JP3429898B2 - Pellicle manufacturing method - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device such as an LSI or a super LSI or a liquid crystal display panel. Periku Le manufacturing method of which it is antistatic in the exposure method using a light relate. 2. Description of the Related Art In the manufacture of semiconductor devices such as LSIs and VLSIs or liquid crystal display panels, patterning is performed by irradiating a semiconductor wafer or a liquid crystal display panel with light, which is used in this case. If there is dust on the exposure master (also called mask or reticle)
This dust absorbs or bends the light, causing the transferred pattern to be deformed and the edges to be rough.In addition, the base is black and the dirt size, quality, appearance, etc. are impaired. Was. [0003] For this reason, these operations are usually performed in a clean room. However, even in this clean room, it is difficult to always keep the exposed original plate clean. A pellicle that adheres well through a pellicle is generally used. In this case, since the dust does not directly adhere to the surface of the exposure original plate but adheres to the pellicle, if the focus is set on the pattern of the exposure original plate during lithography, the dust on the pellicle becomes irrelevant to the transfer. The structure of this pellicle is a pellicle made of a thin film such as nitrocellulose, cellulose acetate, cellulose propionate, etc., or an amorphous fluoropolymer, and a material such as aluminum, stainless steel, plastics, etc. A frame and a good solvent for a pellicle film are applied to the upper portion of the frame and air-dried (see Japanese Patent Application Laid-Open No. 58-219023) or bonded with an adhesive such as an acrylic resin or an epoxy resin (US Pat. No. 4,861,402). And JP-B-63-27707). In addition, an adhesive layer made of polybutene resin, polyvinyl acetate resin, acrylic resin, etc. is provided below the pellicle frame to fix the pellicle to the exposure master, and the surface of the adhesive layer is used to protect the adhesive layer. It has a structure in which separators are bonded together. [0004] In using the pellicle, it is the pellicle film that is directly irradiated with an exposure light source (ultraviolet rays such as g-rays and i-rays or excimer laser light). Since the adhesive for fixing the pellicle film to the pellicle frame may be irradiated by a part of the exposure light source, durability is also considered to be an important property of this adhesive. Since it is necessary to adhere a pellicle film, which is an ultra-thin micron film, to the pellicle frame in a stretched state, it is an important material for the performance of the pellicle. However, conventionally used acrylic adhesives and epoxy adhesives have insufficient bonding strength or inconsistent bonding area, and thus lack reliability such as wrinkles. The adhesive is severely deteriorated by the exposure light source, and if used to some extent, the adhesive solidifies and decomposes, and this becomes a source of dust.
In addition, the pellicle film has the disadvantage of peeling or cracking due to a change in the tension of the pellicle film. Particularly, when an amorphous fluorine-based polymer is used as the material of the pellicle film, the fluorine-based polymer has excellent release properties. Therefore, there is also a problem that practical adhesive strength cannot be obtained with an acrylic adhesive or an epoxy adhesive. Therefore, the present inventors used a fluorine-based adhesive having the same or similar structure as that of the pellicle film as an adhesive for the pellicle film using an amorphous fluorine-based polymer, and used the adhesive at or near the glass transition temperature. When heated above,
It has been proposed that the pellicle film and the adhesive adhere firmly (see Japanese Patent Application Laid-Open No. 6-67409), but in this case, when the film and the frame are adhered, it is necessary to obtain sufficient adhesive strength. When heated above the glass transition temperature of the pellicle film forming polymer, the film itself tends to wrinkle and strain,
When the heating temperature is set to be equal to or lower than the glass transition temperature in order to prevent this, it has been confirmed that there is a disadvantage that the adhesive strength becomes insufficient. [0006] Means for Solving the Problems The present invention relates to a process for the preparation of Periku Le solving such a disadvantage, it is an adhesive made of the pellicle film and the frame from the pellicle film and the equivalent polymer In the step of bonding using the pellicle film, the pellicle film and the frame are brought into close contact with each other via the adhesive, and then an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is formed on the pellicle film from the top surface of the frame. is applied together, the heated contact the pellicle membrane and the frame Chakusu
And it is characterized in the Turkey. That is, the present inventors have conducted various studies to develop a pellicle in which a pellicle film and a frame are firmly bonded and do not generate wrinkles or distortion even after bonding. When bonding using an adhesive composed of a polymer equivalent to the film, the pellicle film and the frame are closely adhered with the adhesive, and then an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied from above the pellicle film. Since the pellicle film and the frame are adhered by heating and applying according to the shape of the frame upper surface, it is found that the pellicle film and the frame are strongly adhered. When the solution is dried, the temperature applied to the film may be lower than the glass transition temperature of this polymer. It was completed by the present invention confirmed that there is no. This will be described in more detail below. The present invention relates to a pellicle and a method for producing the