JP2938692B2 - Pellicle manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a pellicle, and more particularly to a method for manufacturing a pellicle which is used as a dust-repellent when manufacturing a semiconductor device such as an LSI or a super LSI or a liquid crystal display panel. .

[0002]

2. Description of the Related Art In the manufacture of semiconductor devices such as LSIs and VLSIs or liquid crystal display panels, a semiconductor wafer or a liquid crystal master is irradiated with light to form a pattern. If dust adheres, the dust absorbs light or bends the light, so the transferred pattern will be deformed, the edges will be rough, and the white background will be stained black, However, there is a problem that the quality, appearance, and the like are impaired, and the performance and manufacturing yield of semiconductor devices and liquid crystal display panels are reduced. For this reason, these operations are usually performed in a clean room, but it is difficult to keep the exposure master clean even in this clean room, so that the surface of the exposure master often passes light for exposure to avoid dust. A pellicle to be adhered is used.

[0003] In this case, the dust does not directly adhere to the surface of the exposure master, but adheres to the pellicle. Therefore, if the focus is set on the pattern of the exposure master during lithography,
The dust on the pellicle becomes irrelevant for the transfer. For this pellicle, a transparent pellicle film made of nitrocellulose, cellulose acetate, etc., which allows light to pass well, is coated with a good solvent for the pellicle film on the upper part of a pellicle frame made of aluminum, stainless steel, polyethylene, etc., and air-dried. JP-A-58-219023) or bonding with an adhesive such as an acrylic resin or an epoxy resin (see US Pat. No. 4,861,402, Japanese Patent Publication No. 63-27707). In recent years, there is a case where an amorphous fluoropolymer having excellent light resistance is used for a film material or an adhesive.

[0004]

However, in the production of this pellicle film, these film materials are prepared by using a solvent in an amount of 3 to 10%.
After dissolving to a concentration of, a solution casting method using a spin coater or a knife coater is used to form a film on a silicon substrate or a glass substrate.
The pellicle film thus formed is formed into a pellicle by a method in which a pellicle frame is adhered to a film formed on the substrate and then the substrate and the film are peeled off in water.
In this film peeling in water, foreign matter generated from materials that come into contact with water, such as a jig for holding the back surface of the substrate and the frame, as well as water stains, may contaminate the film and the entire frame using water as a medium. There was sex.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing a pellicle which has solved the above-mentioned disadvantages, and comprises a step of removing a pellicle film made of a polymer of a fluorine-containing monomer from a substrate at a temperature of -50.degree. It is characterized in that it is carried out while maintaining the cooling temperature in a gas at 10 ° C.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have conducted various studies on a method of peeling a pellicle film formed on a substrate from a substrate, and as a result, have found that a pellicle film made of a polymer of a fluorine-containing monomer is peeled from the substrate. If the process is performed in a gas having a temperature of −50 ° C. to 10 ° C. without using water as in the related art, contamination such as underwater peeling is reduced, and a drying process is not required. The present inventors have found that a pellicle can be obtained easily and efficiently, and have studied the processing conditions in a gas to complete the present invention.

[0007] This will be described in more detail below. The present invention relates to a method for producing a pellicle film, wherein the step of peeling a pellicle film made of a polymer of a fluorine-containing monomer from a substrate is performed in a gas having a temperature of -50 ° C to 10 ° C. is there. According to this, there is an effect that contamination is reduced and a drying step is not required as compared with the conventional method in which the step of peeling the pellicle film from the substrate is performed in water.

As the polymer of a fluorine-containing monomer, Cytop CTXS type (trade name, manufactured by Asahi Glass Co., Ltd.), which is a polymer of a fluorine-containing monomer having a cyclic perfluoroether group, can be preferably used. The pellicle film forming material is dissolved in a solvent by a conventional method to form a solution having a concentration of 3 to 10%, and this solution is pellicle-coated on a silicon substrate or a glass substrate by a solution casting method using a spin coater or a knife coater. After forming a film, a pellicle frame is adhered to the film, and then the pellicle film is peeled from the substrate to form a pellicle film. In the present invention, the peeling of the pellicle film from the substrate is performed in a gas having a temperature of -50C to 10C.

