CN102736400B - Dustproof pellicle film, manufacturing method thereof, and dustproof pellicle component with pellicle film attached - Google Patents

Dustproof pellicle film, manufacturing method thereof, and dustproof pellicle component with pellicle film attached Download PDF

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Publication number
CN102736400B
CN102736400B CN201210091249.9A CN201210091249A CN102736400B CN 102736400 B CN102736400 B CN 102736400B CN 201210091249 A CN201210091249 A CN 201210091249A CN 102736400 B CN102736400 B CN 102736400B
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Prior art keywords
dustproof film
dustproof
absorbing layer
film
layer
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Expired - Fee Related
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CN102736400A (en
Inventor
関原一敏
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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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
    • 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
    • G03F1/22—Masks or mask blanks for imaging by radiation of 100nm or shorter wavelength, e.g. X-ray masks, extreme ultraviolet [EUV] masks; Preparation thereof
    • 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
    • G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
    • 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
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/708—Construction of apparatus, e.g. environment aspects, hygiene aspects or materials
    • G03F7/70908—Hygiene, e.g. preventing apparatus pollution, mitigating effect of pollution or removing pollutants from apparatus
    • G03F7/70916—Pollution mitigation, i.e. mitigating effect of contamination or debris, e.g. foil traps

Abstract

The invention provides a dustproof pellicle film suitable for photoetching engineering with irradiation of ultraviolet rays in the wavelength field of 350-450nm comprising i ray, h ray, and g ray, and advantaged by cheapness and good light resistance. The pellicle film is the dustproof pellicle film for a dustproof pellicle film component used in the photoetching engineering with irradiation of ultraviolet rays in the wavelength field of 350-450nm. The dustproof pellicle film is characterized in that, for the surface on at least an exposure light source side of a raw material dustproof pellicle film, the average transmittance of the ultraviolet rays in the wavelength field of 350-450nm is more than 90%, and an ultraviolet ray absorption layer is provided, and the average transmittance of the ultraviolet rays in the wavelength field of 200-300nm with respect to the ultraviolet ray absorption layer is less than 50%.

Description

Dustproof film, its manufacture method and the dustproof film component of paying with these film subsides
Technical field
The present invention relates to semiconductor device, IC encapsulation, printed base plate, the dustproof film component using as dustproof thing during the manufacture of liquid crystal display or OLED display etc., particularly relate to as exposure light source, use i line (365nm), the dustproof film using in the ultraviolet photoetching engineering that any of h line (405nm) or g line (436nm) or they are combined with each other, its manufacture method and this film is tightened and pasted the dustproof film component of paying.
Background technology
LSI, the semiconductor of super LSI etc., IC packaging body, the circuit substrate of printed base plate etc., in the manufacture of liquid crystal display and OLED display etc., at semiconductor wafer, base plate for packaging or display arrange photoresist with raw sheet surface, then, by the figuratum photomask of tool, to it, irradiate light, develop with pattern-making.Now photomask used or reticle mask are (following; all claim photomask) if any dust, paying; this dust absorbs light; or make bendingof light; so the pattern of transfer printing will be out of shape, and the edge of pattern will be fuzzy, substrate become Bian ?etc.; the size of final products, quality and outward appearance etc. are impaired.
Therefore, these operations are carried out conventionally in dust free room, but even so will make photomask often clean, are also difficult.Therefore, after paying dustproof film component subsides as the thing that prevents dust, photomask surface expose again.At this Games, close, foreign matter just can directly not paid on the surface of photomask, but is paying on dustproof film component, needs only during photoetching like this on the pattern of photomask in focus, and the foreign matter on dustproof film component has just had nothing to do with transfer printing.
Generally, dustproof film component is transparent dustproof film that light is well seen through by aluminium, and the upper surface of the dustproof film component framework that stainless steel and engineering plastics etc. form is pasted and paid, or bonding making.Further; lower end at dustproof film component framework; installation for photomask; setting is by polybutene resin; polyvinyl acetate base ester resin, acryl resin, the adhesive coating that thermosol sticker or silicone resin etc. form; and according to necessity, what also will arrange to protect this adhesive coating is the release layer (stripping film) of object.
In addition, at dustproof film component, pasted and paid in the state of photomask, in order to make space and outside that dustproof film component inside surrounds there is no draught head, the aperture of air pressure adjustment use is set in a part for dustproof film component framework, in order to prevent bringing foreign matter into by the mobile air of this aperture, filtrator is also set sometimes.
As dustproof film, select the optimum material corresponding with the light source of the use that exposes.For example, ArF laser (193nm), or the Games that KrF laser (248nm) is used closes, and to the light of this wavelength, has sufficient transmitance and sunproof fluorine-type resin to be used (patent documentation 1).
In addition, using i line (365nm), the Games that h line (405nm) and g line (436nm) expose closes, can use nitrocellulose, ethyl cellulose, the cellulosic resin of cellulose propionate etc., polyvinyl acetal resin and cycloolefin resin etc. (patent documentation 2,3 and 4).In these light source, generally use high-pressure mercury-vapor lamp or extra-high-pressure mercury vapour lamp.
High-pressure mercury-vapor lamp and extra-high-pressure mercury vapour lamp, have the characteristic between 254 to 577nm with the wide wavelength at several peaks.Among them, the luminous quantity from photoetching and the viewpoint of luminous energy, the highest Strong degree be i line (365nm), then the light for g line (436nm) and h line (405nm) can be used well, also uses once in a while the light of 313nm.In addition, the Games that the amount that display manufacturing is used etc. is paid attention to especially closes, and does not use the light of specific ripple, but uses for example whole light of 365nm to 436nm.
Above-mentioned fluororesin, does not almost absorb short wavelength, can use short wavelength, and high-octane KrF laser and ArF swash light wavelength, so use the i line lower than their energy, the wavelength of g line etc. is also certainly also completely no problem.But fluororesin has the high shortcoming of cost.Therefore general, the wavelength field at i line to g line, considers all characteristics as dustproof film material, uses cellulosic resin easy to use etc. more.
In addition, the transmittance that also has to improve dustproof film is object, and the situation of the sandwich construction of antireflection film is set on its one or both sides.Particularly, it is all the more so that the many cellulose-based resin of the high reflection of refractive index etc. is used as the occasion of antireflection film of fluorine resin.Separately with, also have the inner face at dustproof film that organosilicon adhering agent layer is set, thus the foreign matter that is attached to dustproof film inner side is fixed, prevent that it from falling the situation (patent documentation 5) on photomask.The transmittance of organosiloxane resins, because its photostability is good, the kind even having also has the high transmission rate to the short light of wavelength, so can be stacked for carrying out on dustproof film.
[prior art document]
[patent documentation]
[patent documentation 1] Unexamined Patent 03-39963
[patent documentation 2] Unexamined Patent 01-100549
[patent documentation 3] Unexamined Patent 01-172430
[patent documentation 4] JP 2010-152308
Patent Document 5 Unexamined Patent 5-88359
In recent years, in photoetching engineering, in order with thinner line, circuit being described, and to improve productivity, to require higher exposure Strong degree.Exposure Strong degree uprises, aging being promoted that the ultraviolet ray of dustproof film causes, thus the Minus of generation thickness is few, the step-down of transmitance, the problem of the generation of Hai Si (ヘ イ ズ) etc.Specifically, by the chromium of photomask (Cr) thus layer shading part owing to not irradiated without any variation by ultraviolet ray, but the part (part that pattern is described) that there is no Cr layer, dustproof film surface is directly irradiated by ultraviolet ray, and the film of this part can damage.
As above-mentioned, exposure light source is being used the Games of high-pressure mercury-vapor lamp or extra-high-pressure mercury vapour lamp to close, and in the light that these light sources occur, not only has the i line of exposure use, h line, g line, the in addition light of other wavelength, it is representational can exemplify 254nm, 302nm, the short-wavelength light of 313nm etc.The light of these short wavelengths' light, particularly 254nm, has than the taller energy of bond energy of the molecule of the formation dustproof films such as cellulosic resin, and its key will be cut off.The cut molecule of key is decomposed, gasification, and dustproof film surface is cut gets, and Mo Hou Minus is few.
The Mo Hou Minus of part dustproof film component is few, the optical path length heterogeneity that becomes, on optics, do not make recognize satisfied, the surface out-of-flatness that becomes, light can scattering, transmitance step-down.In addition, film Strong Du Minus is few, and further serious Games closes, and the heterogeneity that the tension force on dustproof film becomes, on dustproof film surface, wrinkle will occur.