pellicle. As described above, in the step of bonding a pellicle film and a frame with an adhesive made of a polymer equivalent to the pellicle film, the pellicle is used in the step. After adhering the film and the frame with the adhesive, a solution in which the same polymer as the pellicle film is dissolved is applied from above the pellicle film, and heated to adhere the pellicle film and the frame, According to this, the pellicle film and the frame are strongly adhered to the pellicle, and this pellicle film has an advantage that wrinkles and distortion do not occur. In the method for producing a pellicle according to the present invention, when the pellicle film and the frame are adhered to each other by using an adhesive made of a polymer equivalent to the pellicle film, the pellicle film and the frame are brought into close contact with the adhesive, and then the pellicle film and the frame are formed. The pellicle film is applied over the pellicle film using an organic solvent solution in which a polymer is dissolved, and the pellicle film is adhered to a frame. The pellicle membrane may be of any type known in the art, including nitrocellulose, cellulose acetate, cellulose propionate, a perfluoro (butenyl vinyl ether) polymer as an amorphous fluoropolymer, Fluoroethylene and perfluoro (2,2-dimethyl-1,
3-dioxole) and the like. For this, it has been proposed to use a polymer equivalent to a pellicle membrane instead of a conventionally known acrylic resin or epoxy resin. However, in order to obtain a sufficient adhesive strength, it is necessary to heat the polymer to a temperature higher than the glass transition point of the polymer. There was a problem that it was easy. However, when this adhesive is dissolved and bonded with an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved, the adhesive contains a polymer equivalent to the pellicle film, so that the adhesive strength with the pellicle film increases. In addition, since it has viscosity, the positional accuracy of coating and the dissolution speed at the time of melting and bonding are stable, and it is possible to bond at a temperature below the glass transition point of this polymer, so that wrinkles and distortions do not occur on the pellicle film Advantages are given. The concentration of the polymer in the solution in which a polymer equivalent to the pellicle film is dissolved is less than 1.0% by weight in the case of a perfluoro (butenyl vinyl ether) polymer, and the viscosity of the solution is less than 30 cps. This concentration must be 1% by weight or more because it spreads too much during coating and it is difficult to improve the positional accuracy. If it exceeds 15.0% by weight, the viscosity of the solution increases and the pellicle film may not be covered. Sufficient adhesive strength cannot be obtained due to reduced permeability. EXAMPLES Examples of the present invention and comparative examples will now be described. Example 1 A perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type (trade name, manufactured by Asahi Glass Co., Ltd.) was dissolved in CT solv 180 (trade name, manufactured by Asahi Glass Co., Ltd.) as a solvent, and the concentration was 5%. (Concentration represents% by weight, the same applies hereinafter). Then, a 0.84 μm-thick transparent film was formed on the polished quartz substrate having a diameter of 200 mm and a thickness of 3 mm using a spin coater, and dried at 180 ° C. for 15 minutes to form a pellicle film. . Next, a perfluoro (butenyl vinyl ether) polymer is placed on the upper surface of a 120 mm square aluminum frame which is anodized and treated as a pellicle frame.
The CYTOP CTXS type (described above) is used as the solvent and CT so
lv 180 (described above) is coated with a 10% fluoropolymer adhesive, dried at 150 ° C for 1 hour to form an adhesive layer with a thickness of 0.2mm, and then the pellicle film obtained above Is heated to 100 ° C for 3 minutes and pressed to adhere, and from the top of this film, the perfluoro (butenyl vinyl ether) polymer Cytop CTXS type (described above)
Apply a 3% fluoropolymer solution dissolved in solv 180 (shown above) to match the shape of the top surface of the frame from above the pellicle membrane, and use a dryer to keep the frame temperature at 100 ° C.
After heating and drying for 10 minutes to bond the pellicle film and the pellicle frame, the excess film was removed, and a pellicle having good appearance and a film adhesive strength of 150 gf / cm ² was obtained. Example 2 A copolymer of tetrafluoroethylene and perfluoro (2,2-dimethyl-1,3-dioxole), Teflon AF1600 (trade name, manufactured by Dupont, USA) was used as its solvent, Fluorinert FC-75 [ Sumitomo 3M Co., Ltd.) to prepare a 3% concentration solution.
A transparent film having a thickness of 0.84 μm was formed on a polished quartz substrate having a thickness of 3 mm and a thickness of 3 mm using a spin coater.
The pellicle film was formed by drying at 15 ° C. for 15 minutes. Next, the above-mentioned Teflon AF1600 (described above) was placed on the upper surface of a 120 mm square aluminum frame which had been anodized as a pellicle frame.
A fluoropolymer adhesive having a concentration of 10% dissolved in Fluorinert FC-75 (described above) was applied and dried at 150 ° C. for 1 hour to form an adhesive layer having a thickness of 0.2 mm. Heated at 150 ° C. for 3 minutes and pressed against each other, and the Teflon AF1600 (described above) was used as the solvent and Fluorinert FC-
Apply a 1% concentration fluoropolymer solution dissolved in 75 (as described above), and use a dryer so that the flame temperature becomes 150 ° C.
After heating and drying for 10 minutes to bond the pellicle film and the pellicle frame, the excess film was removed. As a result, a pellicle having good appearance and an adhesive strength of the film of 140 gf / cm ² was obtained. Example 3 Cellulose propionate was dissolved in 2-butanone as a solvent to prepare a solution having a concentration of 5%.
