KR20060065231A - Photomask and Method for Manufacturing the Semiconductor Device - Google Patents

Abstract

Disclosed is a photo mask for manufacturing a semiconductor device and a method of manufacturing the same, which attach an ion exchange resin inside a pellicle frame for attaching a pellicle to prevent generation of growth foreign matter on the upper surface of the photo mask. The photomask of the present invention forms a chrome pattern on a transparent substrate, forms a pellicle frame for attaching pellicles to the front surface of the transparent substrate, and attaches an ion exchange resin to the inside of the pellicle frame, and then transmits light on the pellicle frame. By adhering the pellicle of the material, by adsorbing the ions generated by the adhesive resin for attaching the pellicle to the inside of the predetermined space formed between the transparent substrate and the pellicle frame, it prevents the growth of foreign substances on the surface of the photomask. do.

Photomask, pellicle, ion exchange resin, growth foreign substance

Description

Photomask for manufacturing semiconductor device and method of manufacturing the same {Photomask for fabricating semiconductor device and method

1A to 1D are cross-sectional views of a manufacturing process according to an embodiment of a photomask according to the prior art.

1A is a cross-sectional view illustrating a first adhesive resin applied around a light shielding layer pattern formed on a transparent substrate,

FIG. 1B is a cross-sectional view illustrating a pellicle frame formed on an upper surface of the first adhesive resin of FIG. 1A.

FIG. 1C is a cross-sectional view for describing a second adhesive resin applied to the upper surface of the pellicle frame of FIG. 1B.

FIG. 1D is a cross-sectional view for describing a pellicle formed on a front surface of a pellicle frame in contact with the second adhesive resin of FIG. 1C.

2A to 2C are cross-sectional views of a manufacturing process procedure according to an embodiment of a photomask according to the present invention;

FIG. 2A is a cross-sectional view illustrating a pellicle frame formed on a transparent substrate and having an ion exchange resin formed on an inner side thereof in the same manner as in FIG.

FIG. 2B is a cross-sectional view for describing a second adhesive resin applied to the pellicle frame upper surface of FIG. 2A.

FIG. 2C is a cross-sectional view for describing a pellicle formed on the front surface of the pellicle frame in contact with the second adhesive resin of FIG. 2B.

Explanation of symbols on the main parts of the drawings

1, 10: transparent substrate 2, 20: light shielding layer pattern or shift layer pattern

3, 30: first adhesive resin 4, 40: pellicle frame

5, 50: exhaust port 55: ion exchange resin

6, 60: second adhesive resin 7, 70: pellicle

The present invention relates to an apparatus for recycling a pellicle of a photomask, and in particular, ions secreted by an adhesive resin by attaching an ion exchange resin in contact with a side inner surface of a pellicle frame that is adhered and fixed by an adhesive resin to a quartz plate of a photomask. The present invention relates to a pellicle frame device of a photomask for preventing growth of foreign matters or the like on the photomask.

In general, a photomask is a structure of a semiconductor device or an integrated circuit formed on a chromium-deposited glass plate, which is transferred to a wafer by using photolithography (Photo Lithography) to manufacture a semiconductor device. Refers to a substrate device of quartz, in which a semiconductor device circuit is printed.

As described above, there are various types of photomasks, and most of these photomasks have, as described above, a general series in which chromium is coated as a light shielding layer on the upper surface of a quartz substrate (hereinafter referred to as quartz plate), and a molybdenum series There is a phase inversion photomask device that coats the back. A photomask formed by forming a metal pattern such as a circuit board through a predetermined photo process and an etching process on the light-shielding metal film is formed on the wafer through light using a reduction stepper. The pattern of transfer will be formed.

On the upper side of the photomask, a thin, optically transparent fluoropolymer or nitrocellulose film called a pellicle is laminated. The pellicle is supported by the pellicle frame and attached to the photomask, and used to reduce the printing and to remove the defect caused by the foreign matter in the planar image of the exposure apparatus.

