Carbon nanotube self-supporting film, pellicle, exposure original plate with pellicle, method for producing these, exposure method, method for producing semiconductor device, and method for producing liquid crystal display plate

Abstract

The present invention is a method for producing a carbon nanotube self-supporting film, wherein a carbon nanotube self-supporting film (3B) is produced by: forming a carbon nanotube film (3A) on one surface of a membrane filter (7); and separating the carbon nanotube film (3A) from the membrane filter (7) by causing a gas to flow from the other surface of the membrane filter (7) toward said one surface. The present invention thus provides a method for producing a carbon nanotube self-supporting film with which it is possible to stably produce a carbon nanotube self-supporting film that is used particularly as a pellicle film.

Description

Carbon nanotube free-standing film, pellicle, exposure master plate with pellicle, their manufacturing methods, exposure method, method for manufacturing semiconductor device, and method for manufacturing liquid crystal display panel

[0001] The present invention relates to a carbon nanotube free-standing film (in particular, one used as a pellicle film of a pellicle serving as a dust shield for a lithography mask used in manufacturing semiconductor devices such as LSIs and ultra-LSIs, liquid crystal display panels, etc.), a pellicle, an exposure master plate with a pellicle, their manufacturing methods, an exposure method, a method for manufacturing a semiconductor device, and a method for manufacturing a liquid crystal display panel.

[0002] The development of exposure technology called photolithography has enabled higher integration of semiconductor integrated circuits.

[0003] Currently, the commercialized exposure process uses an exposure apparatus utilizing the ArF wavelength band of 193 nm to perform a transfer process and form a fine pattern on a wafer, but since there is a limit to forming a fine pattern of 32 nm or less, various methods such as immersion exposure, double exposure, phase transition, and optical phase correction have been developed. However, it is difficult to realize a further miniaturized circuit line width of 32 nm or less with the exposure technology using the ArF wavelength. Accordingly, EUV photolithography technology using extreme ultraviolet (hereinafter referred to as EUV) light, which uses a wavelength of 13.5 nm that is shorter than the wavelength of 193 nm as the main exposure wavelength, is attracting attention as a next-generation process.

[0004] On the other hand, in the photolithography process, a photomask is used as a master for patterning, and the pattern on the photomask is transferred to a wafer. At this time, if impurities such as particles and foreign matter adhere to the photomask, the exposure light is absorbed or reflected by the impurities, which damages the transferred pattern, leading to deterioration in the performance and yield of semiconductor devices.

[0005] Therefore, a method of attaching a pellicle to the photomask is employed to prevent impurities from adhering to the surface of the photomask. The pellicle is placed on the upper surface of the photomask, and even if impurities adhere to the pellicle, during the photolithography process, the focus coincides with the pattern on the photomask, so dust or foreign matter on the pellicle will not be focused and will not be transferred to the pattern. Recently, with the miniaturization of circuit line widths, the size of impurities that can affect pattern damage has also decreased, and the role of the pellicle in protecting the photomask has become even more important.

[0006] When the pellicle is constructed as a single film, applying a material with a low extinction coefficient to extreme ultraviolet light at 13.5 nm as the pellicle film makes it easy to ensure the transmittance of the pellicle film, but it is extremely difficult to ensure excellent mechanical and thermal properties.

[0007] Pellicle films for EUV spectroscopy are typically manufactured by laminating silicon nitride (SiN) or the like on a silicon wafer. On the other hand, development is underway on pellicles using carbon nanotube films as a material with high transmittance to EUV light and high resistance to EUV. Patent documents 1 and 2 below disclose EUV spectroscopy pellicles using carbon nanotube films.

[0008] However, it is difficult to stably manufacture carbon nanotube self-supporting films, especially those used as pellicle films.

[0009] International Publication No. 2014 / 142125, International Publication No. 2018 / 008594

[0010] This invention has been made in view of the above circumstances, and aims to provide a method for manufacturing a carbon nanotube self-supporting film that can stably produce a carbon nanotube self-supporting film, particularly one used as a pellicle film. It also aims to provide a method for manufacturing a pellicle that can stably produce a pellicle using a carbon nanotube film.

[0011] To achieve the above objective, the present invention provides a method for producing a carbon nanotube self-supporting membrane, characterized by forming a carbon nanotube membrane on one surface of a membrane filter, and separating the carbon nanotube membrane from the membrane filter by flowing a gas from the other surface of the membrane filter toward the one surface, thereby producing the carbon nanotube self-supporting membrane.

[0012] With the method for producing a carbon nanotube self-supporting film according to the present invention, carbon nanotube self-supporting films can be produced stably. Carbon nanotubes have particularly high transmittance to EUV light, as well as excellent mechanical and thermal properties, so the present invention makes it possible to produce self-supporting films useful as pellicle films for EUV exposure.

[0013] Furthermore, when circulating the gas, the flow rate of the gas can be adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less.

[0014] This method more effectively suppresses damage to the carbon nanotube membrane and reduces the adhesion between the membrane filter and the carbon nanotube membrane. As a result, a carbon nanotube self-supporting membrane can be obtained with even higher quality and greater stability.

[0015] Furthermore, a fluorine-based membrane filter can be used. Alternatively, a hydrophobic membrane filter can be used.

[0016] Using such a material makes it easier to separate the carbon nanotube film from the membrane filter.

[0017] Furthermore, when forming the carbon nanotube film, the formation thickness can be set to 10 to 100 nm.

[0018] In this way, a more suitable pellicle film can be obtained.

[0019] Furthermore, the carbon nanotube film formed can have a transmittance of 90% or more for light having a wavelength of 13.5 nm.

[0020] In this way, a more suitable pellicle film for EUV exposure can be obtained.

[0021] Furthermore, the carbon nanotube film can be used for EUV lithography.

[0022] Thus, the present invention makes it possible to manufacture carbon nanotube self-supporting films suitable for EUV lithography.

[0023] The present invention also provides a method for manufacturing a pellicle for photolithography, comprising a pellicle membrane and a frame-shaped member connecting the pellicle membranes, characterized in that the pellicle membrane is a carbon nanotube self-supporting membrane manufactured by the above-described method for manufacturing a carbon nanotube self-supporting membrane.

[0024] In this way, pellicles using a carbon nanotube self-supporting film as the pellicle film can be stably manufactured. Carbon nanotubes have particularly high transmittance to EUV light, as well as excellent mechanical and thermal properties, so this invention makes it possible to manufacture pellicles useful for EUV lithography.

[0025] The present invention also provides a method for manufacturing a pellicle for photolithography, comprising a pellicle membrane and a frame-shaped member to which the pellicle membrane is connected, characterized in that a carbon nanotube membrane is formed on one surface of a membrane filter, the frame-shaped member is connected to the carbon nanotube membrane from the opposite side of the membrane filter, and gas is circulated from the other surface of the membrane filter toward the one surface to separate the carbon nanotube membrane together with the frame-shaped member from the membrane filter, thereby manufacturing a pellicle in which the carbon nanotube membrane connected to the frame-shaped member is the pellicle membrane.

[0026] With the pellicle manufacturing method of the present invention, it is possible to stably manufacture pellicles using carbon nanotube films as the pellicle film. Carbon nanotubes have particularly high transmittance to EUV light, as well as excellent mechanical and thermal properties, so the present invention makes it possible to manufacture pellicles useful for EUV exposure.

[0027] Furthermore, when circulating the gas, the flow rate of the gas can be adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less.

[0028] This method more effectively suppresses damage to the carbon nanotube membrane and reduces the adhesion between the membrane filter and the carbon nanotube membrane. As a result, the carbon nanotube membrane can be separated with even better quality and stability, and a superior pellicle can be obtained.

[0029] Furthermore, a fluorine-based membrane filter can be used. Alternatively, a hydrophobic membrane filter can be used.

[0030] Using such a material makes it easier to separate the carbon nanotube film from the membrane filter.

