Protective film frame, protective film, exposure master with protective film, semiconductor manufacturing method, liquid crystal display panel manufacturing method and exposure method

Abstract

The present invention aims to provide a protective film frame that is sufficiently resistant to hydrogen radicals during EUV exposure, a protective film using the protective film frame, an exposure master with the protective film, a semiconductor manufacturing method, a liquid crystal display panel manufacturing method, and an exposure method. The present invention provides a protective film frame for EUV exposure, characterized in that at least one ventilation section is provided in the protective film frame, and a filter having a porous membrane coated with resin is installed in the ventilation section; a protective film is provided, characterized in that the protective film is stretched on the protective film frame; an exposure master with a protective film is provided for EUV exposure, characterized in that the exposure master is equipped with the protective film; and a semiconductor manufacturing method, a liquid crystal display panel manufacturing method, and an exposure method are provided.

Description

[Technical Field]

[0001] This invention relates to a protective film frame, a protective film, an exposure master with a protective film, a semiconductor manufacturing method, a liquid crystal display panel manufacturing method, and an exposure method. [Previous Technology]

[0002] In recent years, the design rules for Large Scale Integrated Circuits (LSI) have been advancing towards miniaturization in the sub-quarter micron range, accompanied by a trend towards shorter wavelengths of exposure light sources. Specifically, exposure light sources have shifted from mercury lamp-based gamma rays (436 nm) and i-rays (365 nm) to KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), and further, research has been conducted on EUV exposure using extreme ultraviolet (EUV) light with a dominant wavelength of 13.5 nm.

[0003] In the manufacturing of semiconductors such as LSI and super LSI or liquid crystal display panels, patterns are created by irradiating light onto semiconductor wafers or liquid crystal substrates. If dust adheres to the photoresist and reticles (hereinafter collectively referred to as "exposure originals") used at this time, the dust will absorb light or bend the light, thus deforming the transferred pattern or making the edges rough. In addition, there are also problems such as the substrate being stained black and damage to the size, quality, and appearance.

[0004] These operations are usually performed in a clean room, but even so, it is difficult to keep the exposure plate clean at all times. Therefore, a method is generally adopted in which a protective film is attached to the surface of the exposure plate as a dust collector before exposure. In this case, foreign matter does not adhere directly to the surface of the exposure plate, but rather to the protective film. Therefore, if the focus is made on the pattern of the exposure plate during photolithography, the foreign matter on the protective film is irrelevant to the transfer.

[0005] The basic structure of the protective film is as follows: a protective film with high transmittance relative to the light used in the exposure is stretched on the upper surface of a protective film frame containing aluminum or titanium, and an airtight gasket is formed on the lower surface. The airtight gasket generally uses an adhesive layer and is covered with a protective sheet for protecting the adhesive layer. The protective film includes nitrocellulose, cellulose acetate, fluoropolymers, etc., which allow good transmission of light used in the exposure (gamma rays (436 nm), i rays (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), etc.) based on mercury lamps; however, for EUV exposure, extremely thin silicon or carbon films are being researched as protective films.

[0006] Furthermore, as a filter for protective membranes, porous membranes like those used in HEPA (High Efficiency Particulate Air Filter) or ULPA (Ultra Low Penetration Air Filter) filters have been used, depending on their foreign matter repair capabilities. In EUV protective membranes, the use of the same type of filter is being investigated, for example, as described in Patent Document 1.

[0007] However, in order to efficiently remove foreign matter known as stray particles (fragments) generated during EUV light production, the EUV exposure apparatus is filled with hydrogen gas. This hydrogen gas reacts with EUV light to form hydrogen radicals. Therefore, for EUV protective films, sufficient resistance to hydrogen radicals is not required, unlike previous KrF or ArF protective films.

[0008] Generally, filters have porous membranes to trap foreign matter. When gas passes through the gaps in the porous membrane, the membrane traps the foreign matter, allowing only the gas free of foreign matter to pass through. Based on its properties, it is easy to imagine that the porous membrane has the largest surface area among the components used in protective films and is most easily exposed to gases containing hydrogen radicals. Therefore, the porous membrane deteriorates due to hydrogen radicals, and the foreign matter trapping rate may decrease as the gaps increase. Therefore, high hydrogen radical resistance is required for the porous membranes used in filters. [Prior Art Documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2016 / 043292 [Summary of the Invention]

[0010] [Problem to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a protective film frame that is sufficiently resistant to hydrogen radicals during EUV exposure, a protective film using the protective film frame, an exposure master with the protective film, a semiconductor manufacturing method, a liquid crystal display panel manufacturing method, and an exposure method. [Technical Means for Solving the Problem]

[0011] The inventors have made repeated efforts to achieve the above-mentioned objective and have found that, as a protective film frame that is resistant to hydrogen radicals in EUV exposure, a filter having a porous membrane coated with resin is provided in the ventilation section of the protective film frame, preferably a resin formed by forming a porous membrane with silicone resin or epoxy resin, thereby solving the above-mentioned problem and completing the present invention.

[0012] Therefore, the present invention provides the following protective film frame, protective film, exposure master with protective film, semiconductor manufacturing method, liquid crystal display panel manufacturing method, and exposure method. 1. A protective film frame for EUV exposure, characterized in that at least one venting portion is provided in the protective film frame, and a filter having a porous membrane coated with resin is installed in the venting portion. 2. The protective film frame according to claim 1, wherein the porous membrane is a resin-based porous membrane comprising at least one resin selected from the group consisting of fluorinated resin, polyester resin, polyimide resin, polycarbonate resin, and polyolefin resin. 3. The protective film frame according to claim 1, wherein the porous membrane is a polytetrafluoroethylene porous membrane. 4. The protective film frame according to claim 1 or 2, wherein the resin coating the porous membrane is silicone resin or epoxy resin. 5. The protective film frame according to claim 1 or 2, wherein the filter has a breathable support layer supporting the porous membrane. 6. The protective film frame according to claim 1 or 2, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, and adjacent nodes are connected by fibrils. 7. The protective film frame according to claim 5, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, mesh, and mesh. 8. The protective film frame according to claim 1 or 2, wherein the thickness of the protective film frame is less than 2.5 mm. 9. A protective film for EUV exposure, characterized in that the protective film is stretched on a protective film frame according to claim 1. 10. The protective film according to claim 9, wherein the height of the protective film is 2.5 mm or less. 11. The protective film according to claim 9 or 10, wherein the protective film is a frame-supported protective film. 12. An exposure master with a protective film, characterized in that the exposure master is equipped with the protective film according to claim 9. 13. The exposure master with a protective film as described in 12, wherein the exposure master is an EUV exposure master. 14. The exposure master with a protective film as described in 12, which is an exposure master with a protective film for extreme ultraviolet lithography. 15. An exposure method, characterized in that extreme ultraviolet exposure is performed using the exposure master with a protective film as described in 12. 16. A semiconductor manufacturing method, characterized in that it includes a step of performing extreme ultraviolet exposure using the exposure master with a protective film as described in 12. 17. A liquid crystal display panel manufacturing method, characterized in that it includes a step of performing extreme ultraviolet exposure using the exposure master with a protective film as described in 12.18. A protective film frame for use in a hydrogen plasma environment, characterized in that at least one vent is provided in the protective film frame, and a filter having a porous membrane coated with resin is installed in the vent. 19. The protective film frame according to claim 18, wherein the porous membrane is a resin-based porous membrane comprising at least one resin selected from the group consisting of fluorinated resins, polyester resins, polyimide resins, polycarbonate resins, and polyolefin resins. 20. The protective film frame according to claim 18, wherein the porous membrane is a polytetrafluoroethylene porous membrane. 21. The protective film frame according to claim 18 or 19, wherein the resin coating the porous membrane is a silicone resin or an epoxy resin. 22. The protective film frame according to claim 18 or 19, wherein the filter has a breathable support layer supporting the porous membrane. 23. The protective film frame according to claim 18 or 19, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, and adjacent nodes are connected by fibrils. 24. The protective film frame according to claim 22, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, mesh, and mesh. 25. The protective film frame according to claim 18 or 19, wherein the thickness of the protective film frame is less than 2.5 mm. 26. A protective film for use in a hydrogen plasma environment, characterized in that the protective film is stretched within the protective film frame according to claim 18. 27. The protective film according to claim 26, wherein the height of the protective film is 2.5 mm or less. 28. The protective film according to claim 26 or 27, wherein the protective film is a frame-supported protective film. 29. An exposure master with a protective film, used in a plasma environment, characterized in that the exposure master is provided with the protective film as described in 26. 30. An exposure master with a protective film as described in 29, wherein the exposure master is an EUV exposure master. 31. An exposure master with a protective film as described in 29, used in an extreme ultraviolet lithography process. 32. An exposure method, characterized in that exposure is performed in a plasma environment using an exposure master with a protective film as described in 29. 33. A semiconductor manufacturing method, characterized in that it includes the step of performing exposure in a plasma environment using an exposure master with a protective film as described in 29. 34. A liquid crystal display panel manufacturing method, characterized in that it includes the step of performing exposure in a plasma environment using an exposure master with a protective film as described in 29. [The effects of the invention]

[0013] According to the present invention, a protective film frame and a protective film that are sufficiently resistant to hydrogen radicals in EUV exposure can be provided, which is useful for EUV exposure apparatus, exposure system, semiconductor manufacturing system and liquid crystal display panel manufacturing system using the exposure master with the protective film.

Implementation Method

[0014] Hereinafter, the present invention will be described in further detail. The present invention is a frame-shaped protective film frame having an upper end surface on which a protective film is disposed and a lower end surface facing a photoresist, and a protective film using the same.

[0015] If the protective film frame is frame-shaped, its shape corresponds to the shape of the photoresist on which the protective film is installed. It is generally a quadrilateral (rectangular or square) frame. Regarding the shape of the corners (edges) of the protective film frame, it can remain as is and be angular (sharp), or it can be chamfered with R or C and be curved or other shapes.

[0016] In addition, the protective film frame has a surface for setting the protective film (here, the upper surface) and a surface for facing the photoresist when installing the photoresist (here, the lower surface).

[0017] Typically, a protective film is provided on the upper end surface via an adhesive or the like, and an adhesive or the like for attaching the protective film to the photoresist is provided on the lower end surface, but it is not limited to this.

[0018] There are no restrictions on the material of the protective film frame; known materials can be used. In the protective film frame for EUV applications, since there is a possibility of exposure to high temperatures, a material with a low coefficient of thermal expansion is preferred. Examples include Si, SiO2, SiN, quartz, Invar, titanium, and titanium alloys. Among these, titanium or titanium alloys are preferred in terms of ease of processing and lightweight.

[0019] The size of the protective film frame is not particularly limited. The height of the EUV protective film is limited to less than 2.5 mm. Therefore, the thickness of the EUV protective film frame becomes smaller than 2.5 mm.

[0020] Furthermore, considering the thickness of the protective film or photoresist adhesive, the thickness of the protective film frame for EUV is preferably 1.5 mm or less. Additionally, the lower limit of the thickness of the protective film frame is preferably 1.0 mm or more.

[0021] Additionally, clamping holes are typically provided on the side of the protective film frame for handling or peeling the protective film off from the photoresist. The size of the clamping hole is the length (or diameter if circular) in the thickness direction of the frame, ranging from 0.5 mm to 1.0 mm. The shape of the hole is not limited and can be circular or rectangular.

[0022] In this invention, a vent is provided in the protective film frame to mitigate pressure changes inside and outside the protective film. The shape or number of vents is not limited. A filter is provided in the vent to prevent foreign objects from entering the protective film. The location of the filter is not particularly limited; it can be installed inside the protective film frame, inside the vent, or outside the protective film frame.

