Pellicle frame, pellicle, pellicle-equipped exposure master, exposure method, and semiconductor manufacturing method

Abstract

To provide a pellicle frame having satisfactory resistance to hydrogen radicals in EUV exposure, a pellicle comprising the pellicle frame, a pellicle-attached exposure original, an exposure method, and a method for manufacturing a semiconductor.SOLUTION: The present invention provides: a pellicle frame for EUV exposure, characterized in that the pellicle frame is provided with at least one ventilation part, and a filter coated with a crosslinked resin or cured resin on a porous membrane is attached inside the ventilation part; a pellicle, characterized in that a pellicle film is stretched on the pellicle frame; a pellicle-attached exposure original for EUV exposure, characterized in that the pellicle is attached to the exposure original; an exposure method; and a method for manufacturing a semiconductor.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a pellicle frame, a pellicle, an exposure master with a pellicle, a method for manufacturing a semiconductor, a method for manufacturing a liquid crystal display panel, and an exposure method. [Background technology]

[0002] In recent years, LSI design rules have been miniaturized to the sub-quarter micron level, and as a result, the wavelength of exposure light sources has been shortened. That is, exposure light sources have shifted from g-line (436 nm) and i-line (365 nm) from mercury lamps to KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm), and further, EUV (Extreme Ultra Violet) exposure using EUV light with a dominant wavelength of 13.5 nm is being considered.

[0003] In the manufacture of semiconductors such as LSIs and VLSIs, or liquid crystal display panels, patterns are created by irradiating light onto semiconductor wafers or liquid crystal masters. However, if dust adheres to the lithography photomasks and reticles (hereinafter collectively referred to as "exposure masters") used in this process, the dust can absorb or bend the light, causing deformation of the transferred pattern, rough edges, and black staining of the base, resulting in problems such as impaired dimensions, quality, and appearance.

[0004] These operations are usually performed in a clean room, but it is still difficult to keep the exposure master clean at all times. Therefore, a common method is to attach a pellicle to the surface of the exposure master to protect it from dust before exposure. In this case, foreign particles do not adhere directly to the surface of the exposure master, but rather to the pellicle. Therefore, if the focus is aligned on the pattern of the exposure master during lithography, the foreign particles on the pellicle will not affect the transfer.

[0005] The basic structure of this pellicle is a pellicle frame made of aluminum or titanium, with a pellicle film that is highly transmissive to the light used for exposure stretched over the upper surface, and an airtight gasket formed on the lower surface. The airtight gasket generally uses an adhesive layer, and a protective sheet is attached to protect this adhesive layer. The pellicle film is made of materials such as nitrocellulose, cellulose acetate, and fluorine-based polymers that allow good transmission of the light used for exposure (g-line (436 nm) from a mercury lamp, i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), etc.). However, for EUV exposure, ultrathin silicon and carbon films are being considered as pellicle films.

[0006] Meanwhile, porous membranes such as those used in HEPA (High Efficiency Particulate Air) filters and ULPA (Ultra Low Penetration Air) filters have been used as pellicle filters due to their ability to remove foreign matter. The use of similar filters in EUV pellicles is also being considered, as described in Patent Document 1, for example.

[0007] However, the inside of an EUV exposure tool is filled with hydrogen gas to efficiently remove foreign matter called debris, which is generated when EUV light is generated. This hydrogen gas reacts with the EUV light to form hydrogen radicals. Therefore, EUV pellicles must be sufficiently resistant to hydrogen radicals, something that was not required for conventional KrF and ArF pellicles.

[0008] Generally, filters have a porous membrane to capture foreign matter. As gas passes through the gaps in the porous membrane, the membrane captures the foreign matter, allowing only the gas without foreign matter to pass through. Due to its properties, it is easy to imagine that the porous membrane has the largest surface area of ​​all the components used in pellicles and is most exposed to gas containing hydrogen radicals. Therefore, if the porous membrane is degraded by hydrogen radicals and the gaps become larger, the foreign matter capture rate may also decrease. Therefore, the porous membrane used in filters must have high hydrogen radical resistance. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2016 / 043292 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in consideration of the above circumstances, and aims to provide a pellicle frame that is sufficiently resistant to hydrogen radicals during EUV exposure, a pellicle using said pellicle frame, an exposure master plate with a pellicle, a method for manufacturing a semiconductor, a method for manufacturing a liquid crystal display panel, and an exposure method. [Means for solving the problem]

[0011] As a result of extensive research into achieving the above-mentioned object, the inventors of the present invention discovered that the above-mentioned problems can be solved by providing a filter having a resin-coated porous membrane in a ventilation section provided in a pellicle frame to provide a pellicle frame that is resistant to hydrogen radicals during EUV exposure, and that the resin that coats the porous membrane is preferably formed from a silicone resin or an epoxy resin, thereby completing the present invention.