[0031] Furthermore, when forming the carbon nanotube film, the formation thickness can be set to 10 to 100 nm.

[0032] In this way, a pellicle with a more suitable pellicle membrane can be obtained.

[0033] Furthermore, the carbon nanotube film formed can have a transmittance of 90% or more for light having a wavelength of 13.5 nm.

[0034] In this way, a pellicle with characteristics more suitable for use as a pellicle film for EUV exposure can be obtained.

[0035] Furthermore, the carbon nanotube film can be used for EUV lithography.

[0036] Thus, the present invention makes it possible to manufacture a pellicle equipped with a carbon nanotube film suitable for EUV exposure as the pellicle film.

[0037] The present invention also provides a method for manufacturing an exposure master plate and an exposure master plate with a pellicle attached, characterized in that the pellicle is manufactured by the above-described method for manufacturing a pellicle.

[0038] With the method for manufacturing exposure plates with pellicles according to the present invention, exposure plates with pellicles (where the pellicle film is a carbon nanotube film) can be manufactured stably.

[0039] In this case, the exposure master plate can be one for EUV exposure.

[0040] Thus, the present invention makes it possible to manufacture a pellicle-equipped exposure plate with a pellicle film and exposure plate suitable for EUV exposure.

[0041] Furthermore, the present invention provides an exposure method characterized by exposure using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. Furthermore, the present invention provides a method for manufacturing a semiconductor device, characterized by comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. Furthermore, the present invention provides a method for manufacturing a liquid crystal display panel, characterized by comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. Furthermore, the present invention provides a method for manufacturing a semiconductor device, characterized by comprising the step of EUV exposure of a substrate using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. Furthermore, the present invention provides a method for manufacturing a liquid crystal display panel, characterized by comprising the step of EUV exposure of a substrate using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master.

[0042] With the exposure method and the like of the present invention as described above, the use of the exposure master with a pellicle can improve the yield in the exposure process.

[0043] Furthermore, the present invention provides a carbon nanotube free-standing film produced by the above method for producing a carbon nanotube free-standing film. Furthermore, the present invention provides a pellicle produced by the above method for producing a pellicle. Furthermore, the present invention provides an exposure master with a pellicle produced by the above method for producing an exposure master with a pellicle.

[0044] As described above, the carbon nanotube free-standing film and the like of the present invention can be stably produced, and the carbon nanotube free-standing film (pellicle film) particularly has high transmittance for EUV light, as well as excellent mechanical properties and thermal properties, making it suitable for EUV exposure applications.

[0045] With the method for producing a carbon nanotube free-standing film and the like of the present invention, the carbon nanotube free-standing film can be stably produced. Furthermore, with the method for producing a pellicle and the like and the exposure method of the present invention, production of a pellicle and the like and exposure can be stably performed using the carbon nanotube free-standing film.

[0046] This is a schematic diagram showing an example of the exposure master with a pellicle of the present invention. This is a flow chart showing the first embodiment of the method for producing a pellicle of the present invention. This is a plan view of the state after step 2 in the first embodiment. This is a flow chart showing the second embodiment of the method for producing a pellicle of the present invention. This is a plan view of the state after step C in the second embodiment.

[0047] Hereinafter, the present invention will be described in detail by referring to the drawings as an example of the embodiments, but the present invention is not limited thereto. As described above, stable production of a carbon nanotube free-standing film used for a pellicle film and the like, and stable production of a pellicle using a carbon nanotube film are demanded.

[0048] The inventors conducted diligent research and discovered that a method for producing a carbon nanotube self-supporting membrane, which involves forming a carbon nanotube membrane on one surface of a membrane filter and separating the carbon nanotube membrane from the membrane filter by flowing a gas from the other surface of the membrane filter toward the one surface, can stably produce a carbon nanotube self-supporting membrane, thus completing the present invention.

[0049] Furthermore, the present invention was completed by discovering that a pellicle for photolithography can be stably manufactured using a carbon nanotube membrane as the pellicle membrane in a method for manufacturing a pellicle comprising a pellicle membrane and a frame-shaped member to which the pellicle membrane is connected, wherein a carbon nanotube membrane is formed on one surface of a membrane filter, the frame-shaped member is connected to the carbon nanotube membrane from the opposite side of the membrane filter, and gas is circulated from the other surface of the membrane filter toward the one surface to separate the carbon nanotube membrane together with the frame-shaped member from the membrane filter, thereby manufacturing a pellicle in which the carbon nanotube membrane connected to the frame-shaped member is the pellicle membrane.

[0050] Figure 1 shows an example of a pellicle-equipped exposure plate of the present invention. Here, an example for EUV exposure is shown, but the invention is not limited to this. The pellicle of the present invention and the carbon nanotube self-supporting film of the present invention (hereinafter also referred to as the CNT self-supporting film) are also shown. In Figure 1, the self-supporting film is shown connected to a frame-shaped member (hereinafter, in the connected state, it is also referred to as the carbon nanotube film). First, the overall configuration of the pellicle-equipped exposure plate 1 of the present invention will be explained. The pellicle film (carbon nanotube self-supporting film of the present invention) 3 is connected to the upper end surface of the frame-shaped member (hereinafter simply referred to as the frame) 2. This constitutes the pellicle 4 of the present invention. On the other hand, a mask-side adhesive 5 is provided on the lower end surface of the frame 2, and the exposure plate 6 is attached via the mask-side adhesive 5, thus constituting the pellicle-equipped exposure plate 1 of the present invention.

[0051] The following describes each part in detail. The material of frame 2 is not particularly limited, but aluminum or aluminum alloy (5000 series, 6000 series, 7000 series, etc.), titanium, stainless steel, silicon, etc. are preferred. Frame 2 only needs to be frame-shaped, and its shape corresponds to the shape of the exposure master plate 6 on which the pellicle 4 is mounted. Generally, it is a rectangular (or square) frame.

[0052] Furthermore, although the pellicle film 3 is directly connected to the upper end surface of the frame 2 in Figure 1, an adhesive (not shown) may be provided on the upper end surface, and the pellicle film 3 may be connected via this adhesive. The material of the adhesive is not particularly limited, but it is preferably an organic resin material such as silicone resin, acrylic resin, or epoxy resin, and more preferably an organic resin material that is resistant to EUV light.

[0053] Furthermore, there are no restrictions on the material of the mask-side adhesive 5 for attaching the frame 2 to the exposure master plate 6 on the lower end surface; known materials such as silicone adhesives and acrylic adhesives can be used. There are no particular restrictions on the shape of the mask-side adhesive 5; it may be flattened.

[0054] The exposure master plate 6 is a photomask or reticle, and can be specifically designed for EUV exposure.

[0055] As mentioned above, the pellicle film 3 is a CNT film (CNT self-supporting film). The CNT film has high transmittance to EUV light and high resistance to EUV light (good thermal properties). It also has excellent mechanical properties. Therefore, this CNT film, and the pellicle 4 using it, are particularly suitable as a pellicle film and pellicle for EUV exposure. For example, it can have a transmittance of 90% or more for light with a wavelength of 13.5 nm, making it even more suitable for EUV exposure. The higher the transmittance, the better, and there is no upper limit, but it can be 100% in particular.

[0056] Furthermore, the thickness of the pellicle film 3 can be 10 to 100 nm. A thickness of 10 nm or more can further increase the mechanical strength, while a thickness of 100 nm or less can increase the transmittance, making it more suitable as a pellicle film. The thickness of the CNT film, which is the pellicle film 3, can be evaluated using a step meter, such as a stylus-type surface shape measuring instrument (Veeco: Dektak150). The step difference between the CNT film (e.g., 10 mm x 10 mm in size) transferred to the substrate (e.g., silicon wafer) and the substrate can be measured using a step meter, and that value or the average of those values ​​can be used as the thickness of the CNT film.

