JP2006184797A - Method for depositing large-sized pellicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To perform deposition of a pellicle film at a low cost by manufacturing a large-sized depositing substrate whose area is 3,000 cm<SP>2</SP>or more at a low cost and using the depositing substrate. <P>SOLUTION: A method for manufacturing a large-sized pellicle manufactures a pellicle by uniformly applying polymer solution on the depositing substrate and peeling it by using a temporary frame after drying the polymer solution. In the depositing substrate used for the manufacturing method, its area is ≥3,000 cm<SP>2</SP>, and it is obtained by using a blue sheet glass as a material and performing chemical polishing after physical polishing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a large pellicle, and more particularly to a method for forming a large pellicle using a film formation substrate subjected to a special surface treatment.

  The method for forming a large pellicle is as follows. First, a polymer solution generated by dissolving a polymer in a solvent is formed into a film shape on a deposition substrate using a spin coating method or a slit coating method. Next, when the solvent is evaporated by drying, a dried pellicle film is generated on the film formation substrate. Finally, the pellicle film is formed by peeling the dried pellicle film from the deposition substrate.

  A pellicle is manufactured by attaching the film thus obtained to a frame with an adhesive material or a protective film, and cutting off the excess film.

Here, the film formation substrate used when manufacturing the conventional pellicle is a small substrate having an area of less than 3000 cm ^{2 and} is obtained by physical polishing using an abrasive such as aluminum oxide. .

  However, when a pellicle film is formed using such a film formation substrate, the polymer gradually adheres to the substrate surface. Then, fine irregularities are formed on the substrate surface, and the irregularities are transferred to the pellicle film, thereby causing a phenomenon that the pellicle film becomes cloudy. When the film surface of the pellicle film becomes cloudy in this way, there is a problem that it is difficult to detect adhered foreign substances during the film surface inspection. For this reason, the film-formed substrate to which the polymer adheres cannot be used for the formation of the pellicle film. Therefore, it is discarded and a new one is used, or minute irregularities on the substrate surface are formed by re-polishing or washing. By removing it, it was used again as a film formation substrate.

Further, those silicon wafers and area was subjected to a silazane processing on quartz glass substrates of 400 cm ² (e.g., Patent Document 1) and a silicon wafer and the area is a perfluoroalkyl group on the surface of the quartz glass substrate of 400 cm ² There exists what formed the silicon compound which has (for example, patent document 2).

JP 2000-241960 A JP-A-10-39493

However, recently, there has been a demand for a pellicle having a size larger than that of a pellicle used in the past. Along with this, it has become necessary to use a film-forming substrate having a large size of 3000 cm ² or more. However, when a large film-forming substrate of 3000 cm ² or more is used, the following problems occur.

First, when a large film formation substrate having an area of 3000 cm ² is subjected to physical polishing as in the past, the entire surface is caused by non-uniformity of substrate support in the polishing machine and non-uniformity of pressing pressure of the abrasive. It is difficult to polish the pellicle film formation substrate to a level where there is no practical problem without polishing marks. Polishing marks at a level where there is no problem in practical use are 0.5 μm or less in both width and depth.

In addition, since the price of a film-forming substrate increases with the area, a large-sized film-forming substrate with an area of 3000 cm ² or more can be changed to a new one when the film-forming substrate becomes unavailable. Polishing is not practical in cost. Further, it is not preferable to perform cleaning because the number of processes for film formation increases.

  Further, since the contact area between the film and the film formation substrate increases as the film formation substrate becomes larger, a greater force is required to peel the film from the film formation substrate. For this reason, it becomes difficult to peel continuously from the start of peeling to the end of peeling without breaking the film. The film cannot be continuously peeled from the start of peeling to the end of peeling, and the film is locally extended at the place where the peeling speed becomes discontinuous, and streaks are generated on the film surface.

  A large-sized film-forming substrate that does not use silazane treatment or a silicon compound having a perfluoroalkyl group is used, and the structure of the film-forming substrate that is optimal for producing a large-sized pellicle film considering the cost, In addition, the film forming method has not been grasped.

An object of the present invention is to obtain a high-quality pellicle film at a low cost by forming a pellicle film using a large film formation substrate having an area of 3000 cm ² or more.

The first method according to the present invention for achieving the above object is to manufacture a pellicle by uniformly applying a polymer solution on a film formation substrate, drying the polymer solution, and then peeling it using a temporary frame. In the manufacturing method of the large pellicle, the film formation substrate used in the manufacturing method has an area of 3000 cm ² or more, and is obtained by performing chemical polishing after performing physical polishing using soda lime glass as a material. It is characterized by. This effect increases as the substrate area increases, for example, board area is larger and more effective at 5000 cm ^2, in 7000 cm ² further large effect, the effect increases as increases and 10000 cm ^2, 20000 cm ^2.

A second method according to the present invention is a method for producing a large pellicle according to the first method, wherein the film formation substrate is subjected to a surface treatment using silazane represented by the following chemical formula. .

A third method according to the present invention is a method for producing a large pellicle according to the first method, wherein the film formation substrate is subjected to surface treatment using cyclic silazane represented by the following chemical formula. And

A fourth method according to the present invention is a method for producing a large pellicle according to the first method, wherein the film-formed substrate is subjected to a surface treatment using hexamethyldisilazane represented by the following chemical formula. Features.

A fifth method according to the present invention is a method for producing a large pellicle according to the first method, wherein the film formation substrate is subjected to a surface treatment using a silicon compound having a perfluoroalkyl group represented by the following chemical formula. It is characterized by that.

  In the present invention, as described above, a pellicle is manufactured using a film formation substrate produced by performing physical polishing, chemical polishing, and surface treatment using soda lime glass. By using soda lime glass, a film formation substrate can be manufactured at low cost. Further, by performing chemical polishing after physical polishing, it can be polished smoothly to a practical level at low cost.

  In addition, by performing surface treatment such as silazane treatment or perfluoroalkyl layer formation on the film formation substrate, the peelability of the pellicle film from the film formation substrate is improved. Thereby, it is possible to suppress the occurrence of tearing of the pellicle film at the time of peeling, and to perform the peeling efficiently. In addition, it prevents the polymer of the pellicle film from adhering to the surface of the film formation substrate during peeling to form irregularities. As a result, the lifetime of the film formation substrate can be extended.

In this manner, a large film formation substrate having an area of 3000 cm ² or more can be manufactured at low cost, and the pellicle film can be formed at low cost by using the film formation substrate.

  Embodiments of the present invention will be described with reference to the drawings.

(Large pellicle deposition method)
A method for manufacturing a large pellicle will be described. As typical film forming methods for the pellicle film, a spin coating method and a slit coating method will be described as an example. FIG. 1 is an explanatory diagram of the spin coating method, and FIG. 2 is an explanatory diagram of the slit coating method.

  First, the slit coating method will be described. As shown in FIG. 1A, a polymer solution 11 formed by dissolving a polymer in a solvent is dropped almost at the center of a rotationally symmetric film-forming substrate 10, and the film-forming substrate 10 is filled with the polymer solution 11. Next, as shown in FIG. 1B, a thin film is formed by rotating the film formation substrate 10 at a high speed on a turntable 12 and shaking off the excess polymer solution 11.

  Examples of polymers constituting the pellicle membrane include cellulose derivative polymers such as nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose propionate, cellulose acetate butyrate, ethyl cellulose, cyanoethyl cellulose, and cellulose carbonate; Pullulan, cyanoethyl pullulan and other pullulan derivative polymers; polylactic acid polymers; polyvinylidene fluoride, tetrafluoroethylene-vinylidene fluoride copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, ethylene-tetrafluoroethylene copolymers, tetra Fluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene -Perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer or polyvinyl fluoride, fluorine-containing fluorine having a ring structure in the main chain Fluoropolymers such as polymers (CYTOP (trade name, manufactured by Asahi Glass Co., Ltd.), TEFLON AF (trade name, manufactured by DuPont), etc .; polyvinyl acetal polymers such as polyvinyl butyral and polyvinyl propional; 4-methyl-1-pentene Copolymers can be used. The molecular weight of the polymer is selected in consideration of the strength of the pellicle film, the elastic modulus, durability against exposure light, solubility in a solvent, and the like.

  Solvents that dissolve these include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, and ethyl lactate; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; propylene glycol Monomethyl ether acetate; perfluoroalkylamine (FLUORINERT series (product name) manufactured by 3M, CT-Solv series (product name) manufactured by Asahi Glass Co., Ltd.), perfluoroalkylfuran (FLUORINERT series (product made by 3M, product) Name)), hydrofluoroether (Novec series (manufactured by 3M, product name)), perfluoroether (GALDEN (manufactured by SOLVAY SOLEXIS, product name)), hydrofluoroether (H-GALDEN (manufactured by SOLVAY SOLEXIS, Fluorine solvents such as product name)) can be used . These solvents may be used alone or in combination.

  The combination of polymer and solvent is a concentration-viscosity characteristic that is optimal for film formation, taking into account solubility so that filtration can be performed with a desired diameter to remove foreign substances and gels, and obtaining a desired pellicle film thickness. Select with consideration of evaporation rate.

  The pellicle film may be a single layer, or in order to increase the light transmittance, polymers having different refractive indexes may be laminated to form a multilayer film.

  The polymer is dissolved in a solvent by means of heating, pressurization, stirring, etc. to obtain a polymer solution.

  The polymer solution is pressure filtered with dry air, an inert gas such as nitrogen, or a pump to remove foreign substances and gel in the solution. Filters used for filtration include membrane filters and depth filters made of ethylene tetrafluoride, ultrahigh molecular weight polyethylene, nylon, and polypropylene.

  As shown in FIG. 1C, the pellicle film 14 is formed by drying using a hot plate 13 or a heating furnace, drying under reduced pressure, or a combination thereof. Finally, as shown in FIG. 1D, a temporary frame 15 is attached on the film formation substrate 10, and the pellicle film 14 is peeled from the film formation substrate 10. The pellicle film 14 obtained in this manner is attached to a frame with an adhesive material or a protective film, and the pellicle is manufactured by cutting off the excess film.

  Next, the slit coat method will be described. As shown in FIG. 2, the die 21 is moved along the film formation substrate 20 while discharging the pellicle film raw material solution from the die 21 onto the rectangular (rectangular) film formation substrate 20. Thereby, the pellicle film raw material solution is applied. Subsequent drying and peeling are the same as in the spin coating method.

(Material of deposition substrate)
The material of the film formation substrates 10 and 20 used in the film formation method may be soda lime glass, low thermal expansion glass, or quartz glass, but soda lime glass is preferred.

  Since the low thermal expansion glass contains many bubbles in the base material, when the area of the deposition substrate is increased, the probability that bubbles are present on the substrate surface increases. When such bubbles are present on the surface of the film formation substrate, the shape is transferred to the pellicle film. Then, since the shape of the bubble transferred at the film surface inspection cannot be distinguished from the foreign matter attached to the film surface, the pellicle film cannot be used. Here, the film surface inspection is an inspection method in which the film surface is exposed to light from a halogen lamp in a dark room to confirm the presence or absence of minute foreign matter or minute lines on the film surface.

  Although the quartz glass base material has almost no bubbles, quartz glass is very expensive. Moreover, it is difficult to obtain as compared with other glass base materials, and the tendency increases as the substrate area increases. Therefore, when quartz glass is used as a film formation substrate for generating a large pellicle, the film formation substrate becomes very expensive and it may be difficult to obtain it on a regular basis.

  Soda lime glass has few bubbles in the base material. It is also cheap and easy to obtain. However, since the hardness is low, fine streak-like polishing marks are likely to remain after polishing. However, as will be described later, scratches can be resolved to a practical level by applying chemical polishing.

(Manufacturing method of deposition substrate)
A method of manufacturing the film formation substrates 10 and 20 used in the film formation method will be described. The description will be made in the order of the manufacturing process. That is, first, the soda lime glass is processed by physical polishing, then processed by chemical polishing, and finally the surface treatment of the film formation substrate is performed. Although omitted in the description, the substrate may be cleaned or dried in each step as necessary.

The physical polishing process is performed as follows. First, soda lime glass is cut so that the surface area is 3000 cm ² or more to obtain a film formation substrate. Next, the surface of the film-forming substrate is polished while pressing a rotating polishing disk while supplying abrasive grains. The abrasive grains used here are not particularly limited, and aluminum oxide, cerium, and the like can be used.

  In the chemical polishing step, chemicals are supplied to the surface of the film substrate that has been physically polished, which is processed as follows. Then, the chemical dissolves the extreme surface layer on the surface of the film formation substrate. As a result, the surface layer of the film formation substrate becomes smooth. The chemical used here is not particularly limited, but for example, methanol bromide can be used.

  The surface treatment process will be described. There are two types of surface treatment of the film formation substrates 10 and 20 depending on the type of the layer of the pellicle film in contact with the film formation substrate, and a silazane treatment, formation of a perfluoroalkyl layer, or the like is appropriately performed. By performing the surface treatment, adhesion of the polymer to the surface of the film formation substrate can be prevented, and the number of times the film formation substrate can be used can be greatly increased. Further, since the peeling force becomes small, it can be continuously performed from the start of peeling to the end of peeling, and the peeling can be performed without streaking on the film surface.

  First, the types of surface treatment will be described. As shown in FIG. 3, the structure of the pellicle film includes a single-layer structure (FIG. 3A) formed by only the fluorine film 51, and a two-layer structure in which the cellulose derivative 52 is formed under the fluorine film 51 (FIG. FIG. 3B shows a three-layer structure (FIG. 3C) in which a fluorine film 51 is further formed below the two-layer structure. Here, when the layer in contact with the film formation substrate is the cellulose derivative 52, the silazane treatment is performed on the surface 61 of the film formation substrate. When the layer in contact with the deposition substrate is the fluorine film 51, a perfluoroalkyl layer is formed on the surface 62 of the deposition substrate. In the single-layer structure described above, only the fluorine film is formed. However, the single-layer structure may be formed using only the cellulose film.

  First, the silazane process will be described. When the cellulose derivative 52 of the pellicle film is in contact with the film formation substrate, silazane treatment is performed on the surface of the film formation substrate. As silazane used for silazane treatment, silazane as shown in FIG. 4 is used. Here, FIG. 4A is a general silazane, FIG. 4B is a cyclic silazane, and FIG. 4C is hexamethyldisilazane.

  Specific examples of the silazane treatment include spin coating, vapor deposition, dipping, spray coating, and roll coater coating, with the spin coating and vapor deposition being particularly preferred. Here, the spin coating method is a method in which silazane is dissolved alone or in a solvent such as benzene, toluene, hexane or the like so as not to decompose the silazane and spin coating is performed on the surface of the film formation substrate with a diluted solution.

  As conditions for spin coating, spin coating is preferably performed at a rotation speed of 100 rpm to 6000 rpm for 5 seconds to 10 minutes. It is particularly preferable to spin coat at a rotational speed of 300 rpm to 5000 rpm for 20 seconds to 3 minutes.

  The vapor deposition method is a method in which the silazane and the film formation substrate are placed in a dedicated container, and the vapor of the silazane is adhered to the film formation substrate. The pressure is preferably normal pressure or reduced pressure. The deposition temperature is preferably 5 ° C to 200 ° C, more preferably 15 ° C to 120 ° C. The container is preferably sealed, but there may be a vent hole to the outside. The deposition time is preferably 10 seconds to 24 hours, more preferably 1 minute to 1 hour. In either the spin coating method or the vapor deposition method, substrate cleaning and / or drying may be performed before or after silazane treatment, or both.

  Next, formation of a perfluoroalkyl layer will be described. When the fluorine film 51 of the pellicle film is in contact with the film formation substrate, a perfluoroalkyl layer is formed on the surface of the film formation substrate. As the silicon compound having a perfluoroalkyl group, it is preferable to use a solvent having a general formula as shown in FIGS.

  As a specific method for forming the perfluoroalkyl layer, any method may be used, but a spin coating method or a vapor deposition method is preferable, and a vapor deposition method is particularly preferable. The vapor deposition method may be performed under normal pressure, reduced pressure, or increased pressure. The silicon compound having a perfluoroalkyl group and the substrate are placed in a container, and the vapor of the silicon compound having a perfluoroalkyl group is adhered to the substrate surface. The deposition temperature is preferably 5 ° C to 200 ° C, more preferably 20 ° C to 130 ° C. The container is preferably sealed, but it may have a vent hole to the outside. The deposition time is preferably 1 minute to 7 days, more preferably 1 hour to 3 days. In either the spin coating method or the vapor deposition method, substrate cleaning and / or drying may be performed before or after silazane treatment, or both.

  Next, the embodiment and the comparative example will be given and compared to specifically describe the present embodiment.

[Example 1]
A square soda lime glass having a side of 570 mm was prepared and subjected to physical polishing and chemical polishing. This substrate was scrubbed with pure water, subjected to ultrasonic cleaning, dried with hot air, and then subjected to hexamethyldisilazane vapor deposition to obtain a large-sized pellicle film formation substrate. A polymer solution obtained by dissolving cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Company) in ethyl lactate was pressurized to 0.01 MPa with nitrogen and filtered through a membrane filter having a diameter of 0.1 μm by spin coating. It apply | coated on this film-forming board | substrate, and dried with the hotplate. In the spin coating method, 300 g of the polymer solution is supplied onto a glass substrate on a closed cup type spin coater, and the glass substrate is rotated at 350 rpm for 60 seconds. In the drying method, the film formation substrate coated with the polymer solution is placed on a hot plate at 60 ° C. for 30 minutes.

  Thereafter, the pellicle film was peeled off using a temporary frame. The vapor deposition process described here was performed at 100 ° C. for 2 hours in a clean oven and then cooled to room temperature. Next, this substrate and a polyethylene container having an open top with a diameter of 5 cm into which 20 cc of hexamethyldisilazane was introduced were sealed in a clean metal box for 30 minutes at room temperature. After taking out the film formation substrate, it was heated in a clean oven at 100 ° C. for 2 hours.

  This film forming / peeling operation was repeated 100 times. In the peeling method, the double-sided tape is attached to a temporary frame having the same outer diameter as the film-formed substrate, 20 mm in width and 6 mm in thickness. Thus, the film on the film formation substrate was transferred to a temporary frame.

  As a result, the peeling work required only a small peeling force 100 times and could be continuously performed from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, no streaks entered the film surface of 100 pellicle films, and the surface of each pellicle film did not become cloudy. Further, as a result of the film surface inspection of 100 pellicle films, no bright spots were found at the same location, so it can be determined that there are no scratches or bubbles on the substrate surface.

[Example 2]
A square soda lime glass with a side of 1200 mm was prepared and subjected to physical polishing and chemical polishing. This substrate was scrubbed with pure water, subjected to ultrasonic cleaning, dried with hot air, and then subjected to hexamethyldisilazane vapor deposition to obtain a large-sized pellicle film formation substrate. The vapor deposition method is the same as in Example 1.

  The film forming / peeling operation was repeated 100 times. The polymer solution, film formation method, drying method, and peeling method used are the same as those in Example 1.

  As a result, the peeling work required only a small peeling force 100 times and could be continuously performed from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, no streaks entered the film surface of 100 pellicle films, and the surface of each pellicle film did not become cloudy. Further, as a result of the film surface inspection of 100 pellicle films, no bright spots were found at the same location, so it can be determined that there are no scratches or bubbles on the substrate surface.

Example 3
A square soda lime glass having a side of 1400 mm was prepared and subjected to physical polishing and chemical polishing. This substrate was scrubbed with pure water, subjected to ultrasonic cleaning, dried with hot air, and then subjected to hexamethyldisilazane vapor deposition to obtain a large-sized pellicle film formation substrate. The vapor deposition method is the same as in Example 1.

  The film forming / peeling operation was repeated 100 times. The polymer solution, film formation method, drying method, and peeling method used are the same as those in Example 1.

  As a result, the peeling work required only a small peeling force 100 times and could be continuously performed from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, no streaks entered the film surface of 100 pellicle films, and the surface of each pellicle film did not become cloudy. Further, as a result of the film surface inspection of 100 pellicle films, no bright spots were found at the same location, so it can be determined that there are no scratches or bubbles on the substrate surface.

[Comparative Example 1]
A square soda lime glass with a side of 1200 mm was prepared, and only physical polishing was performed. This substrate was scrubbed with pure water, subjected to ultrasonic cleaning, dried with hot air, and then subjected to hexamethyldisilazane vapor deposition to obtain a large-sized pellicle film formation substrate. The vapor deposition method is the same as in Example 1.

  The film forming / peeling operation was repeated 100 times. The polymer solution, film formation method, drying method, and peeling method used are the same as those in Example 1.

  As a result, the peeling work required only a small peeling force 100 times and could be continuously performed from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, the surface of 100 pellicle films did not become cloudy. However, as a result of the film surface inspection of the 100 pellicle films, streaks were observed at the same position on the film surface, and when the corresponding portions of the substrate were observed, streaky polishing marks were observed.

[Comparative Example 2]
A square soda lime glass having a side of 570 mm was prepared and subjected to physical polishing and chemical polishing. This substrate was scrubbed with pure water, then subjected to ultrasonic cleaning and hot air drying to obtain a film substrate for a large pellicle.

  The film forming / peeling operation was repeated 10 times. The polymer solution, film formation method, drying method, and peeling method used are the same as those in Example 1.

  As a result, the peeling operation had a large peeling force at the 10th time, and was discontinuous from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, the surface of the tenth pellicle film was cloudy. Furthermore, streaks due to discontinuity of peeling were found on the film surface. As a result of the film surface inspection of ten pellicle films, no bright spots were found at the same location, so it can be determined that there are no scratches or bubbles on the substrate surface.

[Comparative Example 3]
A square low thermal expansion glass having a side of 800 mm was prepared and subjected to physical polishing and chemical polishing. This substrate was scrubbed with pure water, subjected to ultrasonic cleaning, dried with hot air, and then subjected to hexamethyldisilazane vapor deposition to obtain a large-sized pellicle film formation substrate. The vapor deposition method is the same as in Example 1.

  The film forming / peeling operation was repeated 100 times. The polymer solution, film formation method, drying method, and peeling method used are the same as those in Example 1.

  As a result, the peeling work required only a small peeling force 100 times and could be continuously performed from the start of peeling to the end of peeling. Further, as a result of the film surface inspection of each peeled pellicle film, no streaks entered the film surface of 100 pellicle films, and the surface of each pellicle film did not become cloudy. However, as a result of the film surface inspection of 100 pellicle films, bright spots were found at the same location. When the portion of the substrate was observed, bubbles were observed on the substrate.

  The present invention can be used in a method for forming a large pellicle.

Explanatory drawing of a spin coat method. Explanatory drawing of the slit coat method. The figure explaining the relationship between the structure of a pellicle film and the surface treatment of a film-forming board | substrate. The figure explaining the silazane used for surface treatment. The figure explaining the silicon compound which has the perfluoroalkyl group used for surface treatment.

Explanation of symbols

10… deposition substrate
11… Polymer solution
12… turntable
13… Hot plate
14 Pellicle membrane
15 ... Temporary frame
20… deposition substrate
51… Fluorine membrane
52… Cellulose derivatives
61… Surface
62… Surface

Claims (5)

In a method for producing a large pellicle, a pellicle is produced by uniformly applying a polymer solution on a film formation substrate, drying the polymer solution, and then peeling it using a temporary frame.
A film forming substrate used in the manufacturing method has an area of 3000 cm ² or more, and is obtained by performing chemical polishing after performing physical polishing using soda lime glass as a material, and manufacturing a large pellicle Method. A method for producing a large pellicle according to claim 1,
A method for producing a large pellicle, wherein the film formation substrate is subjected to a surface treatment using silazane represented by the following chemical formula.

A method for producing a large pellicle according to claim 1,
A method for producing a large pellicle, wherein the film formation substrate is subjected to a surface treatment using cyclic silazane represented by the following chemical formula.

A method for producing a large pellicle according to claim 2,
A method for producing a large pellicle, wherein the film formation substrate is subjected to a surface treatment using hexamethyldisilazane represented by the following chemical formula.

A method for producing a large pellicle according to claim 1,
A method for producing a large pellicle, wherein the film formation substrate is subjected to a surface treatment using a silicon compound having a perfluoroalkyl group represented by the following chemical formula.

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