In general, the pellicle is bonded to the distal surface of the pellicle frame by placing the damp pellicle frame on the end plane on the plastic film using an organic solvent capable of dissolving the plastic resin of the pellicle and then drying the air. Alternatively, adhesive resins such as acrylic resins and epoxy resins can of course be used.

1A to 1D are cross-sectional views of a manufacturing process according to an embodiment of a photomask according to the prior art, on a transparent substrate 1 around a light shielding layer pattern 2 formed on the transparent substrate 1 as shown. Applying a first adhesive resin 3 (FIG. 1A), attaching and fixing a pellicle frame 4 to the upper surface of the first adhesive resin 3 (1b), and the pellicle frame 4. Applying a second adhesive resin 6 to the upper surface (FIG. 1C), and fixing and attaching the pellicle 7 to the upper front surface of the pellicle frame 4 in contact with the second adhesive resin 6 ( It is produced through 1d).

Hereinafter, an embodiment of the photomask manufacturing process according to the prior art as described above in more detail.

First, as shown in FIG. 1A, a light shielding layer pattern 2 is formed by depositing and patterning a light shielding layer blocking light emitted on an upper portion of the transparent substrate 1 that transmits light to be irradiated, thereby forming a light shielding layer pattern 2. The first adhesive resin 3 is applied onto the transparent substrate 1 around the area where the light shielding layer pattern 2 is formed. The transparent substrate 1 has a thickness of 2 ~ 7mm. The light shielding layer pattern 2 mainly uses Cr or CrO ₆ in consideration of the adhesive property with the transparent substrate 1, but if necessary, a phase shift material that transmits only a part of light and changes its phase may be used. Examples of shift materials include MoSiON, CrON, WSi and SiN.

The type of the first adhesive resin 3 which bonds the pellicle frame 4 to the upper surface of the transparent substrate 1 is not particularly limited, and may be an acrylic resin, an epoxy resin, a polybutene resin, a polyurethane resin, a cellulose polymer, or a silicone resin. Any one selected from the group consisting of a resin, a fluorocarbon resin and a rubber polymer and a compound thereof can be used.                         

Next, as shown in FIG. 1B, the pellicle frame 4 is adhesively fixed in contact with the upper surface of the first adhesive resin 3. The pellicle frame 4 is a frame made of steel such as aluminum alloy, stainless steel, polyethylene, and has a height of about 5-9 mm. The pellicle frame 4 may include an exhaust port 5 so that a predetermined space formed between the transparent substrate 1 and the pellicle frame 4 can communicate with the outside of the pellicle frame 4.

Then, the second adhesive resin 6 is applied to the upper surface of the pellicle frame 4, as shown in Figure 1c. The type of the second adhesive resin 6 that bonds the pellicle 7 to the pellicle frame 4 is not particularly limited, and may be acrylic resin, epoxy resin, polybutene resin, polyurethane resin, cellulose polymer, silicone resin, Any one selected from the group consisting of fluorocarbon resins and rubber polymers and compounds thereof can be used. However, when the pellicle is made from an amorphous fluorocarbon group-containing polymer, it is common to use a fluorocarbon-containing polymer resin-based adhesive resin having the same or similar type of amorphous chemical structure as the polymer forming the pellicle film having excellent compatibility. to be. Such a fluorocarbon-based amorphous polymer may be used as an adhesive resin in the form of a solution dissolved in a fluorocarbon-based solvent. The second adhesive resin 6 may be made of the same material as the first adhesive resin 3 that attaches and fixes the lower end of the pellicle frame 4 to the transparent substrate 1.

On the other hand, since the second adhesive resin 6 used to bond the pellicle 7 to the pellicle frame 4 is under direct irradiation of exposure ultraviolet rays in the photolithography patterning operation, the second adhesive resin 6 is It is necessary to have high resistance to UV-induced destruction so as to ensure the durability of the pellicle 7 supported by the pellicle frame 4, which otherwise the steady state of a very thin pellicle cannot be maintained for a long time This is because the quality of the reproduction pattern is affected.

Next, as shown in FIG. 1D, the pellicle 7 is finally attached to the upper front surface of the pellicle frame 4 in contact with the second adhesive resin 6 applied to the upper surface of the pellicle frame 4. Complete the mask.

The pellicle 7 is a highly transparent thin film composed of a synthetic plastic resin, and the polymer material forming the pellicle 7 is not particularly limited, and examples thereof include nitrocellulose, poly (trimethyl vinyl silane), and pullulan compound. Of copolymers of tetrafluoroethylene and vinylidene fluoride, terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, of fluorine-containing monolayers having tetrafluoroethylene and cyclic perfluoroether groups Amorphous fluorocarbon group containing polymers, such as a copolymer, silicone modified polyvinyl alcohol, etc. are illustrated, Among these, an amorphous fluorocarbon group containing polymer can be used in a wide range of light wavelengths.

However, as described above, the first adhesive resin for bonding the pellicle frame to the transparent substrate or the second adhesive resin for bonding the pellicle to the pellicle frame are not completely isolated and are exposed to the inside and outside of the pellicle frame, thereby continuously exposing the exposure energy. Some of the organic components, sulfate ions, and ammonium ions generated as a result of photochemical reactions are introduced into a predetermined space formed between the transparent substrate and the pellicle and react with each other by the light of the exposure apparatus during the semiconductor manufacturing process. Form a growth foreign matter, such as a salt of (NH ₃ ) ₂ SO ₄ , on the phase.

Thus, (NH ₃ ) ₂ SO ₄ , a growth foreign material generated on the surface of the photomask, is not removed even after cleaning the photomask after removing the pellicle, which is a protective thin film of the photomask. There is a problem in that the defect of the device and the process yield are reduced.

The present invention is to solve the above problems, after forming a pellicle frame for attaching the pellicle to the front of the transparent substrate, the ion exchange resin is attached to the inside of the pellicle frame and the pellicle of the transparent material on the pellicle frame By adhering, ions generated by adhesive resin for pellicle attachment and adsorbing ions entering into a predetermined space formed between the transparent substrate and the pellicle frame prevent growth foreign matters from occurring on the surface of the photomask, thereby improving process yield and device operation reliability. An improved photomask for manufacturing a semiconductor device and a method of manufacturing the same are provided.

One embodiment of the present invention for achieving the above technical problem provides a photo mask for manufacturing a semiconductor device.

The photomask for manufacturing the semiconductor device may include a transparent substrate, a light shielding layer pattern formed on a surface of the transparent substrate, a pellicle frame formed around the light shielding layer pattern, an ion exchange resin formed on an inner side surface of the pellicle frame, and the upper surface of the pellicle frame It characterized by comprising a pellicle formed on.

Here, the light blocking layer pattern may be formed of a metal material, for example, Cr or CrO _{6. If} necessary, a shift material may be used to transmit only a part of light and change a phase. Examples of shift materials include MoSiON, CrON, WSi and SiN.

The pellicle frame is adhesively fixed on the transparent substrate by a first adhesive resin applied around the light shielding layer pattern formed on the transparent substrate. The type of the first adhesive resin is not particularly limited, and any one selected from the group consisting of acrylic resins, epoxy resins, polybutenes, polyurethane resins, cellulose polymers, silicone resins, fluorocarbon resins and rubber polymers, and compounds thereof It can be one.

The pellicle frame is adhesively fixed to the upper surface of the first adhesive resin. The pellicle frame is a frame made of steel, such as aluminum alloy, stainless steel, polyethylene, and has a height of about 5-9 mm. The pellicle frame may include an exhaust port so that a predetermined space formed between the transparent substrate and the pellicle frame can communicate with the outside of the pellicle frame.

The ion exchange resin may include a cation exchange resin, an anion exchange resin or a cation exchange resin and an anion exchange resin at the same time. The cation exchange resin has a negative charge to adsorb cations in the air such as NH ₄ ⁺ , and the anion exchange resin has a positive charge to adsorb anions in the air such as SO ₄ ^2- . .