[0023] The protective film frame of the present invention is characterized by having a filter comprising a porous membrane coated with a resin having hydrogen radical resistance. There are no particular limitations on the porous membrane; for example, it is preferably selected from at least one resin chosen from the group consisting of fluorinated resins, polyester resins, polyimide resins, polycarbonate resins, and polyolefin resins. Particularly preferred are fluorinated resins with proven use as KrF or ArF protective films, wherein polytetrafluoroethylene (PTFE) is particularly preferred.

[0024] A PTFE porous membrane generally comprises nodes (nodules) that are PTFE aggregates, and numerous fibrils that are microfibril-like structures formed by their two ends joining the nodes. Adjacent nodes are connected by fibrils. The PTFE porous membrane has air permeability in the thickness direction through the spaces (pores) between adjacent fibrils. PTFE porous membranes are also called stretched porous membranes, which are formed by stretching PTFE sheets, which are PTFE aggregates. The nodes and fibrils are formed by stretching the PTFE sheets, and these structures vary, for example, depending on the stretching conditions of the PTFE sheets.

[0025] Regarding the resin used to coat the porous membrane, it is preferable to have sufficient hydrogen radical resistance. Specifically, silicone resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, etc., can be listed. Among these, from the viewpoint of hydrogen radical resistance, silicone resin or epoxy resin is preferred, and silicone resin is more preferred. There are no particular limitations on the method of coating the porous membrane with resin, but it is easier and preferable to adjust the resin solution to contain it in the porous membrane. There are no limitations on the method of containing the resin solution in the porous membrane. For example, the porous membrane can be immersed in the resin solution, the resin solution can be spin-coated onto the porous membrane, or sprayed. By using the resin solution, the solution can easily diffuse into the gaps of the porous membrane, and the fibers of the porous membrane can be coated with resin. Furthermore, in this invention, it is not necessary to cover the entire surface of the porous membrane with resin; the coating amount or coating ratio can be adjusted according to the required hydrogen radical resistance. By using light or heat to crosslink and harden these resins, hydrogen radical resistance can also be improved.

[0026] In this invention, the filter may include any component other than a porous membrane. The component 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 of the main surfaces of the porous membrane. By configuring the breathable support layer, the strength of the filter is improved, and in addition, operability is also improved.

[0027] The breathable support layer is preferably a layer with higher air permeability and moisture permeability in the thickness direction compared to the porous membrane. The breathable support layer can be, for example, made of woven fabric, non-woven fabric, mesh, or a fine mesh. Materials constituting the breathable support layer include, for example, polyester, polyethylene, or aromatic polyamide resin. The shape of the breathable support layer can be the same as or different from that of the porous membrane. The breathable support layer can be configured, for example, by heat-sealing with the porous membrane or by bonding with an adhesive. The breathable support layer can be disposed on one or both main surfaces of the porous membrane. These breathable support layers can also be coated with the resin described above.

[0028] Furthermore, there are no restrictions on the material of the protective film, but it is preferable to use a material with high transmittance and high lightfastness at the wavelength of the exposure light source. For example, an extremely thin silicon film or carbon film can be used for EUV exposure. Examples of carbon films include graphene, diamond-like carbon, and carbon nanotubes. In addition, when it is difficult to operate the protective film separately, a protective film supported by a frame such as silicon can be used. In this case, the protective film can be easily manufactured by bonding the area of ​​the frame to the protective film frame.

[0029] Regarding the protective film of the present invention, the protective film is provided on the upper end face of such a protective film frame via an adhesive or bonding agent. The material of the adhesive or bonding agent is not limited, and known materials can be used. For strong adhesion of the protective film, an adhesive or bonding agent with strong bonding strength is preferred.

[0030] Furthermore, an adhesive for mounting the photoresist is formed on the lower end face of the protective film frame. Generally, the photoresist adhesive is preferably provided throughout the entire circumference of the protective film frame.

[0031] As a photoresist adhesive, known adhesives can be used, and acrylic or silicone adhesives may be suitable. The adhesive can also be processed into any shape as needed.

