WO2011129378A1 - 自立膜、自立構造体、自立膜の製造方法及びペリクル - Google Patents
自立膜、自立構造体、自立膜の製造方法及びペリクル Download PDFInfo
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- WO2011129378A1 WO2011129378A1 PCT/JP2011/059207 JP2011059207W WO2011129378A1 WO 2011129378 A1 WO2011129378 A1 WO 2011129378A1 JP 2011059207 W JP2011059207 W JP 2011059207W WO 2011129378 A1 WO2011129378 A1 WO 2011129378A1
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- self
- supporting film
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
- G03F1/64—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof characterised by the frames, e.g. structure or material, including bonding means therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention provides a self-supporting film such as an antireflection film that can be suitably used in optical design, such as an imaging optical system such as a camera, a projection optical system such as a display device, an observation optical system such as an image display device, and the like.
- the present invention relates to a self-supporting structure using a film and a method for manufacturing a self-supporting film. Further, the present invention manufactures semiconductor devices such as IC (Integrated Circuit), LSI (Large Scale Integration), TFT LCD (Thin Film Transistor, Liquid Crystal Display).
- the present invention relates to a pellicle used for preventing foreign matter from adhering to a photomax or a reticle used in a lithography process.
- antireflection films having fine irregularities at the wavelength level on the surface have been developed in place of conventional antireflection films due to interference.
- the refractive index is as if from the refractive index 1 of air.
- the refractive index of the substrate gradually changes, and reflection occurring at the interface having different refractive indexes can be suppressed.
- Patent Document 2 discloses an antireflection laminate comprising a light-transmitting substrate and an antireflection layer having a moth-eye structure on the light-transmitting substrate.
- the shape of optical elements used is becoming more complicated.
- the shape of the optical element becomes complicated, it is possible to follow an optical element having a complicated shape, specifically, an optical element having a curved cross section in two orthogonal axes such as a spherical shape.
- an antireflective coating there is a need for an antireflective coating.
- the self-supporting film has antireflection characteristics without using a base material or the like, for example, in the pellicle field, a self-supporting film having excellent optical characteristics can be obtained without using a laminated structure.
- Patent Document 1 or Patent Document 2 when a mold having an uneven structure described in Patent Document 1 or Patent Document 2 is filled with an ultraviolet curable resin or a thermosetting resin and cured, and then a self-supporting film is produced by peeling from the mold.
- an ultraviolet curable resin or a thermosetting resin When trying to make a thin film, there was a problem that the film was broken and difficult to produce.
- the self-supporting film when the entire system is thick, when the self-supporting film is attached to a member having a curved cross section in two orthogonal directions, such as a spherical shape, the self-supporting film cannot follow the shape and the gap (air gap) ) May occur, and as a result, the antireflection effect may not be obtained.
- the present invention has been made in view of such problems, and a self-supporting film having excellent optical characteristics can be provided by providing the self-supporting film with an antireflection function.
- the self-supporting film according to the present invention has a concavo-convex structure layer in which a periodic concavo-convex shape is formed on at least one surface.
- the self-supporting film according to the present invention by having the concavo-convex structure layer on at least one surface, the self-supporting film alone can be provided with an antireflection function without using a separate substrate or the like. For this reason, the self-supporting film
- the at least one resin selected from the group consisting of a fluororesin having a perfluoroalkyl ether ring structure, a cellulose derivative, and a cycloolefin resin is used as a main component of the uneven structure layer.
- the self-supporting film according to any one of [4].
- the height of the convex portion in the concavo-convex shape is 0.5 to 2.0 times the periodic interval of the concavo-convex shape, according to any one of [1] to [7] Free-standing membrane.
- a self-supporting structure including the self-supporting film according to any one of [1] to [9] and a peelable body that is provided on a back surface of the self-supporting film and can be peeled off from the self-supporting film.
- a self-supporting structure including the self-supporting film according to any one of [1] to [9] and a pressure-sensitive adhesive layer or an adhesive layer provided on the back surface of the self-supporting film.
- a pellicle in which a frame, an adhesive applied to one end surface of the frame, and a self-supporting film described in any one of [1] to [9] are bonded to the other end of the frame A pellicle having the concavo-convex structure layer on the inner surface side and / or outer surface side of the self-supporting film.
- a self-supporting film having excellent optical characteristics can be provided by providing the self-supporting film with an antireflection function. Furthermore, according to the present invention, by adjusting the thickness, it is possible to provide a self-supporting film having excellent shape following ability, and therefore, the film is pasted on a member whose cross section has a curved shape in two orthogonal axes. It is extremely difficult for gaps to occur.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the self-supporting film of the present invention is a self-supporting film having a concavo-convex structure layer having a periodic concavo-convex shape formed on the surface, and has a concavo-convex structure layer having a periodic concavo-convex shape formed on at least one side.
- the periodic structure includes a periodic structure having irregular shapes and random pitches.
- FIG. 1 is a partially enlarged cross-sectional view of an example of a self-supporting film according to this embodiment.
- a self-supporting film 4 includes an uneven structure layer 1 having a periodic uneven shape 5 formed on one surface, and a thin film layer 2 on the other surface of the uneven structure layer 1.
- the concavo-convex structure layer refers to a layer having a periodic concavo-convex shape on the surface and integrally formed with the concavo-convex shape.
- the surface on which the periodic uneven shape is not provided is defined as the back surface.
- the surface with the larger period of the uneven shape is the back surface, and when the uneven shape has the same period, any one surface is the back surface.
- the self-supporting film of the present embodiment is excellent in shape followability by forming an average thickness of 0.2 ⁇ m or more and 20.0 ⁇ m or less, which is much thinner than the conventional self-supporting film. Further, a gap is extremely unlikely to occur even when affixed to a member having a curved cross section in two orthogonal axes such as a spherical shape. The thinner the average thickness of the free-standing film, the better the shape followability.
- the thickness average of the free-standing film is preferably 0.3 ⁇ m or more and 15.0 ⁇ m or less because of the strength of the free-standing film and the ease of making a uniform film.
- the thickness is preferably 0.5 ⁇ m or more and 10.0 ⁇ m or less, and particularly preferably 0.7 ⁇ m or more and 6.0 ⁇ m or less.
- the average thickness is preferably 20.0 ⁇ m or less from the viewpoint of reducing misalignment due to aberration.
- the positional deviation due to aberration here is caused by the fact that the refractive index of a substance differs depending on the wavelength of light.
- FIG. 4 is a schematic diagram for explaining misalignment due to aberration. Since the refraction angle at the interface when entering the free-standing film from an oblique direction varies depending on the wavelength, the position where transmitted light after passing through the free-standing film is shifted due to the wavelength, and aberration 12 occurs.
- the positional deviation due to this aberration is large, there may be a problem that the optical design after passing through the self-supporting film becomes complicated and that a precise optical design becomes difficult. Since the self-supporting film has an average thickness of 0.2 ⁇ m or more and 20.0 ⁇ m or less, which is much thinner than the conventional self-supporting film, the positional deviation due to aberration is extremely small.
- the shape of the convex portion in the concavo-convex shape is not particularly limited, but it is preferable that the shape of the convex portion is a shape that continuously changes in the height direction because the antireflection effect is enhanced. Moreover, since the minimum value of the transmittance in broadband light is particularly high, the average transmittance is also increased.
- a shape of the convex portion for example, a shape in which the cross-sectional shape in the thickness direction is a trapezoid, a rectangle, a rectangle, a prism shape, a triangle shape, or a semicircular shape can be considered.
- corrugated shape for example, the shape where the cross-sectional shape of the thickness direction is trapezoid, a rectangle, a rectangle, a prism shape, a triangle shape, a semicircular convex shape, a sinusoidal shape, etc.
- a periodic uneven shape can be considered.
- the sinusoidal shape means that it has a curved portion formed by repetition of a concave portion and a convex portion.
- the curved part should just be a curved curve, for example, the shape which has a constriction in a convex part is also included in a sine wave form.
- a triangular shape or a sine wave shape provides a high antireflection effect.
- the cross-sectional shape of the convex portion is a shape that continuously changes in the height direction such as a trapezoid, a rectangle, a square, a prism, a triangle, and a semicircular shape in two orthogonal directions, the incidence of light The difference in the antireflection effect depending on the direction is reduced, which is preferable.
- a polygonal pyramid shape such as a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a conical shape, a truncated polygonal pyramid shape, a truncated conical shape, and the like are conceivable.
- the truncated polygonal pyramid refers to a shape obtained by horizontally cutting the top of the polygonal pyramid
- the truncated cone refers to a shape obtained by horizontally cutting the top of the cone.
- a portion where each surface contacts may be a curved surface
- a connecting portion between adjacent convex shapes may be a curved surface.
- the occupancy ratio of the uneven shape on the free-standing film surface is preferably 70% or more, more preferably 85% or more, and particularly preferably 95% or more.
- the bottom surface shape of the convex portion is a shape that can be spread on a flat surface without any gap. Therefore, the concavo-convex shape is a grid-like concavo-convex shape in which the concavo-convex extends in one axis direction, or a convex portion that can be spread on the bottom surface such as a (pier) triangular pyramid, a (pier) quadrangular pyramid, or a (pier) hexagonal pyramid. A continuously arranged shape is preferred.
- the concave / convex shape is preferably a shape having as little angle dependency as possible for the antireflection effect, and if the concave / convex shape has the same cross-sectional shape in the biaxial direction where the cross-sectional shape in the thickness direction is orthogonal, the angular dependency is reduced. preferable. Therefore, as the shape of the convex portion, it is preferable to use a shape having the same cross-sectional shape in two orthogonal directions such as a polygonal cone shape, a cone shape, a truncated polygonal cone shape, and a truncated cone shape. In particular, from the viewpoint of angle dependency, a conical shape and a truncated cone shape are preferable. On the other hand, from the viewpoint of the antireflection effect, a shape that continuously changes in the height direction is preferable, and a conical shape and a polygonal pyramid shape are preferable.
- the period interval of the concavo-convex shape is equal to or less than the use wavelength because the antireflection effect is enhanced. Since a wavelength of 150 nm to 2000 nm is usually used for an optical element, it is preferable to set the period interval of the concavo-convex shape to 250 nm or less in order to enhance the antireflection effect. More preferably, it is 150 nm or less, Most preferably, it is 75 nm or less, and 1 nm or more is preferable from a manufacturing viewpoint. Moreover, it is possible to obtain good optical characteristics when the height of the convex portion is 0.5 to 2.0 times, particularly 1.0 to 2.0 times the uneven shape periodic interval, which is preferable. .
- the height of the convex portion defined here refers to the difference in height between the concave bottom point and the convex vertex of the periodic concave / convex shape.
- the height of the convex portion is 0.3 times or more of the operating wavelength because a high antireflection effect can be obtained.
- the convex shape is a quadrangular pyramid shape
- the height of the convex portion is 0.5 times or more of the operating wavelength
- the convex shape is a cone
- the height of the convex portion is 0.45 times or more of the operating wavelength and the cone is In the case of a shape overlapping in the horizontal direction, it is preferable that the height of the convex portion is 0.65 times or more because a particularly high antireflection effect can be obtained.
- the height of the convex portion is preferably as high as possible, but a sufficient antireflection effect can be obtained even at 1 ⁇ m or less.
- the concavo-convex shape may be provided on both sides of the self-supporting film and the concavo-convex structure layer not only on one side.
- the antireflection effect can be enhanced more than when the concave and convex shape is provided only on one side, and therefore it is preferable to provide the concave and convex shape on both sides.
- corrugated shape is provided in the surface side which contact
- FIG. 5 is a partially enlarged cross-sectional view of an example of a concavo-convex structure layer according to an embodiment of the present invention.
- the arithmetic mean of the distance from the concave bottom point 13 to the concave-convex structure layer back surface 6 is the thickness variation average.
- the thickness of the uneven structure layer 1 is the thickness from the back of the uneven structure layer to the top of the convex portion.
- the thickness 11 of the concavo-convex structure layer 1 is such that the vertices of the convex portions are extracted from the highest one to several (for example, the fifth), and the concavo-convex structure is obtained from the average height 10 of the extracted vertices.
- the dimensions can be up to the back of the layer.
- the average thickness variation is preferably 100 nm or less, more preferably 50 nm or less. Moreover, when the use in an ultraviolet light region is also assumed, the average thickness variation is preferably 50 nm or less, more preferably 10 nm or less. An average thickness variation of 100 nm or less is preferable from the viewpoint of reducing the appearance of color unevenness when used as a self-supporting film.
- the coating layer 3 may be provided on the surface of the uneven shape 5.
- a hard coat layer As the coating layer, a hard coat layer, a metal thin film layer, other self-supporting layers, a moisture-proof layer, an antistatic layer, an electromagnetic wave shielding layer, a near-infrared absorption layer, an ultraviolet absorption layer, a selective absorption filter layer, etc. can be considered. May be layered.
- a known acrylic polymer, urethane polymer, epoxy polymer, silicone polymer, silica compound, silicon (Si) oxide which is a curable resin that is cured by active energy rays, Examples thereof include nitrides, halides, carbide simple substances or composites thereof, and metal thin film layers.
- metal thin film layer aluminum (Al), chromium (Cr), yttrium (Y), zirconia (Zr), tantalum (Ta), titanium (Ti), barium (Ba), indium (In), tin (Sn), Zinc (Zn), Magnesium (Mg), Calcium (Ca), Cerium (Ce), Copper (Cu), Silver (Ag), Gold (Au) and other metal oxides, nitrides, halides and carbides Or those composites are mentioned.
- Other self-supporting layers include tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene terpolymers and fluororesins having a perfluoroalkyl ether ring structure (in particular, Teflon (registered trademark) manufactured by Du Pont). AF, Asahi Glass's Cytop (trade name), Augmont's Algoflon (trade name), and polyfluoroacrylate are preferred), calcium fluoride, magnesium fluoride, barium fluoride, etc. Examples thereof include a self-supporting layer formed from a material.
- the outermost surface layer of the coating layer that forms the free-standing film surface 7 is desirably a resin layer, and particularly has a durometer hardness (measured according to JIS K7215) of HDA30.
- the resin layer of HDD90 or less is desirable.
- the coating layer is preferably a resin layer over the entire layer, and in particular, the durometer hardness over the entire layer (measured in accordance with JIS K7215). Is desirably a resin layer of HDA30 or more and HDD90 or less.
- the coating layer has a refractive index as close as possible to the concave-convex shape of the concave-convex structure layer because the antireflection effect is enhanced. As is clear from the definition of the uneven structure layer, the coating layer is not included in the uneven structure layer.
- a thin film layer may be laminated on the back surface of the uneven structure layer.
- the thin film layer it is preferable to use the above-mentioned other self-supporting layers, metal thin film layers, and the like.
- the thin film layer may be a single layer or multiple layers. As is clear from the definition of the uneven structure layer, the thin film layer on the back surface is not included in the uneven structure layer.
- a self-supporting structure from the self-supporting film and a peeling body that is provided on the back surface of the self-supporting film and can be peeled off from the self-supporting film.
- the uneven structure layer and the peeled body are in contact with each other.
- Such a self-supporting structure is suitable from the viewpoint of easily handling the antireflection film before use.
- the surface of the peeling body facing the concavo-convex structure layer has a substantially spherical shape (or a spherical shape) because it can be easily peeled from the peeling body.
- a self-supporting structure from the self-supporting film and a pressure-sensitive adhesive layer or an adhesive layer provided on the back surface of the self-supporting film.
- the uneven structure layer is in contact with the pressure-sensitive adhesive layer or the adhesive layer.
- Such a self-supporting structure is suitable from the viewpoint of easily handling the self-supporting film before use.
- the method for producing the self-supporting film is not particularly limited.
- a resin composition having a yield strain of 1% or more and a tensile elongation of 10% or more is dissolved in an organic solvent.
- a method of obtaining a self-supporting film having an average thickness of 0.2 ⁇ m or more and 20.0 ⁇ m or less by applying the polymer solution to a film-forming substrate having a periodic uneven shape on the surface and then drying and peeling. .
- the thickness An uneven structure layer having an average of 0.2 ⁇ m or more and 20.0 ⁇ m or less can be produced.
- the resin contained in the resin composition has a high light transmittance in the visible light region and the ultraviolet region.
- resins include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cross-linked polyethylene resin, polyvinyl chloride resin, polyarylate resin, polyphenylene ether resin, modified polyphenylene ether resin, polyetherimide resin, poly Ether sulfone resin, polysulfone resin, polyether ketone resin, cellulose derivative (cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc., or a mixture of two or more thereof), cycloolefin resin (norbornene polymer) Or copolymers (including hydrogenated ones) such as Apel (registered trademark) (manufactured by Mitsui Chemicals), Topas (registered trademark) (man
- a resin having a yield strain of 1% or more and a tensile elongation of 10% or more as a main component of the resin composition.
- the main component means that the yield strain contained in the resin composition is 1% or more and the amount of the resin component having a tensile elongation of 10% or more is 50% by weight or more.
- fluorine resins having a yield strain of 1% or more and a tensile elongation of 10% or more
- fluorine resins cycloolefin resins and cellulose derivatives having a perfluoroalkyl ether ring structure (particularly cellulose acetate propio).
- cellulose acetate propio cellulose acetate propio
- a fluororesin having a perfluoroalkyl ether ring structure is preferable.
- the amount of the resin component having a yield strain of 1% or more and a tensile elongation of 10% or more contained in the resin composition is preferably 80% or more, more preferably 90% or more, and particularly preferably 95. % Or more.
- the resin composition may contain an ultraviolet absorber, a light stabilizer, an antioxidant for improving the effect of the light stabilizer, and the like according to the purpose of use.
- the concavo-convex structure layer has a periodic surface with a polymer solution (free-standing film material) obtained by dissolving a resin composition having a yield strain of 1% or more and a tensile elongation of 10% or more in an organic solvent. It can be manufactured by applying a film having a predetermined thickness on a film-formation substrate having a concavo-convex shape, drying it, and peeling it from the film-formation substrate.
- the material of the film formation substrate is preferably a material that can ensure sufficient flatness, and synthetic quartz, fused silica, alkali-free glass, low alkali glass, soda lime glass, silicon, nickel plate, and the like are preferable.
- synthetic quartz, fused silica, alkali-free glass, low alkali glass, soda lime glass, silicon, nickel plate, and the like are preferable.
- the thermal expansion coefficient of the film formation substrate is smaller.
- the linear expansion coefficient at 0 ° C. to 300 ° C. is preferably 50 ⁇ 10 ⁇ 7 m / ° C. or less.
- the uneven shape on the surface of the film formation substrate may be a shape corresponding to the uneven shape of the uneven structure layer described above.
- a photoresist is applied on a transparent substrate (preferably synthetic quartz glass) provided with a chromium thin film layer, and after pre-baking, an uneven shape is drawn on the resist using an electron beam exposure apparatus.
- the concavo-convex shape drawn on the chromium thin film layer is a shape corresponding to the concavo-convex shape of the concavo-convex structure layer.
- the chromium layer portion exposed from the resist pattern is etched, and the resist pattern is transferred to the chromium layer. Finally, the resist residue is washed to produce a reticle.
- stepper After uniformly applying the photoresist on the film formation substrate, pre-bake to solidify the photoresist.
- stepper which is one of the semiconductor device manufacturing equipment, the fine pattern of the previously produced reticle is reduced by a reduction projection lens and projected while moving on a wafer coated with a photoresist. Exposure. Next, the exposed portion of the photoresist is removed by immersion in an organic alkali developer. Further, it is rinsed several times with ultrapure water to remove the exposed residue and then heated. A portion not covered with the photoresist is selectively etched by a dry etching method to produce a fine pattern on the wafer.
- a film-formed substrate having a concavo-convex shape on the substrate surface can be obtained.
- the shape of the periodic unevenness on the film formation substrate can be freely changed by changing the pattern size of the reticle and exposure / etching conditions.
- Examples of the method for applying the polymer solution to the film formation substrate include a spin coating method, a roll coating method, a knife coating method, a casting method, and the like.
- a spin coating method is particularly preferred.
- the film forming method by the spin coat method will be described.
- the concavo-convex structure layer is prepared using a polymer solution in which the above-described film material is dissolved in an organic solvent.
- the solvent those which have very little volatilization at ambient temperature and whose boiling point is not too high are preferable. Considering the above, it is desirable that the solvent has a boiling point of 100 to 200 ° C.
- examples of such a solvent include aliphatic hydrocarbon compounds, aromatic compounds, halogenated hydrocarbons such as chlorinated hydrocarbons, ester compounds, and ketone compounds.
- organic solvents such as saturated aliphatic hydrocarbon compounds such as alicyclic hydrocarbons, aromatic compounds, and halogenated hydrocarbons can be suitably used for cycloolefin resins, and chlorine for cellulose derivatives.
- Soluble in single or mixed organic solvents such as hydrocarbons, ketones, esters, alkoxy alcohols, benzene, alcohols.
- Examples of these organic solvents include organic solvents such as chlorinated hydrocarbons, ester compounds, and ketone compounds.
- chlorinated hydrocarbon methylene chloride, ethylene chloride, propylene chloride and the like are preferably used, and as the ketone compound organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferably used.
- ester compound organic solvent acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.) and lactate esters (ethyl lactate, butyl lactate, etc.) are preferably used.
- benzene, ethanol, methanol, cellosolve acetate, carbitol and the like can be used as a single or mixed solvent.
- the concentration of the polymer solution is preferably 1 to 10% by mass, since the thickness variation of the uneven structure layer during drying is reduced. More preferably, it is 3 to 8% by mass.
- the polymer solution preferably has an absorbance of 0.05 or less.
- the thickness and uniformity (thickness variation) of the concavo-convex structure layer are mainly determined by the liquid temperature of the polymer solution, the ambient temperature / humidity, and the number of rotations of the film formation substrate.
- the temperature of the polymer solution is preferably about the same as the ambient temperature (10 to 30 ° C.), and the temperature of the film formation substrate is also preferably about the same as the ambient temperature. It is preferable that the liquid temperature, the ambient temperature, and the temperature of the film formation substrate are approximately the same because thickness variations can be suppressed.
- the humidity is preferably 30 to 60%.
- the film formation substrate is rotated at a rotational speed of 50 to 5000 revolutions per minute to form a film.
- the number of revolutions is preferably 50 to 500 revolutions per minute, more preferably 75 to 400 revolutions per minute, and still more preferably 100 to 300 revolutions per minute.
- the rotation time is preferably 30 seconds or longer and 120 seconds or shorter, and more preferably 30 seconds or longer and 60 seconds or shorter.
- the film thickness of the concavo-convex structure layer is preferably about 0.2 ⁇ m or more and 20.0 ⁇ m or less, and is preferably 0.3 ⁇ m or more and 15.0 ⁇ m or less from the viewpoint of the strength of the concavo-convex structure layer or the ease of forming a uniform film. It is preferably 5 ⁇ m or more and 10.0 ⁇ m or less. Especially preferably, they are 0.7 micrometer or more and 6.0 micrometers or less.
- the film formation substrate is placed on a hot plate and dried to evaporate the solvent. From the viewpoint of film uniformity, drying is preferably performed in two stages, low temperature drying and high temperature drying. After drying at 30 ° C. to 90 ° C. for about 4 minutes to 15 minutes, the drying is performed at 50 ° C. to 200 ° C. for 4 minutes to It is preferable to dry for about 30 minutes.
- the film is peeled off from the substrate.
- the releasability is important.
- Silane coupling is known as a method for controlling the contact angle of a substrate.
- a silane having an ether bond at the terminal is brought into contact with the substrate surface and reacted.
- the other end group is a group having low affinity with the membrane material, so that the releasability is improved.
- Fluorine is highly effective as a mold release agent, and in order to achieve high mold release properties, the other terminal group is particularly preferably a fluorine terminal.
- the yield strain is more preferably 2% or more, further preferably 4% or more, and particularly preferably 5% or more.
- the tensile elongation is more preferably 50% or more, still more preferably 100% or more, and particularly preferably 160% or more.
- the upper limits of the yield strain and the tensile elongation are not particularly limited. However, if the yield strain is 1% to 30% and the tensile elongation is 10% to 500%, film breakage can be sufficiently suppressed.
- the areas of the self-supporting film and the concavo-convex structure layer are preferably as large as possible, preferably 100 cm 2 or more, more preferably 300 cm 2 or more, still more preferably 700 cm 2 or more, and particularly preferably 1000 cm 2 or more.
- the area of the antireflection film and the uneven structure layer is preferably 35000 cm 2 or less.
- the produced concavo-convex structure layer has a yield strain of 1% or more and a tensile elongation of 10% or more, it can be stretched while being pulled with respect to the member.
- the yield strain is more preferably 2% or more, further preferably 4% or more, and particularly preferably 5% or more.
- the tensile elongation is more preferably 50% or more, still more preferably 100% or more, and particularly preferably 160% or more. There is no upper limit on the yield strain and tensile elongation, but sufficient shape followability can be obtained if the yield strain is 1% to 30% and the tensile elongation is 10% to 500%.
- the self-supporting film according to the present embodiment does not require a base material layer that supports the concavo-convex structure layer due to its manufacturing method, it is possible to directly provide an adhesive layer or an adhesive layer on the back surface of the concavo-convex structure layer. And it becomes a very thin self-supporting structure by providing a pressure-sensitive adhesive layer or an adhesive layer directly on the back of the concavo-convex structure layer.
- the pressure-sensitive adhesive and adhesive it is preferable to use a pressure-sensitive adhesive and adhesive that are suitably used for optical materials.
- the adhesive include urethane adhesives and acrylic adhesives, and specific examples of the adhesive include acrylic adhesives, urethane adhesives, epoxy adhesives, and UV curable adhesives. An agent or the like is preferable.
- the thickness of the pressure-sensitive adhesive and adhesive is preferably as thin as possible so that practical pressure-sensitive adhesion and adhesive strength can be maintained, and deformation of the adherend can be suppressed.
- a peelable body that can be peeled directly from the concavo-convex structure layer on the back surface of the concavo-convex structure layer without providing a pressure-sensitive adhesive layer or an adhesive layer on the back surface of the concavo-convex structure layer.
- a glass substrate, a film base material, an optical element etc. can be considered.
- the peeled body may have a spherical shape as well as a planar shape.
- the self-supporting film is usually in a state where a peelable body that can be peeled off from the self-supporting film is provided on the back surface of the self-supporting film, or an adhesive material layer is provided on the back surface of the self-supporting film, and an antireflection film of the adhesive material layer is further provided. It is stored in a state where a peelable body that can be peeled off from the pressure-sensitive adhesive layer is provided on the surface opposite to the surface it has, and is peeled off from the peelable body during use.
- the self-supporting film according to the present embodiment has a very thin average thickness of 0.2 ⁇ m or more and 20.0 ⁇ m or less and low rigidity. For this reason, as a method for storing the self-supporting film, a self-supporting film and a peeling body that can be peeled off from the self-supporting film provided on the back surface of the self-supporting film and has a curved surface in a cross-section in two orthogonal directions.