The type of the second adhesive resin is not particularly limited, and any one selected from the group consisting of acrylic resins, epoxy resins, polybutenes, polyurethane resins, cellulose polymers, silicone resins, fluorocarbon resins and rubber polymers, and compounds thereof It can be one. However, when the pellicle is made from an amorphous fluorocarbon group-containing polymer, it is common to use a fluorocarbon-containing polymer resin-based adhesive resin having the same or similar type of amorphous chemical structure as the polymer forming the pellicle film having excellent compatibility. to be. Such a fluorocarbon-based amorphous polymer may be used as an adhesive resin in the form of a solution dissolved in a fluorocarbon-based solvent. The second adhesive resin may use the same material as the first adhesive resin that attaches and fixes the lower end of the pellicle frame to the transparent substrate.

On the other hand, since the second adhesive resin used to bond the pellicle to the pellicle frame is under direct irradiation of exposure ultraviolet rays in the photolithographic patterning operation, the second adhesive resin can ensure durability of the pellicle supported by the pellicle frame. To this end, it is necessary to be highly resistant to UV-induced destruction, because otherwise the steady state of very thin pellicles cannot be maintained for a long time, affecting the quality of the regeneration pattern.

The pellicle is a highly transparent thin film composed of a synthetic plastic resin, and the polymer material forming the pellicle is not particularly limited, and examples thereof include nitrocellulose, poly (trimethyl vinyl silane), pullulan compound, and tetrafluoroethylene. Amorphous carbonization such as copolymers of vinylidene fluoride, terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, copolymers of tetrafluoroethylene and fluorine-containing monolayers having cyclic perfluoroether groups Fluorine group containing polymer, silicone modified polyvinyl alcohol, etc. are illustrated, Among these, an amorphous fluorocarbon group containing polymer can be used in a wide range of light wavelengths.

In addition, another embodiment of the present invention for achieving the above technical problem provides a photomask manufacturing method for manufacturing a semiconductor device.

The method of manufacturing a photomask for manufacturing a semiconductor device may include forming a light shielding layer pattern on a surface of a transparent substrate, forming a pellicle frame around the light shielding layer pattern, and forming an ion exchange resin on an inner side surface of the pellicle frame. And forming a pellicle on the pellicle frame upper surface.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed subject matter is thorough and complete, and that the spirit of the present invention to those skilled in the art will fully convey. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like numbers refer to like elements throughout.

Referring to FIG. 2A, after the pellicle frame 40 is formed on the transparent substrate 10 on which the light shielding layer pattern 20 is formed, the ion exchange resin (I) is formed on the inner side of the pellicle frame 40. 55) Attach and secure. The pellicle frame 40 is adhesively fixed on the transparent substrate 10 by a first adhesive resin 30 applied around the light shielding layer pattern 20 formed on the transparent substrate 10.

The type of the first adhesive resin 30 is not particularly limited and is selected from the group consisting of acrylic resins, epoxy resins, polybutenes, polyurethane resins, cellulose polymers, silicone resins, fluorocarbon resins and rubber polymers, and compounds thereof. Any one selected can be used.

The pellicle frame 40 is adhesively fixed in contact with the upper surface of the first adhesive resin 30. The pellicle frame 40 is a frame made of steel, such as aluminum alloy, stainless steel, polyethylene, and has a height of about 5-9 mm. The pellicle frame 40 may include an exhaust port 50 so that a predetermined space formed between the transparent substrate 10 and the pellicle frame 40 can communicate with the outside of the pellicle frame 40.

The ion exchange resin 55 may include a cation exchange resin, an anion exchange resin or a cation exchange resin and an anion exchange resin at the same time. The cation exchange resin has a negative charge to adsorb cations in the air such as NH ₄ ⁺ . The anion exchange resin has a positive charge and can adsorb negative ions in the air such as SO ₄ ^2- .

The ion exchange resin is aligned with the exhaust port 50 so that a predetermined space formed between the transparent substrate 10 and the pellicle frame 40 does not block the exhaust port 50 formed so as to communicate with the outside of the pellicle frame 40. Have an exhaust vent.