[0032] A release layer (separator) for protecting the adhesive may also be attached to the lower end face of the photoresist adhesive. There are no particular limitations on the material of the release layer; for example, polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polyethylene (PE), polycarbonate (PC), polyvinyl chloride (PVC), polypropylene (PP), etc., can be used. Additionally, depending on the need, a silicone-based release agent or a fluorinated release agent may be coated onto the surface of the release layer.

[0033] The protective film of the present invention can not only serve as a protective component for inhibiting foreign matter from adhering to the exposure plate within an EUV exposure apparatus, but also as a protective component for protecting the exposure plate during storage or handling. Methods for attaching the protective film to an exposure plate such as a photoresist and manufacturing an exposure plate with the protective film include methods such as attachment using the photoresist adhesive, electrostatic adsorption, and mechanical fixing.

[0034] The method for manufacturing a semiconductor or liquid crystal display panel according to this embodiment includes a step of exposing a substrate (semiconductor wafer or liquid crystal substrate) using the exposure master with the protective film. For example, in the lithography step, which is one of the manufacturing steps of a semiconductor device or liquid crystal display panel, the exposure master with the protective film is placed on a stepper for exposure in order to form a photoresist pattern corresponding to integrated circuits, etc., on the substrate. Generally, in EUV exposure, EUV light is reflected by the exposure master and guided to the substrate by a projection optical system, which is performed under reduced pressure or vacuum. Therefore, even if foreign matter adheres to the protective film in the lithography step, these foreign matter will not be imaged on the wafer coated with photoresist, thus preventing short circuits or open circuits in integrated circuits, etc., caused by the image of foreign matter. Therefore, by using the exposure master with the protective film, the yield in the lithography step can be improved. [Example]

[0035] Hereinafter, embodiments and comparative examples are shown to specifically illustrate the present invention, but the present invention is not limited to the following embodiments.

[0036] [Evaluation of Hydrogen Radical Resistance of Filters] A filter (TEMISH S-NTF1033-N01 manufactured by Nitto Denko Corporation) was prepared, consisting of a 15 cm square porous membrane made of polytetrafluoroethylene (PTFE porous membrane) and a polypropylene mesh support. A 1% by mass solution of each of the following resins (1) to (6) was spin-coated onto the filter at 800 rpm for 60 seconds, and then air-dried at room temperature for 12 hours to allow the solvent to evaporate. (1) Silicone resin adhesive (2) Epoxy resin adhesive (3) Acrylic resin adhesive (4) Fluoropolymer (5) Polyurethane resin adhesive (6) Untreated

[0037] The filter coated with the resin was subjected to hydrogen plasma irradiation using the following apparatus. (Hydrogen plasma irradiation conditions) Apparatus: FlexAL (Oxford Instruments) Plasma source: ICP (Inductively Coupled Plasma) Processing conditions: Pressure 80 mTorr, H2 flow rate 50 sccm Power: 200 W Processing temperature: 100℃ Processing time: 600 s

[0038] The filter after hydrogen plasma irradiation was observed using a microscope (Nikon ECLIPSE LV150) and the following judgments were made. The results are shown in Table 1. (Judgment Criteria) A: The presence of a PTFE porous membrane was confirmed, and the filter structure remained unchanged. B: The disappearance of the PTFE porous membrane was confirmed.

[0039] [Table 1] Types of resins Judgment result (1) Silicone resin A (2) Epoxy resin A (3) Acrylic resin B (4) Fluoropolymer B (5) Polyurethane resin B (6) Unprocessed B

[0040] Based on the results in Table 1, it can be confirmed that filters with porous membranes coated with silicone resin or epoxy resin exhibit excellent hydrogen plasma resistance. Furthermore, under the aforementioned conditions, the porous membranes of filters with porous membranes coated with acrylic resin, fluororesin, and polyurethane resin disappear due to hydrogen plasma. However, by reducing the power of the hydrogen plasma, lowering the temperature, or shortening the processing time, its superiority can be confirmed compared to untreated filters.

