平となるように前記ペリクルを配置した状態において、前記ペリクル膜上の第１基準点であって、平面視で前記ペリクルフレームの前記辺部の長辺部の内縁の中央点から当該長辺部の内縁と直交する方向に３０ｍｍ離れた第１基準点上に１０．６ｇの重りを載せた場合の当該第１基準点の沈み量が０．４ｍｍ以上、２．４ｍｍ以下である。
    条件Ｂ：前記ペリクル膜が略水平となるように前記ペリクルを配置した状態において、前記ペリクル膜上の第２基準点であって、平面視で前記ペリクルフレームの前記辺部の短辺部の内縁の中央点から当該短辺部と直交する方向に３０ｍｍ離れた第２基準点上に１０．６ｇの重りを載せた場合の当該第２基準点の沈み量が０．３ｍｍ以上、２．３ｍｍ以下である。
    　条件Ｃ：前記第１基準点の前記沈み量と前記第２基準点の前記沈み量との差の絶対値が０．４ｍｍ以下である。     The pellicle according to claim 6 or 7, wherein a film tension having a magnitude that satisfies all of the following conditions A, B, and C is applied to the pellicle film.
    Condition A: a first reference point on the pellicle film in a state where the pellicle film is arranged substantially horizontally, and an inner edge of the long side part of the side part of the pellicle frame in plan view 1. When the weight of 10.6 g is placed on the first reference point 30 mm away from the center point of the long side in the direction orthogonal to the inner edge of the long side portion, the sinking amount of the first reference point is 0.4 mm or more. 4 mm or less.
    Condition B: a second reference point on the pellicle film in a state where the pellicle film is arranged substantially horizontally, and an inner edge of the short side portion of the side portion of the pellicle frame in plan view The sinking amount of the second reference point when the weight of 10.6 g is placed on the second reference point that is 30 mm away from the central point in the direction orthogonal to the short side portion is 0.3 mm or more and 2.3 mm or less. It is.
    Condition C: The absolute value of the difference between the sinking amount of the first reference point and the sinking amount of the second reference point is 0.4 mm or less.
  9. 　（ａ）基板上に成膜された高分子材料からなるペリクル膜を、開口部を有する枠体に当該開口部を覆うように貼り付ける工程と、
    　（ｂ）前記枠体に貼り付けられた前記ペリクル膜を、前記基板から剥離する工程と、
    　（ｃ）四つの辺部により略矩形の枠状に形成されたペリクルフレームであって、少なくとも一対の前記辺部が前記ペリクルフレームの外側に膨出しており、前記辺部の長辺幅／長辺長の割合が、０．３％以上２．２％以下であり、前記辺部の短辺幅／短辺長の割合が０．３％以上３．８％以下である、ペリクルフレームを用意する工程と、
    　（ｄ）前記ペリクルフレームの前記少なくとも一対の前記辺部に外力を付与することにより、当該少なくとも一対の前記辺部が略直線状になるように当該少なくとも一対の前記辺部を弾性変形させる工程と、
    　（ｅ）前記工程（ｄ）の後に、前記少なくとも一対の前記辺部が略直線状になるように弾性変形している状態の前記ペリクルフレームに、当該ペリクルフレームの開口部を覆うように前記枠体に貼り付けられた前記ペリクル膜を貼り付ける工程と、
    　（ｆ）前記工程（ｅ）の後に、前記少なくとも一対の前記辺部に付与している前記外力を取り除くことにより、前記ペリクル膜を前記ペリクルフレームによって展張支持する工程と、
    　（ｇ）前記工程（ｅ）の後に、前記ペリクル膜の余剰部分及び前記枠体を除去する工程と、
    を備える、ペリクルの製造方法。
          (A) attaching a pellicle film made of a polymer material formed on a substrate to a frame having an opening so as to cover the opening;
    (B) peeling off the pellicle film attached to the frame from the substrate;
    (C) A pellicle frame formed in a substantially rectangular frame shape by four sides, wherein at least a pair of the sides protrudes outside the pellicle frame, and the long side width / length of the sides A pellicle frame having a side length ratio of 0.3% to 2.2% and a short side width / short side length ratio of the side part of 0.3% to 3.8% is prepared. And a process of
    (D) applying an external force to the at least one pair of the side portions of the pellicle frame to elastically deform the at least one pair of the side portions so that the at least one pair of the side portions are substantially linear; ,
    (E) After the step (d), the frame so that the pellicle frame is elastically deformed so that the at least one pair of the side portions are substantially linear so as to cover the opening of the pellicle frame. Attaching the pellicle film attached to the body;
    (F) After the step (e), by removing the external force applied to the at least one pair of side portions, the pellicle film is stretched and supported by the pellicle frame;
    (G) after the step (e), removing the excess portion of the pellicle film and the frame;
    A method for manufacturing a pellicle.
PCT/JP2013/058173 2012-03-21 2013-03-21 Pellicle, pellicle frame, and method for manufacturing pellicle WO2013141325A1 (en)

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