[0012] Therefore, the present invention provides the following pellicle frame, pellicle, pellicle-equipped exposure master, semiconductor manufacturing method, liquid crystal display panel manufacturing method, and exposure method. 1. A pellicle frame for EUV exposure, characterized in that the pellicle frame has at least one ventilation section, and a filter having a porous membrane coated with resin is attached within the ventilation section. 2. The pellicle frame according to 1 above, wherein the porous membrane is a resin porous membrane made of at least one resin selected from the group consisting of fluororesin, polyester resin, polyimide resin, polycarbonate resin and polyolefin resin. 3. The pellicle frame according to the above item 1, wherein the porous membrane is a polytetrafluoroethylene porous membrane. 4. The pellicle frame according to 1 or 2 above, wherein the resin coating the porous membrane is a silicone resin or an epoxy resin. 5. The pellicle frame according to 1 or 2 above, wherein the filter has an air-permeable support layer that supports the porous membrane. 6. A pellicle frame according to 1 or 2 above, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, and adjacent nodes are connected by fibrils. 7. The pellicle frame according to 5 above, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, net, and mesh. 8. A pellicle frame according to 1 or 2 above, wherein the thickness of the pellicle frame is less than 2.5 mm. 9. A pellicle for EUV exposure, characterized in that a pellicle film is stretched over the pellicle frame described in 1 above. 10. The pellicle according to claim 9, wherein the height of the pellicle is 2.5 mm or less. 11. A pellicle according to claim 9 or 10, wherein the pellicle membrane is supported by a frame. 12. An exposure master with a pellicle, characterized in that the pellicle described in 9 above is attached to the exposure master. 13. The exposure master with pellicle according to the above item 12, wherein the exposure master is an exposure master for EUV. 14. A pellicle-equipped exposure master according to the above item 12, which is a pellicle-equipped exposure master used in EUV lithography. 15. An exposure method comprising carrying out EUV exposure using the pellicle-equipped exposure master described in 12 above. 16. A method of manufacturing a semiconductor, comprising a step of EUV exposure using the pellicle-equipped exposure master described in 12 above. 17. A method for manufacturing a liquid crystal display panel, comprising a step of EUV exposure using the pellicle-equipped exposure master described in 12 above. 18. A pellicle frame for use in a hydrogen plasma environment, characterized in that the pellicle frame has at least one ventilation section, and a filter having a porous membrane coated with resin is attached within the ventilation section. 19. The pellicle frame according to the above item 18, wherein the porous membrane is a resin porous membrane made of at least one resin selected from the group consisting of fluororesin, polyester resin, polyimide resin, polycarbonate resin and polyolefin resin. 20. The pellicle frame according to the above item 18, wherein the porous membrane is a polytetrafluoroethylene porous membrane. 21. The pellicle frame according to the above item 18 or 19, wherein the resin coating the porous membrane is a silicone resin or an epoxy resin. 22. The pellicle frame according to claim 18 or 19, wherein the filter has an air-permeable support layer that supports the porous membrane. 23. A pellicle frame according to 18 or 19 above, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, and adjacent nodes are connected by fibrils. 24. The pellicle frame according to claim 22, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, net, and mesh. 25. A pellicle frame according to claim 18 or 19, wherein the thickness of the pellicle frame is less than 2.5 mm. 26. A pellicle for use in a hydrogen plasma environment, characterized in that a pellicle film is stretched over the pellicle frame of claim 18. 27. A pellicle according to claim 26, wherein the height of the pellicle is 2.5 mm or less. 28. A pellicle according to claim 26 or 27, wherein the pellicle membrane is supported by a frame. 29. An exposure master with a pellicle for use in a hydrogen plasma environment, characterized in that the pellicle according to claim 26 is attached to the exposure master. 30. The exposure master with pellicle according to 29 above, wherein the exposure master is an exposure master for EUV. 31. A pellicle-equipped exposure master according to claim 29, which is a pellicle-equipped exposure master used in EUV lithography. 32. An exposure method characterized in that exposure is carried out in a hydrogen plasma environment using the pellicle-equipped exposure master described in 29 above. 33. A method for manufacturing a semiconductor, comprising a step of exposing in a hydrogen plasma environment using the pellicle-equipped exposure master described in 29 above. 34. A method for manufacturing a liquid crystal display panel, comprising a step of exposing in a hydrogen plasma environment using the pellicle-equipped exposure master described in 29 above. [Effects of the Invention]