When the pellicle film is peeled from the substrate, since the pellicle film is adhered to the pellicle frame, the pellicle film can be easily peeled from the substrate only by pulling the substrate side in the peeling process chamber. This peeling step is performed in a gas.

This gas may be in air, but may also be in nitrogen gas, oxygen gas, other gases, or a mixture thereof. The pressure of this gas may be under reduced pressure or under high pressure, but it is preferable to be under atmospheric pressure from the viewpoint of easiness of operation.

However, when the temperature of the gas is lower than −50 ° C., the peelability of the gas is rather deteriorated, and the gas becomes brittle depending on the material of the film. If the temperature is higher than ℃, sufficient releasability cannot be obtained, so the temperature needs to be in the range of −50 to 10 ° C. The preferred temperature range is -20 to 0 ° C.

There is no particular limitation on the humidity of the gas in the stripping step in this gas. However, if the humidity is too high, dew condensation occurs, and foreign matter adheres to the droplets, and uneven drying easily occurs. This humidity is in a range where dew condensation does not occur.

In the production of the pellicle film according to the present invention, as described above, the pellicle film is separated from the substrate at a temperature of -50 ° C. to 10 ° C.
It is performed in the gas of. According to this, when peeled off in water, foreign matter generated from a jig for holding down the back surface of the substrate or the frame of the pellicle frame eliminates the conventional defect of contaminating the pellicle film and the pellicle frame through water. In addition, the pellicle film and the pellicle frame can be obtained in a clean state, and a post-drying step which is indispensable for underwater peeling becomes unnecessary.

[0014]

Next, examples of the present invention and comparative examples will be described. Examples 1 to 4 and Comparative Examples 1 to 3 Polymers of fluorinated monomers, Cytop CT × S type [trade name of Asahi Glass Co., Ltd.] were used as their solvents and CT Solve.
It was dissolved in [trade name of Asahi Glass Co., Ltd.] to prepare a solution having a concentration of 6.0%.

Next, 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. A film was formed. On the other hand, anodized
A fluorine-containing diorganopolysiloxane composition is applied on the upper surface of a 120 mm square aluminum pellicle frame, and the pellicle formed on the quartz substrate obtained above on the fluorine-containing diorganopolysiloxane composition application surface. The membrane was adhered.

Next, this was heated at 150 ° C. for 10 minutes to fix the pellicle frame and the pellicle film, and then the pellicle film was peeled off from the substrate in the air at the temperature shown in Table 1. The results as shown in FIG. 1 were obtained, and it was confirmed that the film could be advantageously peeled in the range of −50 ° C. to 10 ° C.

[0017]

[Table 1]

[0018]

According to the present invention, the water-mediated contamination that occurs when the conventionally known underwater peeling is prevented,
The desired pellicle film can be obtained in a clean state, and the subsequent drying step is not required.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Satoshi Shirasaki 2-3-1-1, Isobe, Annaka-shi, Gunma Prefecture Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Laboratory (72) Inventor: Shu Kashida Annaka-shi, Gunma 2-13-1 Isobe Shin-Etsu Chemical Industry Co., Ltd.Precision Functional Materials Research Laboratory (72) Inventor Yoshihiro Kubota 2-13-1 Isobe Isobe, Annaka-shi Gunma Prefecture Shin-Etsu Chemical Co., Ltd.Precision Functional Materials Research Laboratory (56 References JP-A-1-166045 (JP, A) JP-A-3-39963 (JP, A) JP-A-3-67262 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) G03F 1/14

Claims (1)

(57) [Claims] The method according to claim 1] made of a polymer of a fluorine-containing monomer Bae Riku <br/> le film board or these stripping steps, temperature is in keeping the cooling temperature in -50 ° C. to 10 ° C. gas method for producing <br/> Periku Le, characterized in that Nau line.