Prevent such problem, in the light occurring at exposure light source, by 254nm, 302nm, the obsolete short wavelengths' of patterning such as 313nm light is removed.As its method, for example, can exemplify in the light path from exposure light source to photomask, insert the filtrator of only these short-wavelength lights being removed, or, the reflective mirror that insertion is reflected the light beyond these short wavelength's light etc.In addition, in the side that there is no the pattern plane of photomask, the additional layer with same filter function also can.These filter function, the opposition side at the filtrator of quartz glass etc. by substrate and the autologous pattern plane of photomask, for example, by TiO 2, ZnO 2, CeO 2deng in short wavelength field, have an inorganic material of absorption, by the method for evaporation and sputter etc., just paying and can obtain.But the cost of such processing is not necessarily cheap, and these material to have refractive index high, reflection is large, ding the harm of the Strong degree step-down of the light that the exposure of making used.Therefore, not the correspondence of carrying out in exposure machine and photomask side, but will carry out correspondence in dustproof film component side.
But it is very difficult that above-mentioned inorganic material is paid on dustproof film.Evaporation and sputter while carrying out are necessary dustproof film to take in and be necessary in vacuum chamber, during when Zhe Shi You Yu Minus presses and to atmospheric restoration of old ways, in middle vacuum chamber, the membership that goes out of a large amount of air occurs, and has thus a large amount of foreign matters paying on dustproof film.But dustproof film is different from glass substrate etc., can not clean.Therefore, requiring to have on the dustproof film of high cleanliness has the Games that foreign matter is being paid to close, and can become immediately bad.
Due to above-mentioned reason, up to now, also there is using the dustproof film of cheap cellulosic resin formation, the dustproof film good to the permanance of short wavelength's light.Therefore,, before problem occurs, this method of trading in of dustproof film just has to adopt.
Summary of the invention
Therefore the 1st object of the present invention, be to provide a kind of to using i line, h line, the exposure of g line is suitable, to 254nm, high, the cheap dustproof film of short wavelength ultraviolet patience of 313nm etc.
The 2nd object of the present invention, is to provide in the ultraviolet lithography engineering in a kind of 350 to 450nm wavelength field and is used, the manufacture method of the cheap and dustproof film that permanance is good.
Further the 3rd object of the present invention, is to provide operable, cheap dustproof film component in the ultraviolet photoetching engineering in a kind of 350 to 450nm wavelength field.
Above-mentioned all objects of the present invention are just to provide the dustproof film component dustproof film being used in a kind of ultraviolet photolithography engineering of the wavelength field in use 350 to 450nm, this dustproof film is, raw material dustproof film at least on the surface of exposure light source side, there is UV-absorbing layer, this UV-absorbing layer, the ultraviolet mean transmissivity in the wavelength field to above-mentioned 350 to 450nm is more than 90%, is below 50% to the ultraviolet mean transmissivity in 200 to 300nm wavelength field simultaneously.The dustproof film component that the present invention also provides the manufacture method of this dustproof film and uses this dustproof film.
In the present invention, preferably in above-mentioned UV-absorbing layer upper, further there is antireflection layer.In addition, above-mentioned UV-absorbing layer has silicone resin to be configured to preferably, and the refractive index of UV-absorbing layer be take below 1.50 as preferred.
the effect of invention
Dustproof film of the present invention, although use cheap material as in the past, such as cellulosic resin, polyvinyl acetal resin, cycloolefin resin etc., but to high as the light patience of the composition below the 300nm that composition does not exist in exposure light, compare with dustproof film in the past and improved significantly sunproof good thing.For this reason, can use exposure intensity higher, the raising of exposure quality and amount can be reached.In addition, also can be little to the minimizing of the thickness in using, the problem of wrinkle and fuzzy generation etc. also can prevent, the quality of can long term maintenance exposing.
Accompanying drawing explanation
Fig. 1 is for representing the sectional view of the essential structure of dustproof film component of the present invention;
Fig. 2 is the sectional view with the dustproof film of the present invention of UV-absorbing layer;
Fig. 3 is in UV-absorbing layer, further adds the sectional view of the dustproof film of the present invention of antireflection layer;
Fig. 4 is the approximate three-dimensional map of dustproof film component of the present invention.
[explanation of mark]
11 dustproof film component frameworks
12 adhesive coatings
13 adhesive linkages
14 stripping films
15 have the dustproof film of the present invention of UV-absorbing layer
21 raw material dustproof films
22 UV-absorbing layer
23 antireflection layers
40 dustproof film components of the present invention
41 dustproof film component frameworks
42 ditches
43 fixture caves
44 adhesive coatings
45 adhesive linkages
46 air holes
47 filtrators
48 have the dustproof film of the present invention of UV-absorbing layer
Embodiment
Form the material of the raw material dustproof film of dustproof film of the present invention, can in known material, carry out suitable selection, can exemplify the cellulosic resin of nitrocellulose, ethyl cellulose, cellulose ethanoate, cellulose propionate and acetyl cellulose propionate etc., polyvinyl acetal resin and cycloolefin resin etc., can be used cheap material as in the past.These material, has sufficient patience to be used the light of 350 to 450nm wavelength in patterning, but to as in exposure light not need the patience of the short wavelength below 300nm that composition exists low, aging fast thus.In the present invention, the UV-absorbing layer that the light incident side of dustproof film surface arranges, can prevent that above-mentioned short wavelength's composition from arriving raw material dustproof film, and photostability is significantly improved thus.