[0013] According to the present invention, a pellicle frame and a pellicle that are sufficiently resistant to hydrogen radicals during EUV exposure can be provided, and these pellicle-equipped exposure masters are useful in EUV exposure methods, semiconductor manufacturing methods, and liquid crystal display panel manufacturing methods. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a plan view showing an example of a pellicle frame of the present invention. [Figure 2] FIG. 2 is a cross-sectional view taken along line AA of the pellicle frame, showing a ventilation section and a filter section. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in more detail below. The present invention relates to a frame-shaped pellicle frame having an upper end surface on which a pellicle membrane is provided and a lower end surface facing a photomask, and a pellicle using the same.

[0016] If the pellicle frame is frame-shaped, its shape corresponds to the shape of the photomask to which the pellicle is attached. Generally, it is a quadrilateral (rectangular or square) frame. The corners (edges) of the pellicle frame may be angular (sharp) as they are, or may be chamfered, such as with an R-chamfer or C-chamfer, to form a curved shape or other shape.

[0017] The pellicle frame also has a surface for providing a pellicle film (here referred to as the upper end surface) and a surface facing the photomask when the photomask is mounted (here referred to as the lower end surface).

[0018] Typically, a pellicle film is provided on the upper end surface via an adhesive or the like, and a pressure sensitive adhesive or the like for attaching the pellicle to a photomask is provided on the lower end surface, but this is not limited to this.

[0019] There are no limitations on the material of the pellicle frame, and known materials can be used. Because EUV pellicle frames may be exposed to high temperatures, materials with a low thermal expansion coefficient are preferred. Examples include Si, SiO2, SiN, quartz, invar, titanium, and titanium alloys. Among these, titanium and titanium alloys are preferred due to their ease of processing and light weight.

[0020] The dimensions of the pellicle frame are not particularly limited, but since the height of the EUV pellicle is limited to 2.5 mm or less, the thickness of the EUV pellicle frame is smaller than that, being less than 2.5 mm.

[0021] Furthermore, the thickness of the pellicle frame for EUV is preferably 1.5 mm or less, taking into consideration the thickness of the pellicle film, mask adhesive, etc. Furthermore, the lower limit of the thickness of the pellicle frame is preferably 1.0 mm or more.

[0022] Typically, a jig hole is provided on the side of the pellicle frame for use in handling and peeling the pellicle from the photomask. The size of the jig hole is 0.5 to 1.0 mm in length in the thickness direction of the frame (or diameter if circular). There are no restrictions on the shape of the hole, and it can be circular or rectangular.

[0023] In the present invention, the pellicle frame is provided with a vent for mitigating pressure changes inside and outside the pellicle. There are no restrictions on the shape or number of the vent. A filter is provided in the vent to prevent foreign matter from entering the pellicle. There are no particular restrictions on where the filter is installed, and the filter can be installed inside the pellicle frame, inside the vent, or outside the pellicle frame.

[0024] The pellicle frame of the present invention is characterized by having a filter with a porous membrane coated with a resin resistant to hydrogen radicals. The porous membrane is not particularly limited, but is preferably selected from at least one resin selected from the group consisting of fluororesins, polyester resins, polyimide resins, polycarbonate resins, and polyolefin resins. Fluororesins that have a proven track record of use as KrF pellicles and ArF pellicles are particularly preferred, and polytetrafluoroethylene (PTFE) is particularly preferred.