- a method of storing a self-supporting film as a laminated body, or a self-supporting film, an adhesive material layer provided on the back surface of the antireflection film, and a surface of the adhesive material layer opposite to the surface having the self-supporting film A method of storing the laminate as a laminate including a release body provided on the surface and capable of being peeled from the pressure-sensitive adhesive layer and having a curved cross section in two orthogonal directions is preferable.
- the peeled body has a curved surface in the two perpendicular directions
- the peeled body or the self-supporting film or the peeled body having a curved shape for example, a roll shape having a curved surface only in the one-axis direction.
- an adhesive material layer can be directly provided on the back surface of the concavo-convex structure layer, or a form in which a peelable body that can be peeled from the self-supporting film on the back surface of the concavo-convex structure layer and has a curved surface in a biaxial direction perpendicular to each other.
- a release body is provided on the surface opposite to the surface having the concavo-convex structure layer of the pressure-sensitive adhesive layer and can be peeled from the pressure-sensitive adhesive layer, and the cross-section has a curved shape in the two perpendicular directions.
- the self-supporting film of the present invention has excellent shape followability, image display devices such as touch panels, liquid crystal display panels, plasma displays, and organic EL displays, projection optical systems such as projectors, observation optical systems such as optical lenses, and imaging optics such as cameras It can be suitably used for optical elements such as systems, polarization beam splitters, light emitting part tips of light emitting diodes, and the surface of solar cell panels.
- the self-supporting film according to the present invention is used for a pellicle film of a pellicle.
- a pellicle that can easily be used for removing foreign substances attached to the pellicle film and that can be used repeatedly is required.
- the conventional pellicle film is difficult to remove foreign matter adhering to the pellicle surface, and it is necessary to blow air at a high pressure and high flow rate to remove the foreign matter. The problem of tearing and the problem that the pellicle film adheres to the photomask due to the pressure of air have arisen.
- FIG. 10 is a cross-sectional view of a pellicle according to the second embodiment.
- the pellicle 20 according to the second embodiment includes a frame body 27, an adhesive 28 applied to one end surface of the frame body 27, and a self-supporting film on the other end surface of the frame body 27.
- the pellicle film 21 is adhered.
- FIG. 6 is a partial enlarged cross-sectional view of an example of a self-supporting film according to an embodiment of the present invention.
- the pellicle film 21 according to this embodiment is characterized in that a plurality of convex structures 22 are provided on at least one side.
- the convex structure 22 corresponds to the convex part forming the concave and convex shape
- the layer including the convex structure 22 corresponds to the concave and convex structure layer on which the concave and convex shape is formed. .
- convex structure interval 6 the distance between the apexes of one convex structure and the convex structure closest to the convex structure. Since the contact area between the foreign matter and the pellicle film is reduced when a large foreign matter adheres, it is difficult for the foreign matter to adhere to the pellicle membrane, and even if foreign matter adheres to the pellicle membrane, the foreign matter is removed during air blowing. Becomes easier.
- the convex structure here refers to a convex shape with a height of 30 nm or more, and the convex structure height 25 here is the difference between the vertex 23 of the convex structure and the bottom 24 of the convex structure. Point to.
- the interval between the convex structures refers to the vertex interval between the target convex structure and the convex structure closest to the convex structure.
- the shape of the convex structure is not particularly limited.
- the sinusoidal shape means that it has a curved portion formed by repetition of a concave portion and a convex portion.
- the curved part should just be a curved curve, for example, the shape which has a constriction in a convex part is also included in a sine wave form.
- a triangular shape or a sine wave shape is preferable because the effect of suppressing the adhesion of foreign matters is high and the removal of foreign matters during air blowing is particularly easy.
- This also has the advantage that the pellicle film having a convex structure has a high reflection suppressing effect described later.
- the convex structure may be provided only on one side of the pellicle film or on both sides. When provided on both sides, the effect of suppressing the adhesion of foreign matter can be imparted to both sides of the pellicle film. Moreover, since the antireflection effect mentioned later can be heightened compared with the case where a convex structure is provided only on one side, it is preferable.
- an antireflection layer may be provided on the surface opposite to the surface of the convex structure or the surface on which the convex structure of the pellicle film is provided.
- the antireflection layer may be a single layer or a multilayer.
- Materials for the antireflection layer include terpolymers of tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene, fluorine-based resins having a perfluoroalkyl ether ring structure (in particular, Teflon (registered trademark) AF manufactured by Du Pont).
- CYTOP trade name
- Algoflon trade name
- materials having low refractive index such as calcium fluoride, magnesium fluoride, and barium fluoride. It can be preferably used.
- the film material of the pellicle film and the material used for the convex structure are not particularly limited, but preferably have a high light transmittance at the exposure wavelength at which the pellicle film is used.
- a cellulose derivative cellulose acetate, Cellulose acetate propionate, cellulose acetate butyrate, etc., or a mixture of two or more thereof
- cycloolefin resins nonene polymers or copolymers (including hydrogenated ones), for example, Appel (registered trademark) ) (Mitsui Chemicals), Topas (registered trademark) (polyplastics Co., Ltd.), Zeonex (registered trademark) or Zeonoa (registered trademark) (manufactured by Nippon Zeon), Arton (registered trademark) (manufactured by JSR) Etc.), fluororesin (tetrafluoroethylene-vinylidene fluoride-hexafluoropropyl) A
- a fluororesin having a perfluoroalkyl ether ring structure, cellulose acetate propionate, cellulose acetate butyrate or cycloolefin resin is used as a main component of a pellicle film material and a material used for a convex structure
- the pellicle film and the convex structure are well formed and particularly preferred.
- the main component means that the amount of the target resin component contained in the pellicle film material is 50% by weight or more.
- nitrocellulose when nitrocellulose is a main component, when a wavelength of 300 nm or less is irradiated, deterioration is accelerated and light resistance is deteriorated. Therefore, although the transmittance is high, it is not preferable because the lifetime of the film is shortened. In addition, since nitrocellulose itself has explosive properties, it cannot be easily produced as the content increases.
- the film material of the pellicle film and the material of the convex structure may be the same material, or a different material, that is, a structure in which an uneven structure layer having a convex structure formed of a material different from the pellicle film is provided on the pellicle film may be used. . From the viewpoint of ease of manufacturing, the film material of the pellicle film and the material of the convex structure are preferably the same.
- the convex structures are arranged with a certain periodic interval, because foreign matter removal at the time of air blowing is particularly easy and the antireflection effect described later is enhanced.
- the reason why it is particularly easy to remove foreign matters during air blowing if the convex structure is arranged with a certain periodic interval is not clear, but if it is a periodic convex structure, the air flow during air blowing is a smooth flow. Therefore, it is considered that foreign matter can be removed with a lower blow pressure.
- the period of the convex structure does not need to be a constant period on the entire surface of the pellicle film, and a partially different periodic convex structure may be provided.
- the periodic interval is preferably 1.0 ⁇ m or less.
- the reflection suppression effect can be enhanced in addition to the above-described foreign matter adhesion suppression effect.
- the reflection suppression effect is an effect of suppressing reflection at the interface of the pellicle film when exposure light is incident on the pellicle film.
- the reflection is suppressed, not only stray light is reduced but also a substantial amount of transmitted light.
- loss of light intensity during exposure can be prevented.
- a wavelength of 500 nm or less, particularly 200 nm or less is used with the recent microstructuring. Therefore, it is preferable to set the periodic interval of the convex structure to 500 nm or less, and more preferably to increase the reflection suppressing effect.
- the lower limit value of the periodic interval is not particularly limited. However, considering that the manufacturing cost increases as the periodic interval becomes shorter, it is preferable to set the lower limit value to 50 nm or more from the balance between performance and manufacturing cost.
- the height of the convex structure if the height of the convex structure is 30 nm or more, a sufficient foreign matter adhesion suppressing effect can be obtained, but the higher the convex structure height, the foreign matter adhesion suppressing effect and the reflection suppressing effect. Is preferable. More preferably, it is 70 nm or more, Most preferably, it is 100 nm or more. In addition, since the height of the convex structure is 0.5 to 2.0 times the periodic interval of the convex structure, and particularly 1.0 to 2.0 times, a particularly high reflection suppressing effect can be obtained. preferable. In addition, the periodic interval of a convex structure respond
- the height of the convex structure is 0.3 times or more of the operating wavelength because a high reflection suppressing effect can be obtained.
- the convex structure is a quadrangular pyramid, the height is 0.5 times or more of the operating wavelength, and when it is conical, the height is 0.45 or more of the operating wavelength, and the cone overlaps in the horizontal direction.
- the ratio is 0.65 or more, a particularly high antireflection effect can be obtained, which is preferable.
- the upper limit value of the height of the convex structure is not particularly limited, but a sufficient antireflection effect can be obtained at 1 ⁇ m or less.
- the shape of the convex structure is not particularly limited, but a shape that continuously changes in the height direction is particularly preferable because of its high foreign matter adhesion suppressing effect and reflection suppressing effect.
- a shape may be a pyramid shape or a cone shape.
- the occupation ratio of the convex structure on the pellicle film surface is preferably 70% or more, more preferably 85% or more, and particularly preferably 95% or more.
- the bottom shape of the convex structure is preferably a shape that can be spread on the plane of the pellicle film without any gap.
- the convex structure a grid-like convex structure in which the convex structure extends in a uniaxial direction, and when using a pyramid shape or a truncated polygonal pyramid shape, the bottom surface has a shape that can be laid down such as a triangle, a quadrangle, a hexagon, etc. Preferably it is.
- a cone or frustoconical shape it is preferable to have a hexagonal close-packed structure. Furthermore, as shown in FIG. It is preferable to arrange them together.
- the pellicle film of the present invention is formed by applying a pellicle film material to the surface of a pellicle film formation substrate having a concave shape on the surface to form a pellicle film, and then forming the pellicle film from the pellicle film formation substrate.
- the pellicle film can be manufactured by peeling off.
- the material for the pellicle film forming substrate is preferably a material that can ensure sufficient flatness, and synthetic quartz, fused silica, alkali-free glass, low alkali glass, soda lime glass, silicon, nickel plate, and the like are preferable.
- silicon because the flatness of the substrate surface with high accuracy can be secured and the unevenness on the substrate surface can be easily produced.
- the film formation substrate has a smaller thermal expansion coefficient.
- the linear expansion coefficient at 0 ° C. to 300 ° C. is preferably 50 ⁇ 10 ⁇ 7 m / ° C. or less.
- the convex shape or concave shape of the film formation substrate surface may be provided with a shape corresponding to the convex structure described above.
- a photoresist (photosensitive material) is applied onto a synthetic quartz glass having a chromium thin film layer, and after prebaking, a concave shape is drawn on the resist using an electron beam exposure apparatus.
- the concave shape to be drawn is a shape corresponding to the convex structure on the pellicle film.
- the chromium layer portion exposed from the resist pattern is etched, and the resist pattern is transferred to the chromium layer. Finally, the resist residue is washed to produce a reticle.
- stepper which is one of the semiconductor element manufacturing equipment
- the fine pattern of the reticle produced earlier is reduced by a reduction projection lens, and projected exposure while moving on a resist-coated wafer.
- stepper Immerse in an organic alkali developer to remove the exposed resist, rinse several times with ultrapure water, completely remove the exposed residue, and then heat.
- a portion not covered with the resist is selectively etched by a dry etching method to produce a fine pattern on the wafer.
- a film-formed substrate having a convex shape or a concave shape on the substrate surface can be obtained.
- the concave shape on the deposition substrate can be freely changed by changing the pattern size of the reticle and exposure / etching conditions.
- the pellicle film having a convex structure on the film can be produced by applying a pellicle film material to a predetermined film thickness on the concave-shaped film formation substrate.
- the pellicle film For the production of the pellicle film, it is preferable to use a polymer solution in which the pellicle film material is dissolved in an organic solvent.
- the solvent those which have very little volatilization at ambient temperature and whose boiling point is not too high are preferable. Considering the above, it is desirable that the solvent has a boiling point of 100 to 200 ° C.
- solvents examples include aliphatic hydrocarbon compounds, aromatic compounds, halogenated hydrocarbons such as chlorinated hydrocarbons, ester compounds, and ketone compounds.
- organic solvents such as saturated aliphatic hydrocarbon compounds such as alicyclic hydrocarbons, aromatic compounds, and halogenated hydrocarbons can be suitably used for cycloolefin resins, and chlorine for cellulose derivatives.
- Soluble in single or mixed organic solvents such as hydrocarbons, ketones, esters, alkoxy alcohols, benzene, alcohols. Examples of these organic solvents include organic solvents such as chlorinated hydrocarbons, ester compounds, and ketone compounds.
- the chlorinated hydrocarbon methylene chloride, ethylene chloride, propylene chloride and the like are preferably used, and as the ketone compound organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferably used.
- the ester compound organic solvent acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.) and lactate esters (ethyl lactate, butyl lactate, etc.) are preferably used.
- benzene, ethanol, methanol, cellosolve acetate, carbitol and the like can be used as a single or mixed solvent.
- the polymer solution in which the pellicle film material is dissolved preferably has an absorbance of 0.05 or less in order to increase the light transmittance of the pellicle film and reduce foreign substances in the pellicle film.
- the pellicle film formation method and the convex structure production method are not particularly limited, such as spin coating method, roll coating method, knife coating method, casting method, etc., but from the viewpoint of uniformity and management of foreign matter, spin coating method Is preferred.
- spin coating method Is preferred.
- the film forming method by the spin coat method will be described.
- the film thickness and flatness of the pellicle film are mainly determined by the liquid temperature of the polymer solution, the ambient temperature / humidity, and the number of rotations of the film formation substrate.
- the temperature of the polymer solution is preferably about the same as the ambient temperature (10 to 30 ° C.), and the temperature of the film formation base is also preferably about the same as the ambient temperature. It is preferable that the liquid temperature, the ambient temperature, and the temperature of the film formation base are about the same because unevenness in film thickness can be suppressed.
- the humidity is preferably 30 to 60%. After a suitable amount of polymer solution is dropped on the film formation substrate, the film formation substrate is rotated at a rotational speed of 50 to 5000 rotations to form a film.
- the thickness of the pellicle film is preferably about 0.2 ⁇ m or more and 10 ⁇ m or less. In the pellicle film according to the present invention, it is preferably 0.3 ⁇ m or more and 8 ⁇ m or less in view of the strength of the pellicle film and the ease of forming a uniform film.
- the film thickness refers to the distance from the apex of the convex structure to the surface having no convex structure, and the convex structure is provided on both sides of the pellicle film. The distance from the apex of the convex structure on one surface to the apex of the convex structure on the other surface is the shortest distance.
- the film formation substrate is placed on a hot plate and dried to evaporate the solvent. After the film is dried, the film is peeled off from the substrate. At this time, since stress is applied to the film, the film material preferably has extensibility. When the film is peeled off from the substrate, the releasability is important. In order to facilitate film formation and easy separation after film formation, it is necessary to optimize the contact angle between the film material and the substrate. Silane coupling is known as a method for controlling the contact angle of a substrate. In order to couple a substrate made of an inorganic material, it is preferable that silane having an ether bond at the terminal is brought into contact with the substrate surface for reaction.
- the other end group is a group having low affinity with the membrane material, so that the releasability is improved.
- Fluorine is highly effective as a mold release agent, and it is particularly desirable to use fluorine as a terminal group in order to achieve high release properties.
- the material of the convex structure and the pellicle film material do not have to be the same. However, if the material of the convex structure and the pellicle film material are the same, the convex structure and the pellicle film material can be manufactured in one manufacturing process. preferable. In the case where the convex structure material and the pellicle film material are different from each other, the convex structure material may be applied to the deposition substrate, semi-dried or dried, and then the pellicle film material may be stacked.
- a pellicle film having a convex structure can be manufactured by pressing a pellicle film material having fluidity to the substrate and transferring the concave shape of the substrate to the resin. It is.
- the pellicle film material used at that time is preferably in a state where the resin is made to have fluidity by containing 0 to 30 wt% of a solvent. Then, by removing the film from the substrate, the concave shape of the substrate can be transferred to the film.
- a film material that is extensible as a main component
- materials that satisfy these conditions include amorphous fluororesins, and in particular, parts such as CYTOP (trade name) manufactured by Asahi Glass Co., Ltd.
- CYTOP trade name
- a fluororesin having a fluoroalkyl ether ring structure is preferred.
- Example 1 A photoresist (photosensitive material) was applied on a synthetic quartz glass having a chromium thin film layer, and after pre-baking, a fine pattern was drawn on the photoresist in an area of 40 mm ⁇ 80 mm using an electron beam exposure apparatus.
- the drawing shape inside the 40 mm ⁇ 80 mm region is 300 ⁇ m ⁇ 100 ⁇ m as one element, and the inside of the 40 mm ⁇ 80 mm region is filled and drawn without overlapping between adjacent elements.
- the chromium layer portion exposed from the resist pattern was etched, and the resist pattern was transferred to the chromium layer. Finally, the resist residue was washed to produce a reticle.
- a photoresist was uniformly applied on a silicon substrate (12 inches, 300 mm ⁇ ) with a spin coater and then pre-baked to solidify the photoresist.
- stepper which is one of the semiconductor element manufacturing apparatuses
- the fine pattern of the previously produced reticle is reduced to 1 ⁇ 4 by the reduction projection lens, and the wafer is coated with a resist.
- the projection exposure was carried out while moving. Thereafter, the resist was immersed in an organic alkali developer to remove the exposed resist. After rinsing several times with ultrapure water, the exposed residue was completely removed and then heated.
- the portion not covered with the resist was selectively etched by a dry etching method to produce a fine pattern on the wafer.
- CYTOP CTX-809SP2 (trade name, produced by Asahi Glass Co., Ltd., yield strain of about 5%, tensile elongation of about 175%), which is a solution containing an amorphous fluororesin having a perfluoroalkyl ether ring structure as a film material, is added. Dilution adjustment was performed with fluorotributylamine (Fluorinert FC-43, trade name, manufactured by Sumitomo 3M Limited).
- the concentration of the amorphous fluororesin having a perfluoroalkyl ether ring structure contained in the polymer solution was 3% by mass.
- the prepared polymer solution was dropped on a 30 cc film formation substrate, and then spin-coated on a spin coater under conditions of a rotation speed of 300 rpm and a rotation time of 50 seconds.
- the film formation substrate was dried on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each, and the dried film was peeled off from the film formation substrate to obtain an uneven structure layer (self-supporting film) having an area of 706.5 cm 2 . .
- the resulting uneven structure layer had an average thickness of 0.7 ⁇ m, and the uneven structure layer had an average thickness variation of 10 nm.
- the center part of the finished concavo-convex structure layer was cut out with a square of 5 cm ⁇ 5 cm, and the thickness average of the cut-out concavo-convex structure layer and the average thickness variation of the concavo-convex structure layer were measured.
- the thickness average of the concavo-convex structure layer was 0.7 ⁇ m.
- the average thickness variation of the structural layer was 5 nm.
- AFM a periodic concavo-convex shape having a height of 180 nm and a period length of 150 nm was formed.
- the produced concavo-convex structure layer had a yield strain of 5% and a tensile elongation of 175%.
- the concavo-convex structure layer was cut into 5 cm ⁇ 5 cm square.
- a transmission spectral film thickness meter (Otsuka Electronics Co., Ltd., FE1300) is formed at the center of each square divided into 25 equal parts by drawing a straight line so that an arbitrary side of the cut-out square and a side perpendicular to the one side are equally divided into 5 parts. ). Measurements were performed using wavelengths of 248 nm and 365 nm. When the transmittance at a wavelength of 248 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 1%. Further, when the transmittance at a wavelength of 365 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 0.5%.
- Example 2 A polymer solution was prepared by dissolving cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Company, yield strain about 4%, tensile elongation about 15%) in ethyl lactate.
- CAP 480-20 cellulose acetate propionate
- the concentration of cellulose acetate propionate contained in the polymer solution was 8% by mass.
- silane coupling was performed on the surface of the film formation substrate prepared in Example 1, the prepared polymer solution was dropped onto the 30 cc film formation substrate and rotated on a spin coater under conditions of a rotation speed of 300 rpm and a rotation time of 30 seconds. Applied.
- the film formation substrate was dried on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each, and the dried film was peeled off from the film formation substrate to obtain an uneven structure layer (self-supporting film) having an area of 706.5 cm 2 . .
- the resulting uneven structure layer had an average thickness of 1.5 ⁇ m, and the uneven structure layer had an average thickness variation of 61 nm.
- the center part of the finished concavo-convex structure layer was cut out with a 5 cm ⁇ 5 cm square, and the thickness average of the cut-out concavo-convex structure layer and the average thickness variation of the concavo-convex structure layer were measured.
- the average thickness variation of the structural layer was 53 nm.
- the concavo-convex structure layer was cut into 5 cm ⁇ 5 cm square.
- a transmission spectral film thickness meter (Otsuka Electronics Co., Ltd., FE1300) is formed at the center of each square divided into 25 equal parts by drawing a straight line so that an arbitrary side of the cut-out square and a side perpendicular to the one side are equally divided into 5 parts. ). Measurements were performed using wavelengths of 248 nm and 365 nm. When the transmittance at a wavelength of 248 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 3%. Further, when the transmittance at a wavelength of 365 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 5%.
- Example 3 Zeonor 1060R (trade name, produced by Nippon Zeon Co., Ltd., yield strain: about 4%, tensile elongation: about 60%), which is a solution containing cycloolefin resin as a membrane material, is diluted with limonene (Wako Pure Chemical Industries, Ltd.) Thus, a polymer solution was prepared.
- the concentration of the cycloolefin resin contained in the polymer solution was 8% by mass.
- the prepared polymer solution is dropped on the film formation substrate, and spin-coated on a spin coater under the conditions of a rotation speed of 300 rpm and a rotation time of 30 seconds. did.
- the film formation substrate was dried on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each, and the dried film was peeled off from the film formation substrate to obtain an uneven structure layer (self-supporting film) having an area of 706.5 cm 2 . .
- the resulting uneven structure layer had an average thickness of 3.0 ⁇ m, and the uneven structure layer had an average thickness variation of 111 nm.
- the center part of the finished concavo-convex structure layer was cut out with a 5 cm ⁇ 5 cm square, and the thickness average of the cut-out concavo-convex structure layer and the average thickness variation of the concavo-convex structure layer were measured.
- the average thickness variation of the structural layer was 103 nm.
- AFM a periodic concavo-convex shape having a height of 180 nm and a period length of 150 nm was formed.
- the produced concavo-convex structure layer had a yield strain of 4% and a tensile elongation of 60%.
- the concavo-convex structure layer was cut into 5 cm ⁇ 5 cm square.
- a transmission spectral film thickness meter (Otsuka Electronics Co., Ltd., FE1300) is formed at the center of each square divided into 25 equal parts by drawing a straight line so that an arbitrary side of the cut-out square and a side perpendicular to the one side are equally divided into 5 parts. ). Measurements were performed using wavelengths of 248 nm and 365 nm. When the transmittance at a wavelength of 248 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 7%. Further, when the transmittance at a wavelength of 365 nm at the 25 points was measured, the difference between the point with the highest transmittance and the point with the lowest transmittance was 4%.
- a polymer solution was prepared by dissolving polymethyl methacrylate (Mitsubishi Rayon Co., Ltd., no yield strain, tensile elongation of about 6%) in a toluene solution. At this time, the concentration of polymethyl methacrylate contained in the polymer solution was 6% by mass.
- the prepared polymer solution was dropped onto the 30 cc film formation substrate and rotated on a spin coater under conditions of a rotation speed of 300 rpm and a rotation time of 50 seconds. Applied.
- the film formation substrate was dried on a hot plate at 80 ° C. and 180 ° C. for 5 minutes each, and when the dried film was peeled off from the film formation substrate, the film was broken.
- Photoresist (photosensitive material) is coated on a synthetic quartz glass having a chromium thin film layer, and after pre-baking, a fine pattern is applied to the resist in an area of 40 mm x 80 mm using an electron beam exposure apparatus. Drawn. The drawing shape inside the 40 mm ⁇ 80 mm region is 300 ⁇ m ⁇ 100 ⁇ m as one element, and the inside of the 40 mm ⁇ 80 mm region is filled and drawn without overlapping between adjacent elements. After the development process, the chromium layer portion exposed from the resist pattern was etched, and the resist pattern was transferred to the chromium layer. Finally, the resist residue was washed to produce a reticle.
- a resist was uniformly applied on a silicon substrate (12 inches, 300 mm ⁇ ) with a spin coater and then pre-baked to solidify the resist.
- stepper which is one of the semiconductor element manufacturing apparatuses
- the fine pattern of the previously produced reticle is reduced to 1 ⁇ 4 by the reduction projection lens, and the wafer is coated with a resist.
- the projection exposure was carried out while moving. Thereafter, the resist was immersed in an organic alkali developer to remove the exposed resist. After rinsing several times with ultrapure water, the exposed residue was completely removed and then heated.
- the portion not covered with the resist was selectively etched by a dry etching method to produce a fine pattern on the wafer.
- Cytop CTX-809SP2 which is a solution containing an amorphous fluororesin having a perfluoroalkyl ether ring structure (Asahi Glass Co., Ltd., trade name) diluted with perfluorotributylamine (Fluorinert FC-43, Sumitomo 3M Co., Ltd.) at 2% was added dropwise and spin-coated on a spin coater at 300 rpm. , And dried on a hot plate at 80 ° C. and 180 ° C. for 5 minutes to obtain a concavo-convex structure layer (self-supporting film) having a thickness of 3.1 ⁇ m.
- This concavo-convex structure layer (self-supporting film) is spread and applied to an aluminum frame (outside, length 149 mm ⁇ width 122 mm ⁇ height 5.5 mm, frame width 2 mm) with an adhesive applied to the upper edge surface (the other end surface).
- the unnecessary portion of the concavo-convex structure layer (self-supporting film) protruding from the frame body was cut and removed.
- AFM a convex structure having a random period with a height of 180 nm and an interval of 0.9 ⁇ m to 1.1 ⁇ m was produced.
- the concavo-convex structure layer (self-supporting film) was allowed to stand for 10 days under the condition of cleanliness class 10000, and waited for foreign matter to adhere to the concavo-convex structure layer (self-supporting film). After leaving the concavo-convex structure layer (self-supporting film) for 10 days, the surface of the concavo-convex structure layer (self-supporting film) was observed with a condensing lamp to mark 20 foreign matters having a size in the range of 1 ⁇ m to 10 ⁇ m.
- Example 5 A concavo-convex structure layer (self-supporting film) was produced by the same production method as in Example 1 except that the periodic interval of the concave shape on the silicon wafer was set to a constant period of 1.0 ⁇ m. When the resulting concavo-convex structure layer (free-standing film) was observed, a convex structure having a constant period of 180 nm in height and 1.0 ⁇ m in period interval was produced.
- the concavo-convex structure layer (self-supporting film) was allowed to stand for 10 days under the condition of cleanliness class 10000, and waited for foreign matter to adhere to the concavo-convex structure layer (self-supporting film). After leaving the concavo-convex structure layer (self-supporting film) for 10 days, the surface of the concavo-convex structure layer (self-supporting film) was observed with a condensing lamp to mark 20 points of foreign matter having a size in the range of 1 ⁇ m to 10 ⁇ m. .
- Example 6 A concavo-convex structure layer (self-supporting film) was produced by the same production method as in Example 1 except that the period interval of the concave shape on the silicon wafer was set to a constant period of 150 nm. When the resulting concavo-convex structure layer (free-standing film) was observed, a convex structure having a constant period of 180 nm in height and 150 nm in period interval was produced.
- the concavo-convex structure layer (self-supporting film) was allowed to stand for 10 days under the condition of cleanliness class 10000, and waited for foreign matter to adhere to the concavo-convex structure layer (self-supporting film). After leaving the concavo-convex structure layer (self-supporting film) for 10 days, the surface of the concavo-convex structure layer (self-supporting film) was observed with a condensing lamp to mark 20 points of foreign matter having a size in the range of 1 ⁇ m to 10 ⁇ m. .
- Example 3 A concavo-convex structure layer (self-supporting film) was produced by the same production method as in Example 4 except that a silicon wafer having a smooth surface was used.
- Cytop CTX-809SP2 (trade name, manufactured by Asahi Glass Co., Ltd.), which is a solution containing an amorphous fluororesin on the obtained film, is perfluorotributylamine (trade name, manufactured by Fluorinert FC-43 Sumitomo 3M Co., Ltd.).
- a solution diluted to 4% was dropped, spin-coated on a spin coater at 300 rpm, and then dried at 80 ° C. and 180 ° C. to obtain an uneven structure layer (self-supporting film) with a reflection suppressing layer having a thickness of 800 ⁇ m.
- the concavo-convex structure layer (self-supporting film) was allowed to stand for 10 days under the condition of cleanliness class 10000, and waited for foreign matter to adhere to the concavo-convex structure layer (self-supporting film). After leaving the concavo-convex structure layer (self-supporting film) for 10 days, the surface of the concavo-convex structure layer (self-supporting film) was observed with a condensing lamp to mark 20 points of foreign matter having a size in the range of 1 ⁇ m to 10 ⁇ m. .
- Example 7 Manufacture of synthetic quartz glass substrate with concave shape Apply photoresist (photosensitive material) on synthetic quartz glass with chrome thin film layer, pre-bake, and finely squeeze resist in the area of 800mm ⁇ 920mm using electron beam exposure equipment I drew a pattern.
- the drawing shape inside the 800 mm ⁇ 920 mm region was a line and space shape of 150 nm ⁇ 150 nm at a full pitch, and the inside of the 800 mm ⁇ 920 mm region was filled and drawn without overlapping between adjacent elements.
- the chromium layer portion exposed from the resist pattern was etched, and the resist pattern was transferred to the chromium layer. Finally, the resist residue was washed to produce a reticle.
- a resist was uniformly applied on a synthetic quartz glass substrate (800 mm ⁇ 920 mm) with a spin coater and then pre-baked to solidify the resist.
- a reduction projection type exposure apparatus stepper
- the fine pattern of the previously produced reticle is reduced to 1 ⁇ 4 by a reduction projection lens, and a synthetic quartz coated with a resist is applied.
- Projection exposure was performed while moving on a glass substrate.
- the resist was immersed in an organic alkali developer to remove the exposed resist. After rinsing several times with ultrapure water, the exposed residue was completely removed and then heated.
- the portion not covered with the resist was selectively etched by a dry etching method to produce a fine pattern on the substrate.
- silane coupling is performed on the surface of the synthetic quartz glass substrate to improve the release property of the pellicle film, and then cellulose acetate propionate (CAP 480-20, manufactured by Eastman Chemical Co., yield strain about 4%, tensile)
- CAP 480-20 manufactured by Eastman Chemical Co., yield strain about 4%, tensile
- a polymer solution was prepared by dissolving about 15% elongation) in ethyl lactate.
- the concentration of cellulose acetate propionate contained in the polymer solution was 8% by mass.
- the prepared polymer solution was dropped onto the film formation substrate, spin-coated on a spin coater under the conditions of a rotation speed of 250 rpm and a rotation time of 200 seconds, and dried. .
- a fluorine-based polymer solution is applied onto the film by spin coating and dried to provide an antireflection layer, and the concavo-convex structure layer (self-supporting film) having the antireflection layer formed on the concavo-convex structure film is peeled off from the substrate and thickened.
- An uneven structure layer (self-supporting film) having a thickness of 4.0 ⁇ m was obtained.
- the concavo-convex structure layer (self-supporting film) was allowed to stand for 10 days under the condition of cleanliness class 10000, and waited for foreign matter to adhere to the concavo-convex structure layer (self-supporting film). After leaving the concavo-convex structure layer (self-supporting film) for 10 days, the surface of the concavo-convex structure layer (self-supporting film) was observed with a condensing lamp to mark 20 foreign matters having a size in the range of 1 ⁇ m to 10 ⁇ m.
- the transmittance was measured in the same manner as in Example 1.
- the wavelength was 290 nm to 700 nm broadband, and the point with the lowest transmittance was 92%.
- the average transmittance was 96%, and it was found that the concavo-convex structure film was effective even at a broadband wavelength.
- the self-supporting film of the present invention is a self-supporting film having excellent shape followability, such as a touch panel, a liquid crystal display panel, a plasma display, an organic EL display, a projection optical system such as a projector, an observation optical system such as an optical lens, a camera, etc. It can be suitably used for optical elements such as an imaging optical system, a polarizing beam splitter, the tip of a light emitting part of a light emitting diode, and the surface of a solar cell panel.
- the pellicle of the present invention is a pellicle film that hardly adheres to foreign matter and can be easily removed by air blow even if foreign matter is attached, so that it can be used repeatedly and is economically superior. .
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Abstract
Description
まず、本発明の第1の実施形態について説明する。図1は、本実施態様に係る自立膜の一例の部分拡大断面図である。図1において自立膜4は、一方の表面に周期凹凸形状5が形成された凹凸構造層1を備え、凹凸構造層1の他方の表面に、薄膜層2を備える。
次に、本発明の第2の実施形態について説明する。
(1)(自立膜の)厚み平均(μm)
図3に示すように、測定対象の自立膜4を面内で面積が最大となるように長方形で切り出した後、切り出した長方形の長辺と短辺をそれぞれ5等分するように直線を引いて25等分割し、各長方形の中心点を位置決めした。当該中心点の厚みを、透過分光膜厚計(大塚電子株式会社、FE1300)を用いて測定した(測定波長248nm)。測定された25点の測定値の平均値を厚み平均とした。
上述したように25等分割された試験片の各々について、AFM(Atomic Force Microscope:原子間力顕微鏡)を用いて凹凸面の表面形状を測定した。各試験片について、凹部底点間の、凹凸構造層の層厚方向に沿った距離の平均値を算出した。さらに、25個の試験片について算出されたそれら平均値の平均値を、厚みばらつき平均とした。
JIS K 7113に準拠し、引張速度1mm/minの条件で測定した。測定には島津製作所製 AGS-50Gを使用した。
(4)凹凸構造層の降伏歪み(%)、引張伸度(%)
JIS K 7127に準拠し、引張速度1mm/minの条件で測定した。測定には島津製作所製 AGS-50Gを使用した。
クロム薄膜層を有する合成石英ガラス上にフォトレジスト(感光性物質)を塗布し、プレベーク後、電子ビーム露光装置を用いて40mm×80mm領域でフォトレジストに微細パタンを描画した。40mm×80mm領域内部の描画形状は、300μm×100μmを1つの素子とし、隣り合う素子間は重なり合うことなく40mm×80mm領域内部を充填的に配列描画した。現像処理後、レジストのパタンから露出しているクロム層部分をエッチングし、レジストパタンをクロム層に転写した。最後にレジスト残渣を洗浄しレティクルを作製した。
セルロースアセテートプロピオネート(CAP 480-20、Eastman Chemical Company製、降伏歪み約4%、引張伸度約15%)を乳酸エチルに溶かしたポリマー溶液を作製した。
シクロオレフィン系樹脂を膜材として含む溶液であるZeonor1060R(日本ゼオン(株)製商品名、降伏歪み約4%、引張伸度約60%)をリモネン(和光純薬工業(株)製)で希釈し、ポリマー溶液を作製した。
ポリメタクリル酸メチル(三菱レイヨン(株)製、降伏歪み無し、引張伸度約6%)をトルエン溶液に溶かしたポリマー溶液を作製した。この時、ポリマー溶液中に含まれるポリメタクリル酸メチルの濃度は6質量%であった。
ポリマー溶液の成膜基板上に滴下量とスピンコーターの回転数を調節して、5cm×5cm角における凹凸構造層の厚み平均を5.0μmとした以外は実施例1と同様の作製方法で凹凸構造層を作製した。ポリマー溶液の滴下量は30cc、スピンコーターの回転数は500rpm、回転時間は30秒とした。
・凹形状を有するシリコンウエハの作製
クロム薄膜層を有する合成石英ガラス上にフォトレジスト(感光性物質)を塗布し、プレベーク後、電子ビーム露光装置を用いて40mm×80mm領域でレジストに微細パタンを描画した。40mm×80mm領域内部の描画形状は、300μm×100μmを1つの素子とし、隣り合う素子間は重なり合うことなく40mm×80mm領域内部を充填的に配列描画した。現像処理後、レジストのパタンから露出しているクロム層部分をエッチングし、レジストパタンをクロム層に転写した。最後にレジスト残渣を洗浄しレティクルを作製した。
シリコンウエハ上の凹形状の周期間隔を1.0μmの一定周期にした以外は実施例1と同様の製造方法で凹凸構造層(自立膜)を作製した。出来上がった凹凸構造層(自立膜)上を観察したところ、高さ180nm、周期間隔が1.0μmの一定周期を持つ凸構造が作製されていた。
シリコンウエハ上の凹形状の周期間隔を150nmの一定周期にした以外は実施例1と同様の製造方法で凹凸構造層(自立膜)を作製した。出来上がった凹凸構造層(自立膜)上を観察したところ、高さ180nm、周期間隔が150nmの一定周期を持つ凸構造が作製されていた。
表面が平滑なシリコンウエハを用いた以外は実施例4と同様の製造方法で凹凸構造層(自立膜)を作製した。次に得られた膜上にアモルファスフッ素樹脂を含む溶液であるサイトップ CTX-809SP2(旭硝子(株)製商品名)をパーフルオロトリブチルアミン(フロリナートFC-43 住友スリーエム(株)製商品名)で4%に希釈したものを滴下し、スピンコーター上で、300rpmで回転塗布した後80℃、180℃で乾燥させ、厚み800μmの反射抑制層付き凹凸構造層(自立膜)を得た。
・凹形状を有する合成石英ガラス基板の作製
クロム薄膜層を有する合成石英ガラス上にフォトレジスト(感光性物質)を塗布し、プレベーク後、電子ビーム露光装置を用いて800mm×920mm領域でレジストに微細パタンを描画した。800mm×920mm領域内部の描画形状は、フルピッチで150nm×150nmのライン&スペースの形状とし、隣り合う素子間は重なり合うことなく800mm×920mm領域内部を充填的に配列描画した。現像処理後、レジストのパタンから露出しているクロム層部分をエッチングし、レジストパタンをクロム層に転写した。最後にレジスト残渣を洗浄しレティクルを作製した。
2 薄膜層
3 コーティング層
4 自立膜
5 周期凹凸形状
6 凹凸構造層裏面
7 自立膜表面
8 自立膜裏面
9 抜き取り線
10 頂点平均高さ
11 凹凸構造層の厚み
12 収差による位置ずれ
13 凹部底点
14 凹部底点から凹凸構造層裏面までの距離(最大)
15 凹部底点から凹凸構造層裏面までの距離(最小)
16 凹凸構造層の厚みばらつき
17 周期間隔
20 ペリクル
21 ペリクル膜
22 凸構造
23 凸構造の頂点
24 凸構造の底点
25 凸構造の高さ
26 凸構造の間隔
27 枠体
28 粘着材
Claims (18)
- 少なくとも片面に周期的な凹凸形状が形成された凹凸構造層を有することを特徴とする自立膜。
- 厚み平均が0.2μm以上20.0μm以下であることを特徴とする請求項1に記載の自立膜。
- 前記凹凸構造層の降伏歪みが1%以上であり、且つ、引張伸度が10%以上であることを特徴とする請求項1又は2に記載の自立膜。
- 前記凹凸構造層の厚みばらつき平均が100nm以下であることを特徴とする請求項1~3の何れか一項に記載の自立膜。
- 前記凹凸構造層の主成分にパーフルオロアルキルエーテル環構造を有するフッ素系樹脂、セルロース系誘導体、及びシクロオレフィン系樹脂からなる群から選択される少なくとも1つの樹脂を用いることを特徴とする請求項1~4の何れか一項に記載の自立膜。
- 前記凹凸形状における凸部が一定の周期間隔を有して配置されていることを特徴とする請求項1~5の何れか一項に記載の自立膜。
- 前記凹凸形状における凸部の周期間隔が1.0μm以下であることを特徴とする請求項1~6の何れか一項に記載の自立膜。
- 前記凹凸形状における凸部の高さが前記凹凸形状の周期間隔の0.5倍以上2.0倍以下であることを特徴とする請求項1~7の何れか一項に記載の自立膜。
- 前記凹凸形状における凸部の形状が多角錐形状、円錐形状、截頭多角錐形状又は截頭円錐形状であることを特徴とする請求項1~8の何れか一項に記載の自立膜。
- 請求項1~9の何れか一項に記載の自立膜と、前記自立膜の裏面に設けられて前記自立膜に対し剥離可能な剥離体と、を含む自立構造体。
- 前記凹凸構造層と前記剥離体が接していることを特徴とする請求項10に記載の自立構造体。
- 前記剥離体の前記凹凸構造層に対向する表面が、略球面形状を有する請求項10又は11に記載の自立構造体。
- 請求項1~9の何れか一項に記載の自立膜と、前記自立膜の裏面に設けられた粘着剤層又は接着剤層と、を含む自立構造体。
- 前記凹凸構造層と前記粘着剤層又は接着剤層が接していることを特徴とする請求項13に記載の自立構造体。
- 請求項1~9の何れか一項に記載の自立膜の製造方法であって、
降伏歪みが1%以上であり、且つ、引張伸度が10%以上である樹脂組成物を有機溶媒に溶解させてなるポリマー溶液を、表面に周期的な凹凸形状を有する成膜基板上に塗布した後、乾燥させて剥離し、厚み平均が0.2μm以上20.0μm以下である自立膜を得ることを特徴とする、自立膜の製造方法。 - 請求項1~9の何れか一項に記載の自立膜の製造方法であって、
基板表面に凹形状を有する成膜基板上に、自立膜材料を所定の膜厚になるように塗布して自立膜を成形した後、前記成膜基板より該自立膜を剥離することを特徴とする自立膜の製造方法。 - 前記基板表面上にシランカップリングを施すことを特徴とする請求項16に記載の自立膜の製造方法。
- 枠体と、該枠体の一端面に塗着した粘着剤と、該枠体の他端面に請求項1~9の何れか一項に記載された自立膜が接着されたペリクルであって、
前記自立膜の内面側及び/又は外面側に前記凹凸構造層を有することを特徴とするペリクル。
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EP11768899.4A EP2560048A4 (en) | 2010-04-13 | 2011-04-13 | Self-supporting film, self-supporting structure, method for manufacturing self-supporting film, and pellicle |
US13/634,337 US20130004711A1 (en) | 2010-04-13 | 2011-04-13 | Self-supporting film, self-supporting structure, method for manufacturing self-supporting film, and pellicle |
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CN201180018926.8A CN102859397B (zh) | 2010-04-13 | 2011-04-13 | 自支撑膜、自支撑结构体、自支撑膜的制造方法及表膜 |
US15/218,837 US10578962B2 (en) | 2010-04-13 | 2016-07-25 | Self-supporting film, self-supporting structure, method for manufacturing self-supporting film, and pellicle |
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US15/218,837 Division US10578962B2 (en) | 2010-04-13 | 2016-07-25 | Self-supporting film, self-supporting structure, method for manufacturing self-supporting film, and pellicle |
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JP2016143791A (ja) * | 2015-02-03 | 2016-08-08 | 旭硝子株式会社 | マスクブランク用ガラス基板 |
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JP2013257373A (ja) * | 2012-06-11 | 2013-12-26 | Asahi Kasei Corp | 防塵膜の製造方法 |
JP2014010217A (ja) * | 2012-06-28 | 2014-01-20 | Dainippon Printing Co Ltd | 反射防止積層体 |
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JP2020160345A (ja) * | 2019-03-27 | 2020-10-01 | 三井化学株式会社 | ペリクル自立膜の製造方法、ペリクルの製造方法、および半導体装置の製造方法 |
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KR20150008917A (ko) | 2015-01-23 |
US20130004711A1 (en) | 2013-01-03 |
KR101552002B1 (ko) | 2015-09-09 |
TW201210828A (en) | 2012-03-16 |
EP2560048A1 (en) | 2013-02-20 |
CN104597531B (zh) | 2017-04-12 |
CN102859397A (zh) | 2013-01-02 |
EP2560048A4 (en) | 2017-08-23 |
KR20120139797A (ko) | 2012-12-27 |
JPWO2011129378A1 (ja) | 2013-07-18 |
JP2015110806A (ja) | 2015-06-18 |
TWI636080B (zh) | 2018-09-21 |
JP5827217B2 (ja) | 2015-12-02 |
US10578962B2 (en) | 2020-03-03 |
CN102859397B (zh) | 2015-11-25 |
JP6009018B2 (ja) | 2016-10-19 |
TW201716479A (zh) | 2017-05-16 |
TWI579145B (zh) | 2017-04-21 |
US20160334699A1 (en) | 2016-11-17 |
KR101578633B1 (ko) | 2015-12-17 |
CN104597531A (zh) | 2015-05-06 |
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