Above-mentioned UV-absorbing layer, particularly the ultraviolet mean transmissivity in 350 to 450nm wavelength field is more than 90%, is below 50% to be necessary to the ultraviolet mean transmissivity in 200 to 300nm wavelength field simultaneously.The material of such UV-absorbing layer can suitable selection from known thing, in the present invention, particularly, with UV-absorbing layer, with silicone resin, is configured to preferably.When silicone resin is used as UV-absorbing layer, different from inorganic material, the solution state that can dissolve in solvent carries out coating film forming, closes identically with the Games of the manufacture of common dustproof film, and the manufacture of dustproof film of the present invention is also possible.Thus, just can obtain lacking of foreign matter of the present invention, clean dustproof film.In addition, silicone resin photostability is good, has advantages of that the degree aging due to UVA is few.
In dustproof film of the present invention, outside UV-absorbing layer, take and antireflection layer is further set as preferred.Antireflection layer, considers material, thickness and the position of paying according to the refractive index of the above-mentioned UV-absorbing layer of paying.Antireflection layer, can be used as the dustproof film outermost layer of light incident side, and the outermost layer of exiting side or the outermost layer of its both sides arrange, and according to the combination of refractive index, in the middle of UV-absorbing layer and raw material dustproof film, arranges and also can.In addition, the material of antireflection layer is not limited to a kind, can combine by multiple types, antireflection layer is made as to multi-ply construction also passable.
In addition, in the present invention, the refractive index of above-mentioned UV-absorbing layer is below 1.50, also can, when it has UVA function, allow it have as the function of antireflection layer also passable.
Dustproof film of the present invention, preferably among raw material dustproof film, UV-absorbing layer and the antireflection layer of formation dustproof film of the present invention, the material solution of outermost one is coated with in substrate for film deposition, be dried, after solidifying, on the layer of this dry solidification, according to the order of desirable film structure, repeatedly carrying out the same constituent material to each layer is coated with, is dried and curing engineering, finally, by forming the integral body of the dustproof film of lamination in substrate for film deposition, from substrate for film deposition, peel off.This gimmick, same with the manufacture method of common dustproof film, can obtain paying of foreign matter few, there is the dustproof film of the present invention of UV-absorbing layer.
The exposure light source side of dustproof film is the main reason that raw material dustproof film is aging, because dustproof film of the present invention has the UV-absorbing layer to the UVA in 200 to 300nm wavelength field, so raw material dustproof film is not used the fluorine-type resin of high price, can become the dustproof film that photostability is good yet.Particularly, as above-mentioned, as UV-absorbing layer, use the Games of silicone resin to close, can in solvent, dissolve, carry out UV-absorbing layer coating, with the method for the Games contract sample with common dustproof film manufacture, just can be manufactured dustproof film of the present invention, obtain permanance good, simultaneously lacking of foreign matter, cheaply clean dustproof film.
Fig. 1 is the expression sectional view of the profile of dustproof film component of the present invention.Symbol 15 in figure is dustproof film of the present invention, between adhesive linkage 13, dustproof film component framework 11 is pasted and is paid with suitable tension force.Symbol 12 is on photomask, to carry out the adhesive coating that the subsides of dustproof film component are paid while using, and 14 for protecting before use the stripping film of adhesive coating.
Fig. 2 is the amplification sectional view of the dustproof film A portion in Fig. 1.Symbol 21 is raw material dustproof film, and symbol 22 is UV-absorbing layer.Fig. 3 is identical with Fig. 2, is the amplification sectional view of the dustproof film A portion in Fig. 1, for add the situation of the embodiment of antireflection layer 23 in UV-absorbing layer 22.
Dustproof film component of the present invention, in the ultraviolet all photoetching that utilize 350 to 450nm wavelength field, can be used as dustproof film component and uses, and it uses wavelength, purposes, and size waits system to limit.Dustproof film of the present invention pastes the material of the dustproof film component framework 11 of paying, and can be engineering plastics, iron and steel, stainless steel, aluminium alloy, titanium with and alloy, CFRP etc., carry out suitable selection in the material using at known dustproof film component framework.
The material of the raw material dustproof film 21 that dustproof film 15 of the present invention is used carries out suitable selection from known dustproof film material.Also can use the material to the good high price of the photostability of the light below 350nm such as fluorine-type resin, but in the present invention, the cellulosic resin that uses nitrocellulose, ethyl cellulose, cellulose ethanoate, cellulose propionate and cellulose ethanoate propionic ester etc., the cheap things such as polyvinyl acetal resin and cycloolefin resin.
The material of the UV-absorbing layer 22 that the present invention uses, preferably at the applied state of dustproof film, to the ultraviolet mean transmissivity in 350 to 450nm wavelength field, be more than 90%, to the ultraviolet mean transmissivity in 200 to 300nm wavelength field, be that organic substance below 50% forms simultaneously, particularly under ultraviolet irradiation, it is necessary that material aging and that dust do not occur or not.From this viewpoint, in the present invention, as above-mentioned, preferably use not only transparent highly, transmitance is good, and under short wavelength's ultraviolet ray is irradiated, and photostability is good silicone resin also.In addition, presclerotic silicone resin can be dissolved in toluene, and the organic solvent of dimethylbenzene etc., so be easy to coating film forming.
In above-mentioned patent documentation 5, in order to invest the object of stickability, even if select also there is the silicone resin of high transmittance in short wavelength range, still, transmittance during wavelength below the 350nm that in the present invention, has selected not use in exposure swashs the acute silicone resin declining.In addition, although foreign matter is fixed on dustproof film and can improves adhesive reliability, owing to having from substrate for film deposition, peel off difficulty, the extremely difficult problem of manufacturing, so in the present invention, does not invest dustproof film stickability.The above-mentioned silicone resin that the present invention uses, is preferably used the linear siloxanes resin that imports methyl, phenyl, or, import the organically-modified silica alkane resin of polyethers, epoxy, amine, carboxyl, aralkyl and fluoroalkyl etc. etc.In the present invention, for these, consider from the two sides of the characteristic of optics and the characteristic of machinery, to thering is the thing of desired characteristic, select.In addition, the form as resin, is preferably solid, has desirable film Strong degree and flexibility.In the present invention, do not limit the hardening thing of these silicone resins and rubber, heat hardening type, 2 package curing types and paying add response type that all can.
In the present invention, the configuration to dustproof film 15 of the present invention, make the light of exposure before arriving raw material dustproof film 21, just sees through UV-absorbing layer 22, and the light incident side at light has UV-absorbing layer.But, at the Games holding concurrently as the UV-absorbing layer of antireflection film 23, close, further in exiting side, this UV-absorbing layer 22 is overlapped can (without diagram).
In the present invention, as shown in Figure 3, in UV-absorbing layer 22, further add that antireflection layer 23 also can.In the embodiment of Fig. 3, antireflection layer 23 is arranged on the surface of raw material dustproof film 21 of the surface opposite side arranging with UV-absorbing layer 22, but also can use other modes, can, in UV-absorbing layer 22, antireflection layer be further set.In addition, according to the refractive index of UV-absorbing layer 22, in the centre of UV-absorbing layer 22 and raw material dustproof film 21, antireflection layer is set also passable.Dustproof film 15 of the present invention comprises the mode that these are all.
The material of antireflection layer, carries out suitable selection the known material of the low refractive index of refractive index of the layer connecing Bi O from Ju You.For example, the Games that the raw material dustproof film surface forming at general cellulosic resin arranges closes, and the refractive index of cellulosic resin is approximately 1.5, and refractive index is that the fluorine-type resin of 1.3 to 1.35 degree is suitable.In addition, thickness and the number of plies etc., the material according to using, carries out suitable design by known technology.
According to above-mentioned reason, as the refractive index that makes UV-absorbing layer 22 becomes below 1.5, UV-absorbing layer 22 just can have the function of antireflection layer concurrently, thus, antireflection layer just can omit, or embodiment is as shown in Figure 3 such, adds antireflection layer, from the light incident side of light, count, for the form of the composition of 3 layers of UV-absorbing layer (antireflection layer of holding concurrently) → raw material dustproof film → antireflection layer also can.During this forms, film forming is returned several many, and cost is unfavorable, but it is good to obtain photostability, the effect that transmitance is high.Particularly, for the refractive index of the silicone resin of optical applications exploitation take 1.40 to 1.50 as many, suitable utilization.