[0041] [Example 1] A titanium protective film frame (external dimensions 150 mm × 118 mm × 1.5 mm, protective film frame width 4.0 mm) was prepared. As shown in Figures 1 and 2, an L-shaped vent 10 is provided from the outside of the protective film frame 1 to its lower end face. In Figures 1 and 2, symbol 1a represents the upper end face of the protective film frame, and 1b represents the lower end face of the protective film frame. Symbol 20 is a filter provided at the opening of the lower end face of the protective film frame as described later. Although not specifically illustrated, it is coated with a specified resin.

[0042] A filter measuring 10 mm in length and 2.5 mm in width (TEMISH S-NTF1033-N01 manufactured by Nitto Denko Corporation) was prepared, comprising a porous membrane made of PTFE and a mesh support made of polypropylene. Next, 1 part by weight of a hardener (PT-56 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts by weight of a silicone resin adhesive (X-40-3264 manufactured by Shin-Etsu Chemical Co., Ltd.) and stirred. The resulting substance was then dissolved in a hydrocarbon solvent (ISOPARE manufactured by ExxonMobil) to prepare a solution containing 1% by weight. 1 ml of the solution was immersed in the center of the filter and air-dried at room temperature for 2 hours to allow the solvent to evaporate completely. The filter (symbol 20 in Figure 2) was attached to the lower end opening of the protective film frame using double-sided tape.

[0043] The protective film frame is cleaned with a neutral detergent and pure water. A substance obtained by adding 1 part by weight of a hardener (PT-56, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by weight of a silicone resin adhesive ("X-40-3264" manufactured by Shin-Etsu Chemical Co., Ltd.) and stirring is applied to the upper surface of the protective film frame in a manner 1 mm wide and 0.1 mm thick. Additionally, a substance obtained by adding 0.1 part by weight of a hardener ("L-45" manufactured by Soken Chemical Co., Ltd.) to 100 parts by weight of an acrylic resin adhesive ("SK Dine 1499M" manufactured by Soken Chemical Co., Ltd.) and stirring is applied to the lower surface of the protective film frame in a manner 1 mm wide and 0.1 mm thick, covering the entire circumference.

[0044] Then, the protective film frame is heated at 100°C for 12 hours to harden the adhesive on the upper and lower end faces. Next, the ultra-thin silicone film serving as the protective film is pressed onto the adhesive formed on the upper end face of the protective film frame to complete the protective film.

[0045] [Example 2] A filter (TEMISH S-NTF1033-N01 manufactured by Nitto Denko Corporation), measuring 10 mm in length and 2.5 mm in width, comprising a porous PTFE 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 solution containing 1% by mass. 1 ml of the solution was immersed in the center of the filter and air-dried at room temperature for 2 hours to allow the solvent to completely evaporate. The filter was then attached to the lower end opening of the protective film frame using double-sided tape. Otherwise, the protective film was completed in the same manner as in Example 1.

[0046] As can be seen from the above Examples 1 and 2, a protective film including a filter resistant to hydrogen free radicals can be provided. [Simplified Explanation of the Diagram]

[0048] FIG1 is a plan view showing an example of the protective film frame of the present invention. FIG2 is a cross-section along line AA of the protective film frame and is a schematic view showing the venting section and the filter section.

Claims

1. A protective film frame for extreme ultraviolet (EUV) exposure, characterized in that: at least one ventilation section is provided in the protective film frame, and a filter having a porous membrane coated with resin is installed in the ventilation section, the filter having a breathable support layer supporting the porous membrane, the breathable support layer and the porous membrane being coated with resin together.

2. The protective film frame as claimed in claim 1, wherein the porous membrane is a resin-based porous membrane comprising at least one resin selected from the group consisting of fluorinated resins, polyester resins, polyimide resins, polycarbonate resins, and polyolefin resins.

3. The protective film frame as claimed in claim 1, wherein the porous membrane is a polytetrafluoroethylene porous membrane.

4. The protective film frame as claimed in claim 1 or 2, wherein the resin covering the porous film is silicone resin or epoxy resin.

5. The protective film frame as claimed in claim 1 or 2, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, with adjacent nodes connected by fibrils.

6. The protective film frame as claimed in claim 1, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, mesh, and mesh.

7. The protective film frame as claimed in claim 1 or 2, wherein the thickness of the protective film frame is less than 2.5 mm.

8. A protective film for extreme ultraviolet (EUV) exposure, characterized in that: the protective film is stretched on a protective film frame as described in claim 1.

9. The protective film as claimed in claim 8, wherein the height of the protective film is less than 2.5 mm.

10. The protective film as claimed in claim 8 or 9, wherein the protective film is a frame-supported protective film.

11. An exposure master with a protective film, characterized in that: the exposure master is equipped with the protective film as described in claim 8.

12. The exposure master with a protective film as described in claim 11, wherein the exposure master is an exposure master for extreme ultraviolet light.

13. The exposure master with a protective film as described in claim 11, which is an exposure master with a protective film for extreme ultraviolet lithography.

14. An exposure method, characterized in that: extreme ultraviolet exposure is performed using an exposure original with a protective film as described in claim 11.

15. A method for manufacturing a semiconductor, characterized in that it includes a step of extreme ultraviolet exposure using an exposure master with a protective film as described in claim 11.

16. A method for manufacturing a liquid crystal display panel, characterized in that it includes a step of exposing an exposure master with a protective film as described in claim 11 to extreme ultraviolet light.

17. A protective film frame for use in a hydrogen plasma environment, characterized in that: at least one venting section is provided in the protective film frame, and a filter having a porous membrane coated with resin is installed in the venting section, the filter having a breathable support layer supporting the porous membrane, the breathable support layer being coated with resin together with the porous membrane.

18. The protective film frame of claim 17, wherein the porous membrane is a resin-based porous membrane comprising at least one resin selected from the group consisting of fluorinated resins, polyester resins, polyimide resins, polycarbonate resins and polyolefin resins.

19. The protective film frame as claimed in claim 17, wherein the porous membrane is a polytetrafluoroethylene porous membrane.

20. The protective film frame as claimed in claim 17 or 18, wherein the resin covering the porous film is a silicone resin or an epoxy resin.

21. The protective film frame as claimed in claim 17 or 18, wherein the porous membrane has a plurality of nodes and a plurality of fibrils, with adjacent nodes connected by fibrils.

22. The protective film frame as claimed in claim 17, wherein the breathable support layer is at least one selected from the group consisting of woven fabric, nonwoven fabric, mesh, and mesh.

23. The protective film frame as claimed in claim 17 or 18, wherein the thickness of the protective film frame is less than 2.5 mm.

24. A protective film for use in a hydrogen plasma environment, characterized in that: the protective film is stretched on a protective film frame as described in claim 17.

25. The protective film as claimed in claim 24, wherein the height of the protective film is less than 2.5 mm.

26. The protective film as claimed in claim 24 or 25, wherein the protective film is a frame-supported protective film.

27. An exposure master with a protective film, for use in a hydrogen plasma environment, characterized in that: the exposure master is provided with the protective film as described in claim 24.

28. The exposure master with a protective film as described in claim 27, wherein the exposure master is an exposure master for extreme ultraviolet light.

29. The exposure master with a protective film as described in claim 27, which is an exposure master with a protective film for use in extreme ultraviolet lithography processes.

30. An exposure method, characterized in that: exposure is performed in a hydrogen plasma environment using an exposure original with a protective film as described in claim 27 for use in a hydrogen plasma environment.

31. A method for manufacturing a semiconductor, characterized in that it includes a step of exposing a semiconductor in a plasma environment using an exposure template with a protective film as described in claim 27.

32. A method for manufacturing a liquid crystal display panel, characterized in that it includes a step of exposing a protective film-bearing exposure plate used in a hydrogen plasma environment as described in claim 27.

Images