A transparent film having a thickness of 1.4 μm was formed on a 200 mm, 3 mm thick polished quartz substrate using a spin coater,
After drying at 150 ° C. for 20 minutes, a pellicle film was formed. Then, an adhesive solution having a concentration of 20% in which cellulose propionate was dissolved in 2-butanone as a solvent was applied to the upper surface of a pellicle frame formed of a 120 mm square aluminum frame which had been subjected to anodizing.
After drying at 20 ° C. for 20 minutes to form an adhesive layer having a thickness of 0.2 mm, the pellicle film obtained above was heated at 90 ° C. for 3 minutes and pressed to adhere to the adhesive layer. A 2% strength solution of cellulose propionate dissolved in 2-butanone was applied according to the shape, and the flame temperature was adjusted to 90%.
After ℃ and dryer heat drying for 10 minutes so as to the pellicle membrane and the pellicle frame is adhered, was removed the excess film, pellicle adhesive strength of appearance good film is 125gf / cm ² is obtained Was done. Comparative Example 1 A perfluoro (butenyl vinyl ether) polymer, Cytop CTXS type (described above) was used as its solvent, CT so
Dissolve in lv180 (described above) to prepare a 5% concentration solution, and apply this solution to a polished quartz substrate with a diameter of 200 mm and a thickness of 3 mm using a spin coater with a thickness of 0.84 μm. And dried at 180 ° C. for 15 minutes to form a pellicle film. Next, a perfluoro (butenyl vinyl ether) polymer was placed on the upper surface of an alumite-treated 120 mm square aluminum frame as a pellicle frame.
Use CYTOP CTXA type (described above) as solvent CT solv 180
Apply the 10% concentration fluoropolymer adhesive dissolved in (above) and dry at 150 ° C for 1 hour to form an adhesive layer having a thickness of 0.2 mm, and then apply the pellicle film obtained above for 3 minutes. 1
Heat it to 00 ° C and press it tightly, apply the solvent CT solv 100 (shown above) from the top of this film to the shape of the top of the frame, and heat dry with a dryer for 10 minutes so that the frame temperature becomes 100 ° C. After adhering the pellicle film and the pellicle frame, the excess film was removed, and the resulting pellicle was too low in the viscosity of the applied CT solv 100 (described above)
The appearance was poor because the solvent protruded from the width of the frame end face. The adhesive strength of the film was 125 gf / cm ² . Comparative Example 2 In the same manner as in Comparative Example 1, a perfluoro (butenyl vinyl ether) polymer / CYTOP CTXS type (supra)
0.84μm pellicle film was prepared and anodized 120mm square aluminum frame was coated on the top surface of perfluoro (butenyl vinyl ether) polymer Cytop C
TXA type (described above) dissolved in a solvent CT solv 180 (described above) is coated with a 10% concentration fluoropolymer adhesive and applied at 150 ° C.
After drying for 1 hour to form an adhesive layer with a thickness of 0.2mm,
The pellicle film obtained above was heated at 100 ° C. for 3 minutes to be pressed and adhered to the film, and a perfluoro (butenyl vinyl ether) polymer / Cytop CTXS type (see above) was fitted from above the film to the shape of the upper surface of the frame. ) The solvent CT
Apply a 16% fluoropolymer solution dissolved in solv 100 (described above) and heat dry with a drier for 10 minutes so that the frame temperature becomes 100 ° C, and bond the pellicle film and pellicle frame. When the film was removed, the resulting pellicle had an excessively high concentration of the applied solution, resulting in a raised appearance at the place where the coating was applied, resulting in a poor appearance, and insufficient adhesive strength due to the low solubility of the solution, The adhesive strength was also 10 gf / cm ² or less. The present invention relates to a pellicle and a method for manufacturing the pellicle, and as described above, includes a step of bonding a pellicle film and a frame using an adhesive made of a polymer equivalent to the pellicle film. After the pellicle film and the frame are adhered to each other with an adhesive, an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied from above the pellicle film and heated to be adhered. According to this, a pellicle having a strongly bonded film without wrinkles or distortion can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Shirasaki 2-13-1, Isobe, Annaka-shi, Gunma Prefecture Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Laboratory (72) Inventor: Aihiko Nagata Isobe, Annaka-shi, Gunma No.2-13-1 Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Research Laboratories (72) Inventor Shu Shu Kashida 2-3-1-1, Isobe, Annaka-shi, Gunma Prefecture Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Research Laboratory (72 ) Inventor Yoshihiro Kubota 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Laboratory (56) References JP-A-6-67409 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 1/14

Claims (1)

(57) The Claims 1. A pellicle film and the frame in the step of adhering with an adhesive made of the pellicle film and the equivalent polymer, the adhesive of the pellicle membrane and the frame Then, an organic solvent solution in which a polymer equivalent to the pellicle film is dissolved is applied over the pellicle film according to the shape of the upper surface of the frame, and the pellicle film and the frame are bonded by heating. A method for producing a pellicle, comprising: