WO2012004950A1 - ペリクル膜 - Google Patents
ペリクル膜 Download PDFInfo
- Publication number
- WO2012004950A1 WO2012004950A1 PCT/JP2011/003705 JP2011003705W WO2012004950A1 WO 2012004950 A1 WO2012004950 A1 WO 2012004950A1 JP 2011003705 W JP2011003705 W JP 2011003705W WO 2012004950 A1 WO2012004950 A1 WO 2012004950A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pellicle
- film
- pellicle film
- fluorine
- solvent
- Prior art date
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/16—Halogens
- C08F12/20—Fluorine
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Definitions
- the present invention relates to a pellicle membrane and a method for manufacturing the pellicle membrane.
- patterning is formed on a semiconductor wafer using lithography technology. Specifically, the pattern is transferred to the semiconductor wafer by irradiating the photoresist film formed on the surface of the semiconductor wafer with exposure light through the exposure substrate on which the pattern is drawn. If dust adheres to the exposed substrate, the transfer pattern is deformed, and the performance of the semiconductor device and the manufacturing yield are reduced. Therefore, a pellicle, which is a dust-proof cover with very high light transmittance, is attached to the surface of the exposure substrate to prevent dust from adhering to the exposure substrate. Even if dust adheres to the pellicle, the exposure light is focused on the exposure substrate, so that the transfer pattern is not deformed.
- the pellicle 10 includes a pellicle film 12 that is transparent to exposure light, and a pellicle frame 14 to which the pellicle film 12 is attached.
- the material of the pellicle film 12 is generally nitrocellulose, cellulose acetate, a fluororesin, or the like.
- the material of the pellicle frame 14 is generally aluminum, stainless steel, polyethylene, or the like.
- the pellicle film 12 and the pellicle frame 14 may be bonded via an adhesive layer 13.
- the pellicle 10 has an adhesive layer 15 disposed at the lower part of the pellicle frame 14.
- the adhesive layer 15 is attached to the exposure substrate.
- the adhesive layer 15 is made of an adhesive such as polybutene resin, polyvinyl acetate resin, acrylic resin, or silicone resin. Furthermore, you may have a release layer (not shown) which protects the adhesion layer 15. FIG.
- the material of the pellicle film is an organic material, it is likely to undergo photodegradation or photolysis as the wavelength of exposure light becomes shorter.
- the pellicle film is subjected to photodegradation or photolysis, there arises a problem that the film thickness of the pellicle film is reduced and the exposure light transmittance is reduced.
- the polymer chain constituting the pellicle film is cleaved and recombined by radicals of the polymer chain, and the refractive index of the polymer changes. Such changes in transmittance and refractive index cause deterioration in patterning accuracy.
- a pellicle film made of an amorphous perfluoropolymer has been proposed in which the surface thereof is treated with fluorine gas to form a fluorinated layer to suppress photodegradation or photodecomposition (Patent Literature). 1). Further, it is proposed that the pellicle film is made of an amorphous perfluoropolymer, and that photodegradation or photolysis is suppressed by fluorinating the terminal group of the amorphous perfluoropolymer constituting the film. .
- Fluorination of polymer end groups is said to be carried out by blowing a mixed gas of fluorine gas and inert gas into a solution in which an amorphous perfluoropolymer is dissolved in a fluorine-based solvent (see Patent Document 2).
- the pellicle film may be subjected to photodegradation or photolysis by exposure light in lithography.
- photodegradation or photolysis by exposure light in lithography.
- fluorinated layer on the film surface or to fluorinate the polymer terminal to suppress photodegradation or photolysis; these are special treatment steps with fluorine gas
- foreign matter may adhere to the pellicle film during the treatment with fluorine gas.
- an object of the present invention is to more easily manufacture a pellicle film in which photodegradation or photolysis due to exposure light is suppressed.
- a pellicle film containing a certain amount of a fluorine-based solvent suppresses photodegradation or photodegradation due to exposure.
- a pellicle film is a coating film obtained by dissolving a material (for example, a fluorinated resin such as an amorphous fluoropolymer) that constitutes the pellicle film in a fluorine-based solvent. It can be produced by drying it.
- a pellicle film in which photodegradation or photolysis is suppressed can be easily produced by adjusting the drying conditions of the coating film.
- the first of the present invention relates to the pellicle film and pellicle shown below.
- a pellicle film for lithography containing an amorphous fluoropolymer and containing 5 to 800 ppm by mass of a fluorine-based solvent.
- the pellicle membrane according to [1] wherein the fluorinated solvent is soluble in the amorphous polymer.
- the pellicle membrane according to [3], wherein the fluorine-based solvent is perfluorotrialkylamine.
- a second aspect of the present invention relates to a method for manufacturing a pellicle film described below.
- a method for producing a pellicle film comprising: a step A for forming a coating film of a solution containing an amorphous fluoropolymer and a fluorine-based solvent; and a step B for removing the fluorine-based solvent in the coating film.
- a method for producing a pellicle film wherein in the step B, 5 to 800 mass ppm of a fluorinated solvent remains in the coating film.