Referring to FIG. 2B, a second adhesive resin 60 is applied to the upper surface of the pellicle frame 40. The type of the second adhesive resin 60 is not particularly limited and is selected from the group consisting of acrylic resins, epoxy resins, polybutenes, polyurethane resins, cellulose polymers, silicone resins, fluorocarbon resins and rubber polymers, and compounds thereof. Any one selected can be used. However, in the case where the pellicle is made from an amorphous fluorocarbon group-containing polymer, it is common to use a fluorocarbon group-containing polymer resin adhesive resin having an amorphous chemical structure of the same or similar type as the polymer forming a pellicle film excellent in compatibility. . Such a fluorocarbon-based amorphous polymer may be used as an adhesive resin in the form of a solution dissolved in a fluorocarbon-based solvent. The second adhesive resin 60 may be made of the same material as that of the first adhesive resin 30 to fix the lower end of the pellicle frame 40 to the transparent substrate 10.

On the other hand, since the second adhesive resin 60 used to bond the pellicle 70 to the pellicle frame 40 is under direct irradiation of exposure ultraviolet light in the photolithography patterning operation, the second adhesive resin 60 is the pellicle The resistance to UV-induced destruction needs to be high to ensure the durability of the pellicle 70 supported by the frame 40, which otherwise would cause the steady state of a very thin pellicle to be unable to be maintained for a long time, thus regenerating This affects the quality of the pattern.

Referring to FIG. 2C, the pellicle 70 is attached and fixed to the upper front surface of the pellicle frame 40 in contact with the second adhesive resin 60. The pellicle 70 is a highly transparent thin film made of a synthetic plastic resin, and the polymer material forming the pellicle 70 is not particularly limited. Examples thereof include nitrocellulose, poly (trimethyl vinyl silane), and pullulan compound. Of copolymers of tetrafluoroethylene and vinylidene fluoride, terpolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride, of fluorine-containing monolayers having tetrafluoroethylene and cyclic perfluoroether groups Amorphous fluorocarbon group containing polymers, such as a copolymer, silicone modified polyvinyl alcohol, etc. are illustrated, Among these, an amorphous fluorocarbon group containing polymer can be used in a wide range of light wavelengths.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible in the art without departing from the technical spirit of the present invention. It will be clear to those of ordinary knowledge.

 According to the present invention, a photomask for manufacturing a semiconductor device and a method of manufacturing the same are generated by attaching an ion exchange resin to the inside of the pellicle frame and then attaching a pellicle made of a light-transmissive material on the pellicle frame. Therefore, by adsorbing ions introduced into a predetermined space formed between the transparent substrate and the pellicle frame, it is possible to prevent growth foreign matters from occurring on the surface of the photomask, thereby improving process yield and device operation reliability.

Claims (8)

Transparent substrate; A light blocking layer pattern formed on a surface of the transparent substrate; A pellicle frame formed around the light shielding layer pattern; An ion exchange resin formed on the inner side of the pellicle frame; And A photomask for manufacturing a semiconductor device comprising a pellicle formed on the front surface of the pellicle frame. The photomask of claim 1, wherein the pellicle frame has an exhaust port so that a predetermined space formed between the transparent substrate and the pellicle frame can communicate with the outside of the pellicle frame. The photomask of claim 2, wherein the ion exchange resin has an exhaust port aligned with an exhaust port of the pellicle frame. The photomask of claim 1, wherein the ion exchange resin comprises a cation exchange resin, an anion exchange resin, or a cation exchange resin and an anion exchange resin at the same time. Forming a light shielding layer pattern on a surface of the transparent substrate; Forming a pellicle frame around the light shielding layer pattern; Forming an ion exchange resin on an inner side of the pellicle frame; And A method of manufacturing a photomask for manufacturing a semiconductor device comprising the step of forming a pellicle on the front surface of the pellicle frame. The method of claim 5, wherein the pellicle frame has an exhaust port so that a predetermined space formed between the transparent substrate and the pellicle frame can communicate with the outside of the pellicle frame. . 7. The method of claim 6, wherein the ion exchange resin has an exhaust port aligned with an exhaust port of the pellicle frame. The method of claim 5, wherein the ion exchange resin comprises a cation exchange resin, an anion exchange resin, or a cation exchange resin and an anion exchange resin at the same time.

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