[0057] Next, the method for manufacturing the carbon nanotube self-supporting membrane and the method for manufacturing the pellicle of the present invention will be described. Here, the method for use in EUV photolithography will be described. Figure 2 shows an example of the flow of the method for manufacturing the pellicle of the present invention (first embodiment). It mainly consists of the following steps: (Step 1) preparation of the membrane filter, (Step 2) formation of the carbon nanotube membrane, (Step 3) separation by gas flow, and (Step 4) connection of the carbon nanotube self-supporting membrane and the frame-shaped member. Steps 1 to 3 correspond to the method for manufacturing the carbon nanotube self-supporting membrane of the present invention.

[0058] (Step 1: Preparation of the membrane filter) First, prepare the membrane filter 7. The membrane filter 7 is preferably hydrophobic. Furthermore, fluorine-based materials are preferred as components, such as PTFE and PVDF. However, the components of the membrane filter are not limited to those mentioned above. By using such materials, it becomes easier and simpler to separate the CNT film 3A formed on its surface from the membrane filter 7 in subsequent steps.

[0059] Furthermore, while the membrane filter 7 is generally circular, its shape is not particularly limited. It is preferable to select a membrane filter 7 that is larger than the CNT film 3A formed on the membrane filter 7 in a later process. The thickness of the membrane filter 7 is not particularly limited, but it is preferably 50 μm to 1000 μm, and more preferably 100 μm to 500 μm from a handling standpoint. The pore size of the membrane filter 7 is preferably 0.1 μm to 1.0 μm, and more preferably 0.2 μm to 0.5 μm from a handling standpoint. A membrane filter 7 as described above can be prepared, for example, from a commercially available source.

[0060] (Step 2: Formation of carbon nanotube film) Next, a CNT film 3A is formed on the membrane filter 7 (on one of the two surfaces). For example, it can be formed by a suspended catalyst CVD (Chemical Vapor Deposition) method in which a metal catalyst is present in the reaction system, carbon monoxide is used as the carbon raw material, and carbon dioxide is added as the oxidizing agent.

[0061] Specific examples of metal catalysts include metal complexes such as Fe, Co, Ni, and Mo, or combinations thereof. The concentration of carbon dioxide is preferably 0.1% to 1.0% relative to the concentration of carbon monoxide. The reaction temperature between the metal catalyst, carbon monoxide, and carbon dioxide is preferably 700°C to 1000°C. By carrying out the reaction under these conditions, the CNT film 3A can be formed more reliably.

[0062] Figure 3 shows a plan view of the state after step 2 (membrane filter 7 and CNT film 3A). As shown in Figure 3, a rectangular CNT film 3A is formed on a portion of the surface of the rectangular membrane filter 7. Furthermore, it is preferable that the CNT film 3A on the membrane filter 7 be formed in an area roughly the same size as the frame-shaped member (frame 2) used in the subsequent process. For example, it can be an area of ​​about 150.8 × 118.3 mm.

[0063] (Step 3: Separation by gas flow) Next, gas is flowed from the other surface of the membrane filter 7 (the surface opposite to the surface on which the CNT film 3A is formed) towards the other surface (the surface on which the CNT film 3A is formed) to separate the CNT film 3A from the membrane filter 7. This produces the self-supporting CNT film 3B of the present invention.

[0064] Furthermore, when circulating the gas, by adjusting the gas flow rate so that the pressure loss of the membrane filter 7 is 0.3 kPa or less (0 kPa or more), damage to the CNT membrane 3A can be more effectively suppressed during separation, and the adhesion between the membrane filter 7 and the CNT membrane 3A can be reduced. The gas can generally be air, but is not particularly limited. The gas can be circulated, for example, using a blower. The gas flow rate at that time can be, for example, when the size of the membrane filter 7 is 36,000 mm. ２ The size of the CNT film 3A is 17700 mm ２ When the pressure loss coefficient of the membrane filter 7 is 8.0, it is preferable that the pressure loss be within the above numerical range, for example, 12 to 18 m ３ A relatively small flow rate of around / min can be achieved.

[0065] As described above, the CNT self-supporting membrane 3B can be manufactured simply and stably by gas flow.

[0066] (Step 4: Connecting the carbon nanotube self-supporting membrane to the frame-shaped member) The CNT self-supporting membrane 3B manufactured in this way is then connected to the frame 2 as the pellicle membrane 3 to produce the pellicle 4 of the present invention shown in Figure 1. With this manufacturing method, stable production of the pellicle 4 is possible.

[0067] Next, a method for manufacturing a pellicle according to another embodiment (second embodiment) of the present invention will be described. Figure 4 shows an example of the flow of this manufacturing method. It mainly consists of the following steps: (Step A) preparation of the membrane filter, (Step B) formation of the carbon nanotube film, (Step C) connection of the carbon nanotube film to the frame-shaped member, and (Step D) separation by gas flow.

[0068] (Step A: Preparation of membrane filter) and (Step B: Formation of carbon nanotube film) Steps A and B can be carried out in the same manner as steps 1 and 2 of the first embodiment shown in Figure 2. The plan view of the state after step B (membrane filter 7 and CNT film 3A) is the same as that shown in Figure 3 above.

[0069] (Step C: Connecting the carbon nanotube membrane to the frame-shaped member) Next, the frame-shaped member (frame 2) is connected to the CNT membrane 3A from the side opposite to the membrane filter 7. As a result, the CNT membrane 3A is sandwiched between the membrane filter 7 and the frame 2. At this time, the method of connecting the frame 2 and the CNT membrane 3A is not particularly limited. They may be brought into contact and directly bonded (utilizing the adhesiveness of the surfaces of each member). Alternatively, they can be connected more firmly via an adhesive (tack). Figure 5 shows a plan view of the state after step C (membrane filter 7, CNT membrane 3A, and frame 2). As shown in Figure 5, the frame 2 can be connected to the outer peripheral (edge) region of the CNT membrane 3A.

[0070] (Step D) Separation by gas flow Next, gas is flowed from the other surface of the membrane filter 7 (the surface opposite to the surface on which the CNT film 3A is formed) toward the one surface (the surface on which the CNT film 3A is formed) to separate the CNT film 3A together with the frame-shaped member (frame 2) from the membrane filter 7. This produces the pellicle 4 of the present invention shown in Figure 1, in which the CNT film 3A connected to the frame 2 becomes the pellicle film 3 (the pellicle 4 in Figure 4 is shown upside down compared to the pellicle 4 in Figure 1). With this manufacturing method, stable production of the pellicle 4 is possible. Except that the objects to be separated from the membrane filter 7 are the CNT film 3A and the frame 2 connected to the CNT film 3A, the process can be carried out in the same manner as in Step 3 of the first embodiment shown in Figure 2.

[0071] Furthermore, in the method for manufacturing an exposure master plate with a pellicle according to the present invention, the pellicle 4 manufactured according to the first or second embodiment described above is used. That is, the exposure master plate with a pellicle according to the present invention can be manufactured by attaching the pellicle 4 to an exposure master plate 6 prepared separately. When attaching, the mask-side adhesive 5 can be used as an intermediary.

[0072] Furthermore, the exposure method of the present invention involves exposure using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. The method for manufacturing a semiconductor device or liquid crystal display panel of the present invention includes a step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master. Furthermore, the method for manufacturing a semiconductor device or liquid crystal display panel of the present invention includes a step of EUV exposure of a substrate using a pellicle-attached exposure master manufactured by the above-described method for manufacturing a pellicle-attached exposure master.

[0073] For example, in the lithography stage, which is one of the manufacturing processes for semiconductor devices or liquid crystal displays, a pellicle-equipped exposure plate is placed in a stepper and exposed to form a photoresist pattern corresponding to an integrated circuit on a substrate. Generally, in EUV exposure, a projection optical system is used in which EUV light is reflected by the exposure plate and guided to the substrate, and these processes are carried out under reduced pressure or vacuum. As a result, even if foreign matter adheres to the pellicle during the lithography stage, these foreign matter will not form an image on the wafer coated with photoresist, thus preventing short circuits or disconnections of integrated circuits, etc., caused by the image of foreign matter. Therefore, the use of a pellicle-equipped exposure plate can improve the yield in the exposure process of the lithography stage.

[0074] This specification includes the following embodiments: [1] A method for producing a carbon nanotube self-supporting membrane, comprising: forming a carbon nanotube membrane on one surface of a membrane filter; and separating the carbon nanotube membrane from the membrane filter by flowing a gas from the other surface of the membrane filter toward the one surface; thereby producing the carbon nanotube self-supporting membrane. [2] The method for producing a carbon nanotube self-supporting membrane according to [1], wherein the flow rate of the gas is adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less when the gas is flowing. [3] The method for producing a carbon nanotube self-supporting membrane according to [1] or [2], wherein the membrane filter is fluorine-based. [4] The method for producing a carbon nanotube self-supporting membrane according to any one of [1] to [3], wherein the membrane filter is hydrophobic. [5] The method for producing a carbon nanotube self-supporting membrane according to any one of [1] to [4], wherein the thickness of the formed carbon nanotube membrane is 10 to 100 nm. [6]: A method for manufacturing a carbon nanotube self-supporting film according to any one of [1] to [5], wherein the carbon nanotube film formed has a transmittance of 90% or more to light having a wavelength of 13.5 nm. [7]: A method for manufacturing a carbon nanotube self-supporting film according to [6], wherein the carbon nanotube film is for EUV exposure. [8]: A method for manufacturing a pellicle for photolithography, comprising a pellicle film and a frame-shaped member connected to the pellicle film, wherein the pellicle film is a carbon nanotube self-supporting film manufactured by any one of [1] to [7].[9]: A method for manufacturing a pellicle for photolithography, comprising a pellicle membrane and a frame-shaped member connected to the pellicle membrane, wherein a carbon nanotube membrane is formed on one surface of a membrane filter, the frame-shaped member is connected to the carbon nanotube membrane from the opposite side of the membrane filter, and gas is circulated from the other surface of the membrane filter toward the one surface to separate the carbon nanotube membrane together with the frame-shaped member from the membrane filter, thereby making the carbon nanotube membrane connected to the frame-shaped member the pellicle membrane.

[10] : The method for manufacturing a pellicle according to [9], wherein the flow rate of the gas is adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less when the gas is circulated.

[11] : The method for manufacturing a pellicle according to [9] or

[10] , wherein a fluorine-based membrane filter is used.

[12] : The method for manufacturing a pellicle according to any of [9] to

[11] , wherein a hydrophobic membrane filter is used.

[13] : A method for manufacturing a pellicle according to any of [9] to

[12] , wherein the formation thickness of the carbon nanotube film is 10 to 100 nm.

[14] : A method for manufacturing a pellicle according to any of [9] to

[13] , wherein the carbon nanotube film formed has a transmittance of 90% or more to light having a wavelength of 13.5 nm.

[15] : A method for manufacturing a pellicle according to

[14] , wherein the carbon nanotube film is for EUV exposure.

[16] : A method for manufacturing an exposure master plate with a pellicle, wherein the exposure master plate has a pellicle attached, and the pellicle is manufactured by any of the methods for manufacturing a pellicle according to [8] to

[15] .

[17] : A method for manufacturing an exposure master plate with a pellicle according to

[16] , wherein the exposure master plate is for EUV exposure.

[18] : An exposure method which involves exposure using an exposure master plate with a pellicle manufactured by the method for manufacturing an exposure master plate with a pellicle according to

[16] or

[17] .

[19] : A method for manufacturing a semiconductor device, comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master according to

[16] or

[17] .

[20] : A method for manufacturing a liquid crystal display panel, comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the method for manufacturing

[0075] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that has substantially the same technical idea as described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A method for producing a carbon nanotube self-supporting membrane, characterized by forming a carbon nanotube membrane on one surface of a membrane filter, and separating the carbon nanotube membrane from the membrane filter by flowing a gas from the other surface of the membrane filter toward the one surface, thereby producing the carbon nanotube self-supporting membrane.

2. The method for producing a carbon nanotube self-supporting membrane according to claim 1, characterized in that when the gas is circulated, the flow rate of the gas is adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less.

3. The method for producing a carbon nanotube self-supporting film according to claim 1, characterized in that a fluorine-based membrane filter is used as the membrane filter.

4. The method for producing a carbon nanotube self-supporting film according to claim 1, characterized in that a hydrophobic material is used as the membrane filter.

5. The method for producing a carbon nanotube self-supporting film according to claim 1, characterized in that the thickness of the formed carbon nanotube film is 10 to 100 nm.

6. The method for producing a carbon nanotube self-supporting film according to claim 1, characterized in that the carbon nanotube film formed has a transmittance of 90% or more to light having a wavelength of 13.5 nm.

7. The method for producing a carbon nanotube self-supporting film according to claim 6, characterized in that the carbon nanotube film is for EUV exposure.

8. A method for manufacturing a pellicle for photolithography, comprising a pellicle membrane and a frame-shaped member connecting the pellicle membranes, characterized in that the pellicle membrane is a carbon nanotube self-supporting membrane manufactured by the method for manufacturing a carbon nanotube self-supporting membrane described in claim 1.

9. A method for manufacturing a pellicle for photolithography, comprising a pellicle membrane and a frame-shaped member to which the pellicle membrane is connected, characterized in that: a carbon nanotube membrane is formed on one surface of a membrane filter; the frame-shaped member is connected to the carbon nanotube membrane from the opposite side of the membrane filter; and gas is circulated from the other surface of the membrane filter toward the one surface to separate the carbon nanotube membrane together with the frame-shaped member from the membrane filter, thereby manufacturing a pellicle in which the carbon nanotube membrane connected to the frame-shaped member is the pellicle membrane.

10. The method for manufacturing a pellicle according to claim 9, characterized in that when the gas is circulated, the flow rate of the gas is adjusted so that the pressure loss of the membrane filter is 0.3 kPa or less.

11. The method for producing a pellicle according to claim 9, characterized in that a fluorine-based membrane filter is used.

12. The method for producing a pellicle according to claim 9, characterized in that a hydrophobic membrane filter is used.

13. The method for producing a pellicle according to claim 9, characterized in that when forming the carbon nanotube film, the formation thickness is 10 to 100 nm.

14. The method for producing a pellicle according to claim 9, characterized in that the carbon nanotube film formed has a transmittance of 90% or more to light having a wavelength of 13.5 nm.

15. The method for producing a pellicle according to claim 14, characterized in that the carbon nanotube film is for EUV exposure.

16. A method for manufacturing an exposure master plate and an exposure master plate with a pellicle attached, characterized in that the pellicle is manufactured by the method for manufacturing a pellicle described in any one of claims 8 to 15.

17. The method for manufacturing a pellicle-attached exposure plate according to claim 16, characterized in that the exposure plate is for EUV exposure.

18. An exposure method characterized by using an exposure master plate with a pellicle manufactured by the method for manufacturing an exposure master plate with a pellicle described in claim 16.

19. A method for manufacturing a semiconductor device, characterized by comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master described in claim 16.

20. A method for manufacturing a liquid crystal display panel, characterized by comprising the step of exposing a substrate under vacuum or reduced pressure using a pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master described in claim 16.

21. A method for manufacturing a semiconductor device, characterized by comprising the step of performing EUV exposure on a substrate using a pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master described in claim 16.

22. A method for manufacturing a liquid crystal display panel, characterized by comprising the step of EUV exposure of a substrate using a pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master described in claim 16.

23. A carbon nanotube self-supporting membrane produced by the method for producing a carbon nanotube self-supporting membrane according to any one of claims 1 to 7.

24. A pellicle manufactured by the method for manufacturing a pellicle according to any one of claims 8 to 15.

25. A pellicle-attached exposure master manufactured by the method for manufacturing a pellicle-attached exposure master according to claim 16.

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