[0025] A PTFE porous membrane is generally composed of nodes, which are aggregates of PTFE, and countless fibrils, which are fine fibrous structures with both ends connected to the nodes. Adjacent nodes are connected by fibrils. A PTFE porous membrane has air permeability in the membrane thickness direction, with the spaces (pores) between adjacent fibrils serving as ventilation paths. A PTFE porous membrane is also called an expanded porous membrane, and is formed by expanding a PTFE sheet, which is an aggregate of PTFE. Nodes and fibrils are formed by expanding the PTFE sheet, and their configuration changes depending on, for example, the expansion conditions of the PTFE sheet.

[0026] The resin used to coat the porous membrane preferably has sufficient hydrogen radical resistance, and specific examples include silicone resin, epoxy resin, acrylic resin, fluororesin, and urethane resin. Among these, silicone resin or epoxy resin is preferred from the perspective of hydrogen radical resistance, and silicone resin is more preferred. There are no particular limitations on the method for coating the porous membrane with the resin, but preparing a resin solution and impregnating it into the porous membrane is easy and preferred. There are no limitations on the method for impregnating the porous membrane with the resin solution, and methods such as immersing the porous membrane in the resin solution, spin-coating the resin solution onto the porous membrane, or spraying the resin solution are possible. By using a resin solution, the solution easily spreads into the gaps in the porous membrane, allowing the resin to coat the fibers of the porous membrane. In the present invention, the resin coating of the porous membrane does not necessarily need to cover the entire surface of the porous membrane; the coating amount and coating ratio can be adjusted depending on the desired hydrogen radical resistance. Hydrogen radical resistance can also be improved by crosslinking and curing these resins with light or heat.

[0027] In the present invention, the filter may include any member other than the porous membrane. The member may be, for example, a breathable support layer. In this case, the filter includes a porous membrane and a breathable support layer disposed on one main surface of the porous membrane. The provision of the breathable support layer improves the strength of the filter and also improves its ease of handling.

[0028] The breathable support layer is preferably a layer having higher breathability and moisture permeability in the thickness direction than the porous membrane. The breathable support layer may be, for example, a woven fabric, a nonwoven fabric, a net, or a mesh. The breathable support layer may be made of, for example, polyester, polyethylene, or aramid resin. The shape of the breathable support layer may be the same as or different from the shape of the porous membrane. The breathable support layer is arranged, for example, by heat welding to the porous membrane or bonding with an adhesive. The breathable support layer may be arranged on one or both main surfaces of the porous membrane. These breathable support layers may be coated with the resin described above.

[0029] Furthermore, although there are no limitations on the material of the pellicle film, a material with high transmittance at the wavelength of the exposure light source and high light resistance is preferred. For example, an ultrathin silicon film or a carbon film is used for EUV exposure. Examples of carbon films include films of graphene, diamond-like carbon, and carbon nanotubes. Note that if the pellicle film is difficult to handle alone, a pellicle film supported by a frame such as silicon can be used. In this case, the pellicle can be easily manufactured by adhering the frame region to the pellicle frame.

[0030] In the pellicle of the present invention, a pellicle membrane is attached to the upper end surface of the pellicle frame as described above via a pressure-sensitive adhesive or adhesive. There are no restrictions on the material of the pressure-sensitive adhesive or adhesive, and known materials can be used. In order to firmly hold the pellicle membrane in place, a pressure-sensitive adhesive or adhesive with strong adhesive strength is preferred.

[0031] Furthermore, an adhesive for attaching a photomask is formed on the lower end surface of the pellicle frame. In general, it is preferable that the mask adhesive be provided over the entire periphery of the pellicle frame.

[0032] As the masking adhesive, known adhesives can be used, and acrylic adhesives and silicone adhesives are preferably used. The adhesive may be processed into any shape as needed.

[0033] A release layer (separator) may be attached to the lower end surface of the mask adhesive to protect the adhesive. The material of the release layer is not particularly limited, but examples include polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyethylene (PE), polycarbonate (PC), polyvinyl chloride (PVC), and polypropylene (PP). If necessary, a release agent such as a silicone-based release agent or a fluorine-based release agent may be applied to the surface of the release layer.

[0034] The pellicle of the present invention can be used not only as a protective member for preventing foreign matter from adhering to an exposure master in an exposure apparatus, but also as a protective member for protecting the exposure master during storage or transportation of the exposure master. Methods for attaching a pellicle to an exposure master such as a photomask to produce an exposure master with a pellicle include the method of attaching the pellicle with a mask adhesive as described above, as well as electrostatic adsorption and mechanical fixing methods.

[0035] The semiconductor or liquid crystal display panel manufacturing method according to this embodiment includes a step of exposing a substrate (semiconductor wafer or liquid crystal display panel) using the above-described pellicle-attached exposure master. For example, in a lithography process, which is one of the manufacturing processes for semiconductor devices or liquid crystal display panels, the above-described pellicle-attached exposure master is placed on a stepper and exposed to form a photoresist pattern corresponding to an integrated circuit or the like on the substrate. Generally, EUV exposure uses a projection optical system in which EUV light is reflected from the exposure master and directed to the substrate, and this is performed under reduced pressure or vacuum. As a result, even if foreign particles adhere to the pellicle during the lithography process, these particles are not imaged on the wafer coated with photoresist, preventing short circuits or disconnections in the integrated circuits or the like due to the image of the foreign particles. Therefore, the use of the pellicle-attached exposure master can improve yield in the lithography process. [Example]

[0036] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0037] [Evaluation of filter resistance to hydrogen radicals] A filter ("TEMISH S-NTF1033-N01" manufactured by Nitto Denko Corporation) consisting of a 15 cm square polytetrafluoroethylene porous membrane (PTFE porous membrane) and a polypropylene mesh support was prepared. This filter was spin-coated with a 1% by mass solution of each of the following resins (1) to (6) at 800 rpm for 60 seconds, and then air-dried at room temperature for 12 hours to volatilize the solvent. (1) Silicone resin adhesive (2) Epoxy resin adhesive (3) Acrylic resin adhesive (4) Fluorine resin (5) Urethane resin adhesive (6) Untreated

[0038] The resin-coated filter was irradiated with hydrogen plasma using the following device. ( Hydrogen plasma irradiation conditions ) Equipment: FlexAL manufactured by OXFORD INSTRUMENTS Plasma source: ICP (inductively coupled plasma) Processing conditions: pressure 80 mTorr, H2 flow rate 50 sccm Power: 200W Processing temperature: 100℃ Processing time: 600 seconds

[0039] After the hydrogen plasma exposure, the filter was observed under a microscope (Nikon's "ECLIPSE LV150") and judged as follows. The results are shown in Table 1. (judgment criteria) A: It was confirmed that the PTFE porous membrane was present and that the filter structure remained unchanged. B: The disappearance of the PTFE porous membrane was confirmed.

[0040] [Table 1]

[0041] The results in Table 1 confirm that filters with porous membranes coated with silicone resin or epoxy resin have excellent hydrogen plasma resistance. Furthermore, under the above conditions, the porous membranes of filters coated with acrylic resin, fluororesin, and urethane resin were lost to hydrogen plasma. However, by reducing the power of the hydrogen plasma, lowering the temperature, and shortening the treatment time, the superiority of these filters compared to untreated filters can be confirmed.

[0042] Example 1 A titanium pellicle frame (external dimensions: 150 mm x 118 mm x 1.5 mm, pellicle frame width: 4.0 mm) was prepared. As shown in Figures 1 and 2, an L-shaped ventilation section 10 was provided from the outside of the pellicle frame 1 to the bottom end surface. In Figures 1 and 2, reference numeral 1a denotes the top end surface of the pellicle frame, and reference numeral 1b denotes the bottom end surface of the pellicle frame. Reference numeral 20 denotes a filter provided at the opening at the bottom end surface of the pellicle frame, as will be described later, and is coated with a specified resin, although not specifically shown.

[0043] A 10 mm long, 2.5 mm wide filter (Nitto Denko Corporation, "TEMISH S-NTF1033-N01") consisting of a PTFE porous membrane and a polypropylene mesh support was prepared. Next, 100 parts by weight of a silicone resin-based adhesive (Shin-Etsu Chemical Co., Ltd., "X-40-3264") was added to 1 part by weight of a curing agent (Shin-Etsu Chemical Co., Ltd., "PT-56") and stirred. This mixture was then dissolved in a hydrocarbon solvent (Exxon Mobil Corporation, "Isopar E") to prepare a 1% by weight solution. 1 ml of this solution was impregnated into the center of the filter, which was then air-dried at room temperature for 2 hours to completely evaporate the solvent. The filter (reference number 20 in Figure 2) was attached to the opening at the bottom of the pellicle frame with double-sided tape.