- the pellicle film of the present invention In the pellicle film of the present invention, photodegradation or photolysis due to exposure light is suppressed. Therefore, even when the pellicle film of the present invention is used for a pellicle for lithography using short-wave exposure light (for example, ArF vacuum ultraviolet light (ArF excimer laser (193 nm) or the like)), patterning accuracy can be maintained over a long period of time. Moreover, the pellicle film of the present invention can be easily manufactured without adding a special processing step to the normal manufacturing process.
- short-wave exposure light for example, ArF vacuum ultraviolet light (ArF excimer laser (193 nm) or the like
- 6 is a graph showing the relationship between the amount of energy applied to the pellicle film and the amount of decrease in the film thickness of the pellicle film for each amount of fluorine-based solvent contained in the pellicle film. It is a graph which shows the relationship between the fluorine-type solvent amount contained in a pellicle film
- the pellicle film of the present invention contains an amorphous fluoropolymer as a main component.
- amorphous as used in the present application means that a clear diffraction phenomenon is not shown by the X-ray diffraction method. This is because the amorphous fluoropolymer is highly permeable to excimer laser light and has solvent solubility.
- the amorphous fluoropolymer is required to be a resin whose film thickness can be designed to have a transmittance of 99% or more with respect to light having a wavelength of 193 nm.
- the amorphous fluoropolymer is required to be able to exist as a self-supporting film when it is a film having a thickness of 1 ⁇ m or less.
- the possibility of existence as a free-standing film means a film that does not cause wrinkles or slack when attached to a pellicle frame.
- the amorphous fluoropolymer may be a perfluoroalicyclic polymer having a cyclic structure in the main chain, or a chain perfluoropolymer having no cyclic structure in the main chain.
- the perfluoroalicyclic polymer having a cyclic structure in the main chain can be, for example, a polymer having a cyclic perfluoroether group represented by the following chemical formula as a repeating unit.
- This perfluoroalicyclic polymer is specifically shown in Japanese Patent Application Laid-Open No. 2000-275817, and may be referred to.
- m is 0 or 1;
- n is in the range of 10 to 1 ⁇ 10 4 .
- perfluoroalicyclic polymers examples include CYTOP (CYTOP, manufactured by Asahi Glass Co., Ltd.).
- the chain perfluoropolymer having no cyclic structure in the main chain can be, for example, a polymer having a repeating unit represented by the following chemical formula. This chain perfluoropolymer is specifically shown in JP-A-2003-57803, etc., and may be referred to.
- X 1 and X 2 are each independently H or F;
- X 3 is H, F, CH 3 or CF 3 ;
- X 4 and X 5 are each independently H, F, or CF 3 ;
- a, b and c Each independently represents 0 or 1.
- Rf is a linear or branched chain having 4 to 100 carbon atoms, a fluoroalkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms, or a linear or branched chain having 4 to 100 carbon atoms And at least one selected from fluoroalkyl groups containing an ether bond in which at least some of the hydrogen atoms are substituted with fluorine atoms;
- Rf is a linear or branched chain having 3 to 99 carbon atoms, a fluoroalkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms, or a linear or branched chain having 3 to 99 carbon atoms
- the pellicle of the present invention is characterized by containing a fluorinated solvent together with an amorphous fluoropolymer.
- the fluorinated solvent is not particularly limited as long as it can dissolve the amorphous fluoropolymer.
- the fluorine-based solvent may be an aliphatic compound or an aromatic compound.
- the aliphatic fluorine-based solvent include CH 3 CCl 2 F, CF 3 CF 2 CHCl 2 , CClF 2 CF 2 CHClF, perfluoroalkylamines such as perfluorohexane and perfluorotributylamine, perfluoro (2 -Butyltetrahydrofuran), methoxy-nonafluorobutane, fluorinated alcohols, ClCF 2 CFClCF 2 CFCl 2 , tridecafluorooctane, decafluoro-3-methoxy-4 (trifluoromethyl) pentane, and mixed solvents thereof It is.
- aromatic compound used as the fluorine-based solvent examples include 1,3-bistrifluoromethylbenzene, benzotrifluoride, perfluorobenzene, and a mixed solvent thereof.
- the boiling point of the fluorinated solvent is preferably 100 ° C. or higher, and particularly preferably about 180 ° C.
- a fluorine-based solvent having a boiling point of less than 100 ° C. it is difficult to form a coating film having a uniform thickness by spin coating with an amorphous fluoropolymer solution. This is because the solvent volatilizes during the spin operation. Further, the dry film may be clouded or it may be crushed (in a state with irregularities on the surface).
- a fluorinated solvent having a boiling point that is too high it takes a long time to dry the coating film of the amorphous fluoropolymer solution, resulting in a non-uniform film thickness.
- fluorinated solvent examples include perfluoroalkylamine, more preferably perfluorotrialkylamine, and particularly preferably perfluorotributylamine.
- the content of the fluorinated solvent in the pellicle membrane of the present invention is preferably 5 to 800 ppm by mass, more preferably 15 to 800 ppm by mass. If the content of the fluorinated solvent is too small, photolysis or photodegradation due to exposure of the pellicle film cannot be sufficiently suppressed, and for example, the transmittance tends to decrease. If the content of the fluorinated solvent is too large, a non-uniform film thickness tends to occur, color unevenness occurs in the pellicle film, and the lithography is adversely affected.
- the content of the fluorinated solvent in the pellicle membrane can be measured by a headspace gas chromatograph mass spectrometry (GC / MS) method. More specifically, the material for the pellicle film may be accommodated in a glass tube, heated to gasify the fluorinated solvent, and the gasified fluorinated solvent may be quantified by GC / MS.
- GC / MS headspace gas chromatograph mass spectrometry
- the thickness of the pellicle film of the present invention is preferably set to 1 ⁇ m or less. Further, it is preferable that the thickness of the pellicle film is set precisely so as to increase the light transmittance due to the optical interference effect according to the wavelength of the exposure light and the incident angle of the exposure light.
- the thickness of the pellicle film needs to be set very precisely, for example, in nm units. This is because the light transmittance of the pellicle film varies greatly depending on a slight difference of the film thickness in nm units. Therefore, it is necessary to suppress the change of the film thickness during use of the pellicle film as much as possible.
- the conventional pellicle film is irradiated with exposure light for a long period of time, its film thickness is changed, that is, reduced.
- the exposure light has a short wavelength, the decrease rate tends to increase. Therefore, there is a problem that the life of the pellicle film is shortened.
- the pellicle film of the present invention is a long-life pellicle film that is difficult to reduce the film thickness even when irradiated with exposure light having a short wavelength.
- a fluorine-based solvent stabilizes radicals generated by breaking a C—C bond or a C—F bond in a polymer by irradiation of exposure light, thereby suppressing deterioration of the pellicle film.
- the fluorine-based solvent is perfluorotrialkylamine, it is considered that the density of the lone pair of N atoms is reduced by the perfluoroalkyl group, so that the radical can be stabilized.
- a fluorinated solvent acts as a light absorber.
- the pellicle film of the present invention is used as a pellicle by being attached to a pellicle frame in the same manner as a conventional pellicle film.
- FIG. 3 is a diagram schematically showing a pellicle.
- the pellicle frame 14 may be a conventional pellicle frame, and may be made of aluminum, stainless steel, or polyethylene.
- the pellicle having the pellicle film of the present invention can be used to protect the exposure substrate in the lithography process as in the conventional pellicle.
- the pellicle of the present invention can be used in a lithography process using exposure light having a short wavelength.
- the short wavelength exposure light is, for example, vacuum ultraviolet light having a wavelength of 200 nm or less.
- vacuum ultraviolet light include ArF excimer laser light (wavelength 193 nm). Short-wavelength exposure light tends to cause photodegradation or photolysis of a pellicle film that is used for a long time. This is because short wavelength light has high photon energy.
- the film thickness is reduced.
- the ArF excimer laser beam is irradiated at a irradiation density of 1 mJ / cm 2 / pulse (pulse frequency 500 Hz) for a total of 20 KJ / cm 2
- the thickness reduction amount of the pellicle film of the present invention is usually 4 nm or less, preferably 2 .5 nm or less.
- the photodegradation or photodegradation of the pellicle film means that, for example, the light transmittance of the pellicle film is reduced.
- ArF excimer laser beam irradiation dose irradiation intensity: 1 mJ / cm 2 / pulse (pulse frequency: 400 Hz) required for reduction in transmittance of Arf excimer laser beam of the pellicle film of the present invention (99.7 T% ⁇ 98.0 T%)
- the pellicle film of the present invention includes: 1) a step A for forming a coating film of a solution containing an amorphous fluoropolymer and a fluorinated solvent; and 2) a fluorinated solvent in the coating film. Step B to be removed.
- step A first, an amorphous fluoropolymer as a main component of the pellicle film is dissolved in a fluorine-based solvent to obtain a solution.
- a part of the fluorinated solvent may be a solvent remaining in the pellicle.
- the concentration of the amorphous fluoropolymer in the solution is not particularly limited, and may be set so as to have a viscosity capable of forming a uniform coating film; in general, 1 to 20% by mass, preferably 5 to 15% by mass.
- the obtained solution is preferably filtered through a filter to remove foreign substances.
- a coating film of a solution containing an amorphous fluoropolymer and a fluorinated solvent is formed.
- the film formation may be performed by, for example, a spin coating method.
- the substrate to be applied is, for example, a silicon substrate or a quartz glass substrate.
- the coating amount may be set as appropriate according to the desired thickness of the pellicle film.
- the coating film may be dried by heating.
- the heating temperature is not particularly limited, but can be set in the range of 100 ° C to 200 ° C.
- the fluorine-based solvent is left in the coating film in an amount of 5 to 800 ppm by mass, preferably 15 to 800 ppm by mass.
- the residual amount of the fluorinated solvent can be controlled by adjusting the heating temperature and heating time in the drying step.
- the pellicle film of the present invention can be obtained by peeling off the coating film in which a desired amount of the fluorine-based solvent remains from the substrate.
- the coating film when the residual amount is less than the desired amount by removing the fluorine-based solvent from the coating film, the coating film is placed in a fluorine-based solvent atmosphere, and the coating film absorbs the solvent, and the present invention
- the pellicle can also be obtained. However, it may not be preferable in terms of an increase in the number of manufacturing steps for the pellicle.