In addition, the thickness of this UV-absorbing layer 22, close according to the Games of the thickness design of antireflection layer, determines through characteristic not equal to should pay attention to ultraviolet ray.From raw-material wavelength-light transmission rate characteristic, average light transmitance in the scope in the wavelength field of 350nm to 450nm is more than 90%, it is preferably high permeability as far as possible, in addition, considering to make average light transmitance in the scope in 200 to 300nm wavelength field is below 50%, and the decision of carrying out the thickness of UV-absorbing layer 22 is necessary.
Below, the manufacture method of dustproof film of the present invention is described in detail.
Dustproof film of the present invention basically, can carry out coating film forming by the material solution of UV-absorbing layer in the surface of the raw material dustproof film of film forming on level and smooth substrate.Fig. 3 closes and describes the Games of 3 layers of structure of UV-absorbing layer-raw material dustproof film-antireflection film, first, in soda glass, quartz glass, on the substrate that siloxane wafer etc. level and smooth ground, by the solution of UVA material, with method of spin coating, gap and rotary process, the known means of gap coating method etc. are coated with dry, solidify and obtain UV-absorbing layer 22.Thickness, designs decision from transmitance.Then, by the solution of raw material dustproof film material, by optical design, coating in the UV-absorbing layer 22 of above-mentioned film forming, dry solidification, obtains raw material dustproof film 21.Equally, the solution of antireflection member is coated with on raw material dustproof film, and dry solidification, on the raw material dustproof film of above-mentioned film forming, further arranges antireflection layer 23.
Above-mentioned various film forming, according to the structure design of dustproof film of the present invention, carry out just passable, without any restriction.At this, the thin film-forming method of the UV-absorbing layer of substrate is described, antireflection layer is orlop, is raw material dustproof film film forming on it, further on raw material dustproof film, carries out the film forming of UV-absorbing layer.This order, can according to the needs of engineering take just contrary all can, the layer that the fissility with substrate for film deposition is high is preferred as orlop (=substrate for film deposition side).In addition, according to necessity, substrate for film deposition surface, the surface treatment that also can improve fissility.
As above-mentioned, after the dustproof film of the present invention 15 that obtains solidifying in substrate for film deposition, having, the peel jig of the frame shape of the profile identical with contour substrate (without diagram) is bonding, by its at leisure pull-up peel off, just can obtain having the dustproof film of the present invention of UV-absorbing layer.
In addition, be endowed on the dustproof film component framework of adhesive linkage, the dustproof film of the present invention so obtaining is carried out bonding.Can obtain dustproof film component of the present invention.
Below, the present invention is further described with embodiment, but to the present invention without any restriction.
[embodiment 1]
The A5052 aluminium alloy dustproof film component framework 41 use machinings processed of shape are as shown in Figure 4 made.The shape of this dustproof film component framework 41, the outside dimension in each bight is 1146x1392mm, and very little in it is the rectangle of 1124x1370mm, and thickness is 5.8mm, and the shape inner side in each bight is R2, outside is R6.In addition, on long limit, as processing use, the 4 diameter 2.5mm of place are set, the shrinkage pool 43 of degree of depth 2mm, each 2 places on minor face and long limit, arrange height 2mm, the ditch 42 of degree of depth 3mm.Further, on two long limits, the air hole 46 that diameter is 1.5mm arranges at 8 places.
This dustproof film component framework is transported into the dust free room of 10 grades, with surfactant and pure water, carries out good cleaning, drying.Then, an end face of dustproof film component framework arranges siloxane adhesive linkage as dustproof film adhesive linkage 45, another end face is as photomask adhesive coating 44, by dilution with toluene siloxane sticker, (trade name is all KR3700, Shin-Etsu Chemial Co., Ltd's system), with the dispersion machine of air pressurized, be coated with heat hardening.Then, in the mode that the ventilation cave of dustproof film component framework 41 sides 46 is covered, filtrator 47 is pasted and paid.Finally; by mould release, give surface; by the PET film of thickness 150 μ m with parting tool carry out with dustproof film component framework almost same shape cut off processing and fabricating, by photomask adhesive coating for protection stripping film (without diagram) paste pair, frame part completes.
In addition, in the substrate for film deposition of the quartz system of the level and smooth grinding of 1200 * 1500mm * thickness 17mm, raw material dustproof film material solution by cellulose propionate (Sigma-Aldrich system) with the dilution of acetic acid butyl ester, is coated with by gap coating method.Now, coating weight, is set as dry rear thickness 4.0 μ m.Carried out 1 hour standing, make solvent have natural drying to a certain degree after, with 130 ℃ of heating of IR lamp (not shown), raw material dustproof film forms.