[0044] The pellicle frame was washed with neutral detergent and pure water, and a 1 mm wide, 0.1 mm thick coating was applied to the upper surface of the pellicle frame. 100 parts by weight of a silicone resin adhesive ("X-40-3264" manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by weight of a curing agent ("PT-56" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed together. 100 parts by weight of an acrylic resin adhesive ("SK Dyne 1499M" manufactured by Soken Chemical & Engineering Co., Ltd.) and 0.1 parts by weight of a curing agent ("L-45" manufactured by Soken Chemical & Engineering Co., Ltd.) were mixed together. 1 mm wide, 0.1 mm thick coating was applied to the lower surface of the pellicle frame as a masking adhesive.

[0045] The pellicle frame was then heated at 100°C for 12 hours to harden the adhesive on the top and bottom surfaces. An ultrathin silicon film was then pressed onto the adhesive on the top surface of the pellicle frame to complete the pellicle.

[0046] Example 2 A 10 mm long, 2.5 mm wide filter ("TEMISH S-NTF1033-N01" manufactured by Nitto Denko Corporation) consisting of a PTFE porous membrane and a polypropylene mesh support was prepared. Next, an epoxy resin adhesive ("1001T75" manufactured by Mitsubishi Chemical Corporation) was dissolved in toluene to prepare a 1% by mass solution. 1 ml of this solution was impregnated into the center of the filter, and then air-dried at room temperature for 2 hours to completely volatilize the solvent. The filter was attached to the opening on the lower end surface of the pellicle frame with double-sided tape. Otherwise, a pellicle was completed in the same manner as in Example 1 above.

[0047] It can be seen from the above Examples 1 and 2 that a pellicle having a filter that is resistant to hydrogen radicals can be provided. [Explanation of symbols]

[0048] 1 Pellicle frame 1a Upper surface of pellicle frame 1b Bottom surface of pellicle frame 10 Ventilation section 20 filters

Claims

1. A pellicle frame for EUV exposure, the pellicle frame being provided with at least one ventilation part, and a filter being attached to the ventilation part; The filter comprises a porous membrane and an air-permeable support layer arranged on one or both main surfaces of the porous membrane, and is characterized in that the entire surface of the porous membrane is covered with a cross-linked resin or a cured resin.

2. A pellicle frame for use in a hydrogen plasma environment, the pellicle frame having at least one ventilation part provided therein, and a filter attached to the ventilation part; The filter comprises a porous membrane and an air-permeable support layer arranged on one or both main surfaces of the porous membrane, and is characterized in that the entire surface of the porous membrane is covered with a cross-linked resin or a cured resin.

3. 3. A pellicle frame according to claim 1 or 2, wherein the porous membrane is a resin porous membrane made of at least one resin selected from the group consisting of fluororesin, polyester resin, polyimide resin, polycarbonate resin and polyolefin resin.

4. 3. The pellicle frame according to claim 1, wherein the porous film is a porous polytetrafluoroethylene film.

5. 3. The pellicle frame according to claim 1, wherein the resin that coats the porous membrane is a silicone resin or an epoxy resin.

6. 3. The pellicle frame according to claim 1, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, and adjacent nodes are connected by fibrils.

7. 2. The pellicle frame according to claim 1, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, net, and mesh.

8. 3. The pellicle frame according to claim 1, wherein the thickness of the pellicle frame is less than 2.5 mm.

9. A pellicle comprising a pellicle frame according to claim 1 or 2 and a pellicle membrane stretched over the pellicle frame.

10. 10. The pellicle of claim 9, wherein the height of the pellicle is 2.5 mm or less.

11. 10. The pellicle of claim 9, wherein the pellicle membrane is supported by a frame.

12. 10. An exposure master with a pellicle, comprising the pellicle according to claim 9 attached to the exposure master.

13. An exposure method comprising EUV exposure using the pellicle-equipped exposure master plate according to claim 12.

14. A method for manufacturing a semiconductor, comprising the step of performing EUV exposure using the pellicle-equipped exposure master according to claim 12.

15. 13. An exposure method, comprising: performing exposure in a hydrogen plasma environment using the exposure master with a pellicle according to claim 12.

16. 13. A method for manufacturing a semiconductor, comprising the step of exposing in a hydrogen plasma environment using the exposure master with a pellicle according to claim 12.

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