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KR-102962148-B1 - Pellicle

KR102962148B1KR 102962148 B1KR102962148 B1KR 102962148B1KR-102962148-B1

Abstract

The purpose is to provide a pellicle that is less prone to out-gas generation. The pellicle (10) of the present disclosure comprises a pellicle frame (14), a pellicle membrane (12) supported on one end surface of the pellicle frame (14), and an adhesive layer (15) provided on the other end surface of the pellicle frame (14). The degree of swelling of the adhesive layer (15), indicated by the following formula (A), is 200% or less. Formula (A): [(Mass of 10 mg of test specimen taken from the adhesive layer after immersion) / 10 mg] × 100 In the above formula (A), the mass after immersion represents the mass of the test specimen after immersing the test specimen in 10 ml of a decane solution with a capillary column GC concentration of 99.0% or higher for 6 hours.

Inventors

  • 이토 켄
  • 사토 야스시
  • 우네자키 다카시
  • 오노 요스케

Assignees

  • 미쯔이가가꾸가부시끼가이샤

Dates

Publication Date
20260508
Application Date
20220912
Priority Date
20210913

Claims (8)

  1. Pellicle frame and, A pellicle membrane supported on one end surface of the above pellicle frame, and An adhesive layer provided on the other end surface of the above-mentioned pellicle frame Equipped with, The degree of swelling of the above adhesive layer, indicated by the following formula (A), is 200% or less, and A pellicle having a glass transition temperature Tg of the adhesive layer of the above-mentioned amount of -25℃ to 10℃. Formula (A): [(Mass of 10 mg of test specimen taken from the adhesive layer after immersion) / 10 mg] × 100 (In the above formula (A), the mass after immersion refers to the mass of the test specimen after immersing it for 6 hours in 10 ml of a decane solution with a capillary column GC concentration of 99.0% or higher.)
  2. In claim 1, the adhesive layer comprises a copolymer of a (meth)acrylic acid alkyl ester monomer and a monomer having a functional group reactive with at least one isocyanate group, an epoxy group, and an acid anhydride.
  3. In paragraph 2, the (meth)acrylic acid alkyl ester monomer is a pellicle having at least one of an alkyl group having 1 to 3 carbon atoms and a cycloaliphatic alkyl group.
  4. A pellicle according to paragraph 2, wherein the content of the (meth)acrylate alkyl ester monomer is 80 to 99.5 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the copolymer.
  5. A pellicle according to paragraph 2, wherein the content of the monomer having the functional group is 0.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the copolymer.
  6. In paragraph 2, the adhesive layer comprises a reaction product of the copolymer and the crosslinking agent, and A pellicle in which the content of the crosslinking agent is 0.002 to 3.000 parts by mass per 100 parts by mass of the total amount of monomers constituting the copolymer.
  7. A pellicle according to claim 1 or 2, wherein the amount of gas obtained by converting the amount of gas into n-decane when the following (a) to (d) are performed in this order is 1.5 μg or less. (a) Heating the pellicle under conditions of 120°C and 20 hours (b) Sealing the above pellicle in a resin bag and storing it for two weeks under an atmospheric temperature of 25°C. (c) Heating the pellicle under conditions of 50°C and 4 hours to absorb the released gas into the adsorbent (d) Heating the adsorbent for 10 minutes to measure the amount of gas
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Description

Pellicle The present disclosure relates to a pellicle. Along with the advancement of high-performance semiconductor photolithography processes, the miniaturization of pattern widths in semiconductor integrated circuits is progressing. In the photolithography process, if foreign substances such as dust adhere to the photomask, exposure defects occur, raising concerns about a decline in the yield of semiconductor integrated circuits. To prevent foreign substances such as dust from adhering to the surface of the photomask, a pellicle, which serves as a photomask cover, is installed on the photomask. In recent years, as the precision of exposure patterns has increased, the use of shorter-wavelength EUV (Extreme Ultra Violet) light as an exposure light source has expanded, replacing DUV (Deep Ultra Violet) light. With the shortening of the wavelength of such exposure light, the frequency of contamination of the pellicle film or photomask accompanying the exposure (hereinafter referred to as "haze") is increasing. The cause of this haze is thought to be organic gas components (hereinafter referred to as "outgas") generated from adhesives, etc., during exposure. Patent Document 1 discloses a pellicle that effectively prevents the occurrence of haze on a photomask. The pellicle disclosed in Patent Document 1 comprises a pellicle frame, a pellicle film formed on one end surface of the pellicle frame, and an adhesive formed on the other end surface of the pellicle frame. The adhesive is composed of a predetermined adhesive composition. The total mass of the polymerization initiator in the adhesive is 8 ppm or less relative to the total weight of the adhesive. Patent Document 2 discloses a pellicle that prevents the adsorption of organic gases onto a photomask, which causes haze, by imparting organic gas adsorption performance to the adhesive itself used in the pellicle. The pellicle disclosed in Patent Document 2 has a pellicle frame, a pellicle film formed on one end surface of the pellicle frame, and an adhesive formed on the other end surface of the pellicle frame. The weight swelling degree of the adhesive due to toluene is five times or more. "Weight swelling degree" refers to the ratio of increase when the weight of an elastic gel (adhesive) increases due to the absorption of a liquid (solvent). FIG. 1 is a schematic cross-sectional view illustrating a cross-section of a pellicle according to an embodiment. In the present disclosure, a numerical range indicated using “to” means a range that includes the values described before and after “to” as the minimum and maximum values, respectively. In the numerical ranges described stepwise in the present disclosure, an upper or lower limit value described in any numerical range may be substituted with an upper or lower limit value of a numerical range described in another stepwise manner. In the numerical ranges described in the present disclosure, an upper or lower limit value described in any numerical range may be substituted with a value shown in the examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, the amount of each component refers to the total amount of the multiple substances, unless specifically stated otherwise, where multiple substances corresponding to each component exist. In the present disclosure, the term “process” includes not only independent processes but also cases where the intended purpose of the process is achieved, even if it cannot be clearly distinguished from other processes. In the present disclosure, when the expression “(meth)acrylic” is used, it means either or both of “acrylic” and “methacrylic”. (1) Embodiment A pellicle according to an embodiment of the present disclosure comprises a pellicle frame, a pellicle membrane, and an adhesive layer. The pellicle membrane is supported on one end surface of the pellicle frame. The adhesive layer is provided on the other end surface of the pellicle frame. In the pellicle according to the embodiment, the degree of swelling (hereinafter simply referred to as "degree of swelling") of the adhesive layer, as indicated by the following formula (A), is 200% or less. Formula (A): [(Mass of 10 mg of test specimen taken from the adhesive layer after immersion) / 10 mg] × 100 In the above formula (A), the mass after immersion represents the mass of the test specimen after immersing the test specimen in 10 ml of a decane solution with a capillary column GC (gas chromatograph) concentration of 99.0% or higher for 6 hours. In the present disclosure, "swelling degree" refers to the rate of change in mass (%) of a test specimen when the specimen is immersed for 6 hours in 10 ml of a decane solution with a capillary column GC concentration of 99.0% or higher. In the present disclosure, "decane solution with a capillary column GC concentration of 99.0% or higher" refers to a decane solution in which the purity of dec