- the obtained filtrate was applied to the surface of a quartz glass substrate (25 cm square) by spin coating (rotation speed: 700 rpm, rotation time: 60 seconds) to form a coating film.
- the coating film formed on the substrate surface was placed in a clean oven and heated to 165 ° C.
- the heating time was adjusted as shown in Table 1 below (in the range of 80 to 400 seconds) to obtain a dry film.
- a resin release ring was attached to the dry film on the substrate surface, and the dry film was peeled from the substrate to obtain a pellicle film.
- the thickness of the obtained pellicle film was 829 nm.
- the content of the fluorinated solvent contained in the obtained pellicle film was measured by a headspace GC / MS method. Specifically, 100 mg of the membrane material was placed in a glass tube and heated at 180 ° C. for 3 minutes to gasify the fluorinated solvent contained in the pellicle membrane, and the amount of the gasified fluorinated solvent was determined. The measurement results are shown in Table 1.
- the pellicle films obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were irradiated with ArF excimer laser light.
- the irradiation density was 1 mJ / cm 2 / pulse, and the laser oscillation frequency was 500 Hz.
- the graph of FIG. 1 is a graph showing the relationship between the irradiation energy amount (X axis) of ArF excimer laser light and the film thickness reduction amount (Y axis) of the pellicle film.
- Data for Comparative Example 1 (solvent amount: 0.5 mass ppm) is indicated by ⁇ ;
- Data for Comparative Example 2 (solvent amount: 1.8 mass ppm) is indicated by ⁇ ;
- Example 1 (solvent amount: 7 mass ppm) );
- Data of Example 2 (solvent amount: 17 mass ppm) is represented by ⁇ ;
- data of Example 3 (solvent amount: 25 mass ppm) is represented by ⁇ ;
- Example 4 (solvent amount) : 64 mass ppm) is indicated by ⁇ ;
- data of Example 6 (solvent amount: 480 mass ppm) is indicated by ⁇ ;
- data of Example 7 (solvent amount: 800 ppm by mass) is indicated by ⁇
- Comparative Example The data of 3 (solvent amount
- the amount of decrease in film thickness is obtained by measuring the transmittance of light having a wavelength of 180 to 400 nm, obtaining the pellicle film thickness from the relationship with the refractive index of the substance, The amount of reduction was calculated.
- the graph of FIG. 2 shows the amount of fluorine-based solvent (mass ppm) in the pellicle film and the irradiation amount of ArF laser light necessary to reduce the transmittance for ArF laser light from 99.7 T% to 98.0 T%. It is a graph which shows the relationship. It can be seen that the greater the amount of fluorine-based solvent in the pellicle film, the greater the required irradiation amount, that is, the lower the transmittance. However, as described above, when the amount of the fluorinated solvent exceeds 800 ppm by mass, color unevenness occurs on the surface of the pellicle film.
- the film thickness distribution of the pellicle film was measured for Comparative Example 4 in which color unevenness occurred on the film surface of the pellicle film.
- the measurement points were the same 49 points in the region (112 ⁇ 139 mm) 5 mm or more inside from the pellicle frame.
- the maximum value of the film thickness was 835.3 nm and the minimum value was 824.8, and the film thickness variation was large. It is estimated that color unevenness has occurred due to the variation in film thickness.
- Example 5 A pellicle film was obtained in the same manner as in Example 1 except that the drying temperature was 150 ° C. and the drying time was 20 minutes. As in Example 1, the fluorine solvent contained in the pellicle film was gasified, and the amount of the gasified fluorine solvent was determined. The content of the fluorinated solvent was 0.7 mass ppm.
- Example 6 A pellicle film was obtained in the same manner as in Example 1 except that the drying temperature was 180 ° C. and the drying time was 5 minutes. As in Example 1, the fluorine solvent contained in the pellicle film was gasified, and the amount of the gasified fluorine solvent was determined. The content of the fluorinated solvent was 0.7 mass ppm.
- the conditions of Comparative Examples 5 and 6 are general manufacturing conditions for the pellicle film. Under the general manufacturing conditions of the pellicle film, the content of the fluorine-based solvent in the pellicle film was less than 5 mass ppm.
- Example 7 A pellicle film was obtained in the same manner as in Example 1 except that the spin coating conditions were changed and the drying temperature and drying time shown in Table 2 were used. The film thickness of the obtained pellicle film was 281 nm.
- the fluorine solvent contained in the pellicle film was gasified, and the amount of the gasified fluorine solvent was determined. Table 2 shows the content of the fluorinated solvent.
- the pellicle film obtained in Example 11 and Comparative Example 7 was irradiated with ArF excimer laser light as in Example 1.
- the irradiation density was 1 mJ / cm 2 / pulse, and the laser oscillation frequency was 500 Hz.
- FIG. 4 is a graph showing the relationship between the irradiation energy amount (X axis) of ArF excimer laser light and the film thickness reduction amount (Y axis) of the pellicle film.
- Data for Comparative Example 7 (solvent amount: 3 mass ppm) is indicated by ⁇ ; data for Example 11 (solvent amount: 27 mass ppm) is indicated by ⁇ . Even when the thickness of the pellicle film was reduced, it was found that the decrease in film thickness decreased as the amount of remaining solvent increased.