Then, on this raw material dustproof film, as UV-absorbing layer, to carry out pair adding constrictive type silicone rubber (trade name KER-2500, Shin-Etsu Chemial Co., Ltd's system) A, B liquid well mixes, with toluene, carried out after viscosity adjustment, with the coating of gap coating method.Now, thickness becomes 1 μ m after dry and adjusts like that.Thereafter, within 2 hours, level is standing, when making surface smoothing, by the toluene evaporates of dilution use, further, with IR lamp, at 100 ℃, carries out 1 hour, then at 150 ℃, carries out heating in 5 hours, makes its complete reaction sclerosis.The refractive index of this UV-absorbing layer is 1.41.To all be cooled to room temperature, with the same shape of contour substrate, the stainless steel peel jig of frame shape is bonding by UV-absorbing layer, and the pull-up at leisure of Chu electricity limit, limit, obtains dustproof film of the present invention as stripping film.
Then, by UV-absorbing layer to configure like that towards dustproof film adhesive linkage side, on the adhesive linkage 45 of above-mentioned dustproof film component framework 41, by having, the dustproof film of the present invention 48 of UV-absorbing layer is bonding, dustproof film component framework 41 film of not wanting around cuts off and removes with cutting knife, and dustproof film component 40 of the present invention completes.
The dustproof film component of the present invention obtaining, transmitance measuring machine for the light transmission rate of dustproof film (great Zhong Electronics Co., Ltd system) is carried out instrumentation, in the long field of all-wave of wavelength 350-450nm, the transmitance of average out to 95.2%.On the other hand, the wavelength field of wavelength 200 to 300nm, the mean value of transmitance is about 48%.
Further, the dustproof film component of the present invention obtaining, uses high-pressure mercury light irradiation, and photostability is identified.For high-pressure mercury-vapor lamp (oxtail Electric Co., Ltd system), light will be by the order of UV-absorbing layer → dustproof film by such configuration, and dustproof film face is 5000mW/cm with light Strong degree 2ultraviolet ray irradiate, the light transmission rate in above-mentioned wavelength field, variation and the outward appearance of thickness are confirmed.Its result, even if test until cumlative energy 600,000 J, above-mentioned light transmission rate, the outward appearance of thickness and irradiation portion is not found to change.
[embodiment 2]
Similarly to Example 1, outside dimension 280 * 280, inside dimension 270 * 270, the A5052 aluminium alloy dustproof film component framework processed of height 4.8mm is produced, and cleans well bone dry in the dust free room of 10 grades with surfactant and pure water.Thereafter, at an end face, be provided as the siloxane sticker (trade name: X-40-3004A of the adhesive coating that photomask paying, Shin-Etsu Chemial Co., Ltd's system) layer, in other end, as dustproof film of the present invention is carried out to bonding bonding agent, by siloxane sticker (trade name: KR3700, Shin-Etsu Chemial Co., Ltd's system) be coated with baking oven heat hardening.Then, will the PET film of thickness 150 μ m have been carried out to the stripping film of fluorine sex change silicone coating, with framework outside dimension almost the frame shape of same shape cut off, be attached on above-mentioned adhesive coating.
Then, surface is being carried out to level and smooth grinding and carrying out on the quartz base plate of good clean 350x350x thickness 8mm, by fluorine class solvent (trade name: EF-L174, Mitsubshi Materials Corp's system) fluororesin (trade name: CYTOP, Asahi Glass Co., Ltd's system) of dilution is coated with method of spin coating.Make dry after thickness be 0.07 μ m like that thickness adjust.After coating, substrate for film deposition is kept to level, and meanwhile dry until solvent is difficult to flow, then with hot plate, be heated to 180 ℃ solvent is removed completely.
Then, cellulose propionate (Sigma-Aldrich system) is diluted with acetic acid butyl ester, on above-mentioned fluororesin layer, with method of spin coating, be coated with.Thickness is now adjusted, and making dried cellulose resin layer is 4 μ m.Then, on one side substrate for film deposition is kept to level, be dried on one side until solvent is difficult to mobile being dried, then with hot plate, be heated to 130 ℃ solvent is removed completely.
Then, as UV-absorbing layer, A liquid and the B liquid of organically-modified silica alkane resin (trade name: SCR1011, Shin-Etsu Chemial Co., Ltd's system) are well mixed, with toluene, carry out viscosity adjustment, with method of spin coating, be coated with.This time, adjust thickness, make it after dry, become 1 μ m.Thereafter, within 2 hours, level is standing, and surface is coated with flat, the toluene of thinning agent is evaporated simultaneously, further, with IR lamp, at 70 ℃, carries out 1 hour, then at 150 ℃, carries out heating in 5 hours, completely sclerosis.The refractive index of this UV-absorbing layer is approximately 1.5.
After the sclerosis of UV-absorbing layer, will all be cooled to room temperature, bonding with the aluminium alloy frame processed of the same shape of contour substrate, slowly peel off on Chu electricity limit, limit, obtains dustproof film of the present invention.The UV-absorbing layer of the dustproof film of the present invention that obtains will be carried out bonding towards adhesive linkage, the dustproof film in framework outside cuts off and removes with cutting knife, obtains dustproof film component of the present invention.The dustproof film of this dustproof film component, transmitance measuring machine for light transmission rate (great Zhong Electronics Co., Ltd system) is carried out instrumentation, and the mean transmissivity in 350 to 450nm wavelength field is that 95.0%, 200 to 300nm wavelength field is about 35%.
[comparative example]
The same dustproof film component framework of dustproof film component framework using in use and embodiment 1, makes dustproof film component.This time the dustproof film that uses, the cellulose propionate only using in above-described embodiment 1 forms, thickness is the monofilm of 4 μ m.The manufacture method of this dustproof film, except only omitting UV-absorbing layer film formation process, similarly to Example 1.
This dustproof film component, transmitance measuring machine for the light transmission rate of dustproof film (great Zhong Electronics Co., Ltd system) is carried out instrumentation, and the mean transmissivity in 350 to 450nm wavelength field is 95.0%.To this dustproof film component, under the condition of the Games contract sample with embodiment 1, the result of carrying out irradiation experiment, when cumlative energy becomes 600,000 J, the irradiation trace of the circular of frivolous gonorrhoea occurs in irradiation portion.In addition, transmitance, the mean transmissivity in 350 to 450nm wavelength field can be observed approximately 2% step-down, from measuring spectrum, thickness is calculated simultaneously, and the Mo Hou Minus that can confirm 40nm is few.
in industry, utilize possibility
Dustproof film of the present invention, in the ultraviolet photoetching of using wavelength 350 to 450nm, although used the membrane material of cheap cellulosic resin etc., has improved photostability significantly, and the present invention is industrially extremely significant.

Claims (7)

1. a dustproof film, it is used at dustproof film component in the ultraviolet photolithography of 350 to 450nm wavelength coverage, it is characterized in that, this dustproof film is, its raw material dustproof film at least on the surface of exposure light source side, have UV-absorbing layer, the ultraviolet ray of above-mentioned 350 to 450nm wavelength coverage is average more than 90% in this wavelength coverage in the transmitance of this UV-absorbing layer, and 200 to 300nm the ultraviolet transmitance in this UV-absorbing layer is average below 50% in this wavelength coverage simultaneously.
2. dustproof film claimed in claim 1, further has antireflection layer in described UV-absorbing layer upper.
3. the dustproof film described in claim 1 or 2, the resin that forms described UV-absorbing layer is silicone resin.
4. the dustproof film of any one of claim 1-3, the refractive index of described UV-absorbing layer is below 1.50.
5. a manufacture method with the dustproof film of UV-absorbing layer and antireflection layer, wherein in substrate for film deposition by raw material dustproof film, after UV-absorbing layer and antireflection layer 3 layers arrange in any order, described substrate for film deposition is peeled off, it is characterized in that described each layer is by after the material solution coating corresponding with each layer, be dried, solidify, form in turn thus, wherein the ultraviolet ray of 350 to 450nm wavelength coverage is average more than 90% in this wavelength coverage in the transmitance of this UV-absorbing layer, 200 to 300nm the ultraviolet transmitance in this UV-absorbing layer is average below 50% in this wavelength coverage simultaneously.
6. a dustproof film component, is characterized in that the dustproof film of the method manufacture by claim 5 to tighten attaching on dustproof film component framework.
7. a dustproof film component, is characterized in that the described dustproof film of any one of claim 1 to 4 to tighten attaching on dustproof film component framework.
CN201210091249.9A 2011-03-31 2012-03-30 Dustproof pellicle film, manufacturing method thereof, and dustproof pellicle component with pellicle film attached Expired - Fee Related CN102736400B (en)

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