- Example 12 to 15 The pellicle film obtained in Comparative Example 2 was absorbed with a fluorinated solvent by the following method.
- Method The pellicle film obtained in Comparative Example 2 was put in a 6800 ml glass sealed container, and the solvent shown in Table 3 was dropped in the amounts shown in Table 3 respectively, and after adjusting the solvent atmosphere, it was left for 24 hours.
- the amount of solvent absorbed by the pellicle film was measured by the same method as in Example 1 using a GC / MS apparatus. Table 3 shows the type of fluorine-based solvent, the dripping amount of the solvent, and the amount of the fluorine-based solvent absorbed by the pellicle film.
- Solvent 1 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (Asahi Glass Co., Ltd. AC-6000), boiling point: 114 ° C.
- solvent 2 1,1,1,2,2,3,4,5,5,5-decafluoro-3methoxy-4 (trifluoromethyl) -pentane (CT-solv.100E manufactured by Asahi Glass Co., Ltd.)
- Boiling point 97 ° C
- the pellicle film obtained in Example 13 and Example 15 was irradiated with ArF excimer laser light in the same manner as in Example 1.
- the irradiation density was 1 mJ / cm 2 / pulse, and the laser oscillation frequency was 500 Hz.
- the graph of FIG. 5 is a graph showing the relationship between the irradiation energy amount (X axis) of ArF excimer laser light and the film thickness reduction amount (Y axis) of the pellicle film.
- Data for Comparative Example 2 (solvent amount: 1.8 mass ppm) is indicated by ⁇ ;
- data for Example 13 solvent amount: 32 mass ppm) is indicated by ⁇ ;
- Example 15 (solvent amount: 23 mass ppm) Data are indicated by ⁇ . It can be seen that a fluorine-based solvent capable of dissolving the amorphous fluoropolymer, regardless of the type of the solvent, reduces the amount of film thickness reduction and improves the light resistance as the solvent content increases.
- the pellicle film of the present invention is used for a pellicle for lithography using short wavelength exposure light (for example, ArF vacuum ultraviolet light (ArF excimer laser (193 nm), etc.)), photodegradation and photodecomposition are suppressed. Contributes to longer life of pellicle. Further, the pellicle film of the present invention can be manufactured without adding a special processing step to the conventional manufacturing process of the pellicle film, and can be easily manufactured.
- short wavelength exposure light for example, ArF vacuum ultraviolet light (ArF excimer laser (193 nm), etc.
Abstract
Description
[1]非晶質フルオロポリマーを含有するリソグラフィ用ペリクル膜であって、5~800質量ppmのフッ素系溶剤を含有するペリクル膜。
[2]前記非晶質フルオロポリマーが、主鎖に環状構造を有するパーフルオロ脂環式ポリマーである、[1]に記載のペリクル膜。
[3]前記フッ素系溶剤が、前記非晶質ポリマーを可溶である、[1]に記載のペリクル膜。
[4]前記フッ素系溶剤は、パーフルオロトリアルキルアミンである、[3]に記載のペリクル膜。
[5]前記リソグラフィ用ペリクル膜のリソグラフィ露光光の波長は、200nm以下である、[1]に記載のペリクル膜。
[6]前記[1]に記載のペリクル膜と、前記ペリクル膜を貼り付けられたペリクル枠と、を含むペリクル。
前記工程Bにおいて、前記塗布膜中に5~800質量ppmのフッ素系溶剤を残留させる、ペリクル膜の製造方法。
本発明のペリクル膜は、非晶質フルオロポリマーを主成分として含む。本願でいう非晶質とは、X線回折法で明確な回折現象が示されないことを言う。非晶質フルオロポリマーは、エキシマレーザー光に対する透過性が高く、溶剤可溶性を有するからである。非晶質フルオロポリマーは、波長193nmの光に対して透過率が99%以上になる膜厚設計が可能である樹脂であることが求められる。また、非晶質フルオロポリマーは、厚さ1μm以下のフィルムとしたときに、自立膜として存在可能であることが求められる。自立膜として存在可能とは、ペリクル枠に貼り付けたときに、皺や弛みが発生しない膜を意味する。
aが0の場合、Rfは炭素数4~100の直鎖または分岐鎖状で水素原子の少なくとも一部がフッ素原子で置換されているフルオロアルキル基または炭素数4~100の直鎖または分岐鎖状で水素原子の少なくとも一部がフッ素原子で置換されているエーテル結合を含むフルオロアルキル基から選ばれる少なくとも1種;
aが1の場合、Rfは炭素数3~99の直鎖または分岐鎖状で水素原子の少なくとも一部がフッ素原子で置換されているフルオロアルキル基または炭素数3~99の直鎖または分岐鎖状で水素原子の少なくとも一部がフッ素原子で置換されているエーテル結合を含むフルオロアルキル基から選ばれる少なくとも1つである。
1)露光光の照射によりポリマー中のC-C結合またはC-F結合が切断されて発生したラジカルを、フッ素系溶剤が安定化させることで、ペリクル膜の劣化を抑制する。特に、フッ素系溶剤がパーフルオロトリアルキルアミンである場合には、N原子の非共有電子対の密度が、パーフルオロアルキル基によって低下していると考えられるので、ラジカルを安定化させることができる。
2)フッ素系溶剤が光吸収剤として作用する。ペリクルに照射された露光光の大部分はペリクル膜を透過するが、その一部はペリクル膜に吸収される。ペリクル膜に吸収された露光光が、ペリクル膜のポリマーを劣化させると考えられるが、それをフッ素系溶剤が吸収していると考えられる。
本発明のペリクル膜は、1)非晶質フルオロポリマーとフッ素系溶剤とを含む溶液の塗布膜を成膜する工程Aと、2)前記塗布膜中のフッ素系溶剤を除去する工程Bとを含む。
非晶質フルオロポリマーであるサイトップ(型番:CHX809SP2、旭硝子株式会社)を、フッ素系溶剤であるパーフルオロトリブチルアミン(EFL-174S、トーケムプロダクツ)に溶解して、ポリマー含量が6重量%の溶液を得た。得られた溶液を、ポリテトラフルオロエチレン(PTFE)製メンブランフィルター(ポアサイズ:500nm)でろ過して、異物を除去したろ液を得た。
GC/MS装置:AGILENT製 6890/5973-GC-MS
カラム:HT-1
温度プログラム:40℃~320℃に、15℃/分の速度で昇温して5分間保持した。
大塚電子製 発光測定システム MCPD-7000
波長180~400nmの光の透過率を測定し、物質の屈折率との関係から多重干渉による透過率ピークのフィッティングシミュレーションにより膜厚を求めた。
大塚電子製 発光測定システム MCPD-7000
波長193nmの光の透過率を測定した。
乾燥温度を150℃、乾燥時間を20分とした以外は、実施例1と同様にペリクル膜を得た。実施例1と同様に、ペリクル膜に含まれるフッ素系溶剤をガス化させ、ガス化したフッ素系溶剤の量を求めた。フッ素系溶剤の含有量は0.7質量ppmであった。
乾燥温度を180℃、乾燥時間を5分とした以外は、実施例1と同様にペリクル膜を得た。実施例1と同様に、ペリクル膜に含まれるフッ素系溶剤をガス化させ、ガス化したフッ素系溶剤の量を求めた。フッ素系溶剤の含有量は0.7質量ppmであった。
スピンコート条件を変更し、さらに表2に記載の乾燥温度、乾燥時間とした以外は、実施例1と同様にペリクル膜を得た。得られたペリクル膜の膜厚は281nmであった。実施例1と同様に、ペリクル膜に含まれるフッ素系溶剤をガス化させ、ガス化したフッ素系溶剤の量を求めた。フッ素系溶剤の含有量を表2に示す。
比較例2で得られたペリクル膜に、以下の方法でフッ素系溶剤を吸収させた。
(方法)
6800mlのガラス製の密閉容器に比較例2で得られたペリクル膜を入れ、それぞれ表3に示す溶剤を、表3に示す量滴下し、溶剤雰囲気を調整後、24時間放置した。ペリクル膜に吸収された溶剤量をGC/MS装置にて実施例1と同様の方法で測定した。フッ素系溶剤の種類及び溶剤の滴下量、ペリクル膜に吸収されたフッ素系溶剤量を表3に示す。(フッ素系溶剤)・溶剤1:1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン(旭硝子社製 AC-6000)、沸点:114℃・溶剤2:1,1,1,2,2,3,4,5,5,5-デカフルオロ-3メトキシ-4(トリフルオロメチル)-ペンタン(旭硝子社製 CT-solv.100E)、沸点:97℃
図5のグラフは、ArFエキシマレーザー光の照射エネルギー量(X軸)と、ペリクル膜の膜厚減少量(Y軸)との関係を示すグラフである。比較例2(溶剤量:1.8質量ppm)のデータを◆で示し;実施例13(溶剤量:32質量ppm)のデータを■で示し;実施例15(溶剤量:23質量ppm)のデータを▲で示す。非晶質フルオロポリマーを溶解させることができるフッ素系溶剤であれば、溶剤の種類に関係なく、溶剤含有量が増えると、膜厚減少量が少なくなり、耐光性が改善することがわかる。
12 ペリクル膜
13 接着剤層
14 ペリクル枠
15 粘着層
Claims (7)
- 非晶質フルオロポリマーを含有するリソグラフィ用ペリクル膜であって、5~800質量ppmのフッ素系溶剤を含有するペリクル膜。
- 前記非晶質フルオロポリマーが、主鎖に環状構造を有するパーフルオロ脂環式ポリマーである、請求項1に記載のペリクル膜。
- 前記フッ素系溶剤が、前記非晶質ポリマーを可溶である、請求項1に記載のペリクル膜。
- 前記フッ素系溶剤は、パーフルオロアルキルアミンである、請求項3に記載のペリクル膜。
- 前記リソグラフィ用ペリクル膜のリソグラフィ露光光の波長は、200nm以下である、請求項1に記載のペリクル膜。
- 請求項1に記載のペリクル膜と、前記ペリクル膜を貼り付けられたペリクル枠と、を含むペリクル。
- 非晶質フルオロポリマーとフッ素系溶剤とを含む溶液の塗布膜を成膜する工程Aと、前記塗布膜中のフッ素系溶剤を除去する工程Bとを含む、ペリクル膜の製造方法であって、
前記工程Bにおいて、前記塗布膜中に5~800質量ppmのフッ素系溶剤を残留させる、ペリクル膜の製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137000340A KR101370134B1 (ko) | 2010-07-08 | 2011-06-29 | 펠리클 막 |
CN201180030269.9A CN102959468B (zh) | 2010-07-08 | 2011-06-29 | 防护膜 |
US13/805,724 US8815476B2 (en) | 2010-07-08 | 2011-06-29 | Pellicle membrane |
SG2012094231A SG186784A1 (en) | 2010-07-08 | 2011-06-29 | Pellicle membrane |
JP2012523515A JP5608234B2 (ja) | 2010-07-08 | 2011-06-29 | ペリクル膜 |
EP11803291.1A EP2592474B1 (en) | 2010-07-08 | 2011-06-29 | Pellicle film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010156194 | 2010-07-08 | ||
JP2010-156194 | 2010-07-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012004950A1 true WO2012004950A1 (ja) | 2012-01-12 |
Family
ID=45440945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/003705 WO2012004950A1 (ja) | 2010-07-08 | 2011-06-29 | ペリクル膜 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8815476B2 (ja) |
EP (1) | EP2592474B1 (ja) |
JP (1) | JP5608234B2 (ja) |
KR (1) | KR101370134B1 (ja) |
CN (1) | CN102959468B (ja) |
SG (1) | SG186784A1 (ja) |
TW (1) | TWI481623B (ja) |
WO (1) | WO2012004950A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015057594A (ja) * | 2013-08-09 | 2015-03-26 | ダイキン工業株式会社 | 含フッ素表面処理剤を含有する物品の分析方法 |
JP2020166063A (ja) * | 2019-03-28 | 2020-10-08 | 三井化学株式会社 | ペリクルの製造方法 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101918687B1 (ko) | 2014-01-28 | 2018-11-14 | 삼성전자주식회사 | 펠리클 |
TWI556055B (zh) * | 2014-08-12 | 2016-11-01 | Micro Lithography Inc | A mask protective film module and manufacturing method thereof |
KR101970059B1 (ko) * | 2016-04-05 | 2019-04-17 | 아사히 가세이 가부시키가이샤 | 펠리클 |
US11878935B1 (en) | 2022-12-27 | 2024-01-23 | Canon Kabushiki Kaisha | Method of coating a superstrate |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03174450A (ja) * | 1989-09-06 | 1991-07-29 | E I Du Pont De Nemours & Co | アモルファスフッ素ポリマー薄膜 |
JPH06230561A (ja) * | 1993-01-29 | 1994-08-19 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクル膜の製造方法 |
JPH09319073A (ja) * | 1996-05-27 | 1997-12-12 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクルの製造方法およびリソグラフィー用ペリクル |
JP2000000025A (ja) | 1998-06-17 | 2000-01-07 | Iseki & Co Ltd | コンバインの穀粒搬出装置 |
JP2000275817A (ja) | 1999-01-22 | 2000-10-06 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクルおよびその製造方法 |
JP2003057803A (ja) | 2001-08-10 | 2003-02-28 | Daikin Ind Ltd | リソグラフィー用ペリクル膜 |
JP2006039408A (ja) * | 2004-07-29 | 2006-02-09 | Asahi Glass Co Ltd | ペリクル |
JP2008216616A (ja) * | 2007-03-05 | 2008-09-18 | Mitsui Chemicals Inc | フッ素含有樹脂膜の製造方法およびそれをもちいたペリクル |
JP2008276195A (ja) * | 2007-04-04 | 2008-11-13 | Shin Etsu Chem Co Ltd | ペリクルの製造方法及びペリクル |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3020320B2 (ja) * | 1991-07-23 | 2000-03-15 | 信越化学工業株式会社 | リソグラフィ−用ペリクル |
JP2915744B2 (ja) * | 1993-04-13 | 1999-07-05 | 信越化学工業株式会社 | ペリクル |
TW420770B (en) * | 1998-09-22 | 2001-02-01 | Mitsui Chemicals Inc | Pellicle film, method of preparing the same and exposure method |
JP2000162761A (ja) * | 1998-09-22 | 2000-06-16 | Mitsui Chemicals Inc | ペリクル、その製法及び露光方法 |
JP4000231B2 (ja) | 1999-03-10 | 2007-10-31 | 信越化学工業株式会社 | 耐光性を改良したリソグラフィー用ペリクル |
JP2000305255A (ja) | 1999-04-23 | 2000-11-02 | Shin Etsu Chem Co Ltd | フッ素エキシマレーザーリソグラフィー用ペリクル |
JP2001264957A (ja) | 2000-03-22 | 2001-09-28 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクル |
US20050202252A1 (en) | 2004-03-12 | 2005-09-15 | Alexander Tregub | Use of alternative polymer materials for "soft" polymer pellicles |
EP1978405A1 (en) | 2007-04-04 | 2008-10-08 | Shin-Etsu Chemical Co., Ltd. | Pellicle and method for preparing the same |
JP5311331B2 (ja) * | 2008-06-25 | 2013-10-09 | ルネサスエレクトロニクス株式会社 | 液浸リソグラフィの現像処理方法および該現像処理方法を用いた電子デバイス |
-
2011
- 2011-06-29 SG SG2012094231A patent/SG186784A1/en unknown
- 2011-06-29 WO PCT/JP2011/003705 patent/WO2012004950A1/ja active Application Filing
- 2011-06-29 CN CN201180030269.9A patent/CN102959468B/zh active Active
- 2011-06-29 JP JP2012523515A patent/JP5608234B2/ja active Active
- 2011-06-29 EP EP11803291.1A patent/EP2592474B1/en not_active Not-in-force
- 2011-06-29 US US13/805,724 patent/US8815476B2/en active Active
- 2011-06-29 KR KR1020137000340A patent/KR101370134B1/ko active IP Right Grant
- 2011-07-06 TW TW100123877A patent/TWI481623B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03174450A (ja) * | 1989-09-06 | 1991-07-29 | E I Du Pont De Nemours & Co | アモルファスフッ素ポリマー薄膜 |
JPH06230561A (ja) * | 1993-01-29 | 1994-08-19 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクル膜の製造方法 |
JPH09319073A (ja) * | 1996-05-27 | 1997-12-12 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクルの製造方法およびリソグラフィー用ペリクル |
JP2000000025A (ja) | 1998-06-17 | 2000-01-07 | Iseki & Co Ltd | コンバインの穀粒搬出装置 |
JP2000275817A (ja) | 1999-01-22 | 2000-10-06 | Shin Etsu Chem Co Ltd | リソグラフィー用ペリクルおよびその製造方法 |
JP2003057803A (ja) | 2001-08-10 | 2003-02-28 | Daikin Ind Ltd | リソグラフィー用ペリクル膜 |
JP2006039408A (ja) * | 2004-07-29 | 2006-02-09 | Asahi Glass Co Ltd | ペリクル |
JP2008216616A (ja) * | 2007-03-05 | 2008-09-18 | Mitsui Chemicals Inc | フッ素含有樹脂膜の製造方法およびそれをもちいたペリクル |
JP2008276195A (ja) * | 2007-04-04 | 2008-11-13 | Shin Etsu Chem Co Ltd | ペリクルの製造方法及びペリクル |
Non-Patent Citations (1)
Title |
---|
See also references of EP2592474A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015057594A (ja) * | 2013-08-09 | 2015-03-26 | ダイキン工業株式会社 | 含フッ素表面処理剤を含有する物品の分析方法 |
JP2020166063A (ja) * | 2019-03-28 | 2020-10-08 | 三井化学株式会社 | ペリクルの製造方法 |
JP7190953B2 (ja) | 2019-03-28 | 2022-12-16 | 三井化学株式会社 | ペリクルの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
SG186784A1 (en) | 2013-02-28 |
KR20130042545A (ko) | 2013-04-26 |
CN102959468B (zh) | 2014-11-19 |
EP2592474A1 (en) | 2013-05-15 |
JPWO2012004950A1 (ja) | 2013-09-02 |
TW201213346A (en) | 2012-04-01 |
KR101370134B1 (ko) | 2014-03-04 |
EP2592474A4 (en) | 2013-11-27 |
CN102959468A (zh) | 2013-03-06 |
US20130095417A1 (en) | 2013-04-18 |
US8815476B2 (en) | 2014-08-26 |
EP2592474B1 (en) | 2015-04-08 |
TWI481623B (zh) | 2015-04-21 |
JP5608234B2 (ja) | 2014-10-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5608234B2 (ja) | ペリクル膜 | |
US6566021B2 (en) | Fluoropolymer-coated photomasks for photolithography | |
JP2005519346A (ja) | 真空紫外で高い透明性を有するフッ素含有化合物 | |
JP6326056B2 (ja) | ペリクル膜、それを用いたペリクル、露光原版および露光装置、ならびに半導体装置の製造方法 | |
JP5442008B2 (ja) | レジストパターンの形成方法および現像液 | |
TWI519889B (zh) | Microsurgical surface film, mask attached to the mask and exposure treatment methods | |
KR101699635B1 (ko) | 펠리클 | |
JP2010211064A (ja) | フォトマスク及びその製造方法 | |
JP4185233B2 (ja) | リソグラフィー用ペリクル | |
JP4000231B2 (ja) | 耐光性を改良したリソグラフィー用ペリクル | |
US20050202252A1 (en) | Use of alternative polymer materials for "soft" polymer pellicles | |
KR101682467B1 (ko) | 펠리클의 분리방법 및 장치 | |
JP2004226476A (ja) | ペリクルの製造方法 | |
US20040137371A1 (en) | Method of making a semiconductor device using a pellicle that is transparent at short wavelengths | |
JP7125835B2 (ja) | ペリクル | |
KR101168333B1 (ko) | 포토마스크를 이용한 웨이퍼 노광 방법 | |
US20100233591A1 (en) | Process for producing pellicle, and pellicle | |
JP2006351824A (ja) | 液浸露光プロセス用液浸媒体、および該液浸媒体を用いたレジストパターン形成方法 | |
JPH11160885A (ja) | リソグラフィにおける露光方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180030269.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11803291 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012523515 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011803291 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13805724 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20137000340 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |