JP2020166063A - Method for producing pellicle - Google Patents

Abstract

To provide a method for producing a pellicle capable of removing a foreign matter generated after a pellicle film is pasted on a pellicle frame.SOLUTION: There is provided a method for producing a pellicle having a pellicle film and a pellicle frame on which the pellicle film is pasted, which comprises: a pasting step of pasting a pellicle film having a larger outer diameter than a pellicle frame to the pellicle frame; a trimming step of trimming the pellicle film which protrudes from the outer periphery of the pellicle frame; and a solvent application step of applying a nonaqueous solvent containing a compound having a specific structure to the pellicle frame after the trimming step.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a pellicle.

In the manufacturing process of semiconductor devices such as LSIs (large-scale integrated circuits) and superLSIs, or liquid crystal display plates, light is irradiated through a mask (exposure original plate) to form various patterns. At this time, if foreign matter adheres to the mask, the foreign matter absorbs the light or refracts the light. As a result, the patterning accuracy is lowered and the quality and appearance of the obtained device are impaired. Therefore, it is common to attach a pellicle to the mask surface to prevent foreign matter from adhering to the mask.

The pellicle is usually composed of a pellicle film capable of transmitting light for patterning and a pellicle frame that supports the outer circumference of the pellicle film. The pellicle frame is made of aluminum, stainless steel, polyethylene, or the like. On the other hand, the pellicle film is generally composed of a film made of nitrocellulose, cellulose acetate, fluororesin or the like (for example, Patent Document 1).

International Publication No. 2012/004950

As described above, the pellicle is a member for preventing foreign matter from adhering to the mask in the semiconductor lithography process. Therefore, measures have been taken such as manufacturing in a clean room so that foreign matter does not adhere to the pellicle itself. However, in the process of manufacturing the pellicle, there is a problem that dust is easily generated and this easily adheres to the pellicle frame. In a general method for manufacturing a pellicle, a pellicle film having an outer diameter larger than that of the pellicle frame is attached to the pellicle frame via an adhesive or the like. Then, the portion protruding from the pellicle frame is cut and removed (trimmed) with a knife or the like. At the time of this trimming, a piece of the pellicle film became fine dust and adhered to the pellicle frame, and it was easy to become a foreign substance. Further, when trying to physically remove the dust generated after the pellicle film is attached, it takes a lot of time and effort, and it is difficult to completely remove the dust. Therefore, there is a problem that the pellicle cannot be produced efficiently.

An object of the present invention is to provide a method for producing a pellicle, which can easily remove foreign substances generated after the pellicle film is attached to the pellicle frame.

（一般式（１）において、Ｘ^１〜Ｘ^６は、フッ素原子、水素原子、フッ素原子を有するアルキル基、アルキル基、アルケニル基、またはアルキニル基のいずれかを表し、
Ｘ^１〜Ｘ^６のうち、４つ以上がフッ素原子である）

（一般式（２）において、Ｙ^１〜Ｙ^６は、フッ素原子、水素原子、フッ素原子を有するアルキル基、アルキル基、アルケニル基、またはアルキニル基のいずれかを表し、
Ｙ^１〜Ｙ^６のうち、３つ以下がフッ素原子である（ただし、Ｙ^１〜Ｙ^６のうち１つ以下がフッ素原子である場合、Ｙ^１〜Ｙ^６のうち少なくとも１つがフッ素原子を有するアルキル基である））を有する、ペリクルの製造方法。 The present invention provides the following methods for producing pellicle.
[1] A method for manufacturing a pellicle having a pellicle film and a pellicle frame to which the pellicle film is attached, wherein the pellicle film having an outer diameter larger than that of the pellicle frame is attached to the pellicle frame. A trimming step of trimming the pellicle film protruding from the outer periphery of the pellicle frame, and a compound represented by the following general formula (1) and / or the following general formula (2) at the end of the pellicle frame after the trimming step. ), And a solvent application step of applying a non-aqueous solvent containing the compound represented by).

(In the general formula (1), X ^{1 to} X ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group.
Of X ^{1 to} X ⁶ , 4 or more are fluorine atoms)

(In the general formula (2), Y ^{1 to} Y ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group.
If 3 or less of Y ^{1 to} Y ⁶ are fluorine atoms (provided that 1 or less of Y ^{1 to} Y ⁶ are fluorine atoms, then at least one of Y ^{1 to} Y ⁶ has a fluorine atom. A method for producing a pellicle having an alkyl group)).

[2] The method for producing a pellicle according to [1], wherein the non-aqueous solvent to be applied in the solvent coating step contains a compound represented by the general formula (1).
[3] The non-aqueous solvent to be applied in the solvent coating step is tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene, perfluorotoluene and 2,3. The method for producing a pellicle according to [1] or [2], which comprises any compound selected from the group consisting of 4,5,6-pentafluoro-pentafluoroethylbenzene.

[4] The method for producing a pellicle according to any one of [1] to [3], wherein the non-aqueous solvent applied in the solvent coating step contains 30 to 50% by mass of hexafluorobenzene.
[5] The pellicle frame has a chamfered portion at the outer peripheral end of the surface to which the pellicle film is attached, and the non-aqueous solvent is applied to the chamfered portion in the solvent application step [1] to [4]. The method for producing a pellicle according to any one of.

According to the method for producing a pellicle of the present invention, foreign matter generated after the pellicle film is attached to the pellicle frame can be removed, and a pellicle without foreign matter adhering can be manufactured.

It is a figure which shows an example of the pellicle frame included in the pellicle of this invention.

Hereinafter, the method for producing the pellicle of the present invention will be described.
The pellicle produced by the production method of the present invention has a pellicle film and a pellicle frame to which the pellicle film is attached.

As described above, the pellicle is required to be free of foreign matter. However, when a pellicle film having an outer diameter larger than that of the pellicle frame is attached and then the pellicle film is trimmed to produce a pellicle, a piece of the pellicle film tends to cause a foreign substance.

On the other hand, in the method for producing a pellicle of the present invention, (a) a sticking step of sticking a pellicle film having an outer diameter larger than that of the pellicle frame to the pellicle frame, and (b) trimming the pellicle film protruding from the outer periphery of the pellicle frame. The trimming step is performed, and (c) a solvent coating step of applying a non-aqueous solvent containing a compound having a specific structure to the end portion of the pellicle frame after the trimming step is included. As a result of diligent studies by the present inventors, a compound having a specific structure (non-aqueous solvent) can dissolve the pellicle membrane very efficiently, and the foreign matter derived from the pellicle membrane that causes the foreign matter is found. It became clear that can be removed.

That is, according to the method for producing a pellicle of the present invention, foreign matter derived from the pellicle film adhering to the pellicle frame can be easily removed. Hereinafter, each step of the method for producing a pellicle film of the present invention will be described.

(A) Pasting step In (a) pasting step of the method for producing a pellicle of the present invention, a pellicle frame and a pellicle film are prepared, and the pellicle film is pasted on the pellicle frame.

A plan view of an example of the pellicle frame 11 used in this step is shown in FIG. 1A, and a side view of the pellicle frame 11 is shown in FIG. 1B. The shape of the pellicle frame 11 is appropriately selected according to the application of the pellicle, that is, the shape of the mask to which the pellicle is attached. For example, it may be a square frame or the like that surrounds the light irradiation surface of the mask (not shown). The width of the pellicle frame 11 is not particularly limited as long as it can sufficiently support the pellicle film (not shown) to be attached. Further, the height of the pellicle frame 11 is not particularly limited as long as it does not interfere with the pattern arranged on the mask.

In the present invention, it is particularly preferable to have the chamfered portion 11A at the outer peripheral end of the surface of the pellicle frame 11 on the side to which the pellicle film is attached. When the pellicle frame 11 has the chamfered portion 11A, as will be described later, in the solvent coating step, the pellicle frame 11 does not apply a non-aqueous solvent to the surface to which the pellicle film (not shown) and the pellicle frame 11 are attached. The non-aqueous solvent can be applied only to the chamfered portion 11A and the side surface 11B of the pellicle frame 11. As a result, only the foreign matter adhering to the chamfered portion 11A of the pellicle frame 11 or the side surface of the pellicle frame 11 can be dissolved (removed) without dissolving the pellicle film (not shown).

The angle and width of the chamfered portion 11A are not particularly limited as long as the object and effect of the present invention are not impaired, but it is particularly preferable that the pellicle frame 11 is C chamfered. When the chamfered portion 11A is a C chamfered region, when the non-aqueous solvent is applied to the chamfered portion 11A, it becomes difficult for the non-aqueous solvent to flow into the adhesion surface between the pellicle film and the pellicle frame 11.

Here, the material of the pellicle frame is not particularly limited as long as the pellicle film can be attached via an adhesive or the like. Examples of pellicle frames include aluminum, aluminum alloys, magnesium alloys, titanium, brass, iron, stainless steel and the like. Of these, aluminum alloys are preferable from the viewpoints of weight, workability, durability and the like.

A mask adhesive layer for attaching the pellicle to the mask may be arranged on the surface of the pellicle frame 11 on the side where the pellicle film is not attached. The mask adhesive layer is the same as a known mask adhesive layer, and examples thereof include a double-sided adhesive tape, a silicone resin adhesive, an acrylic adhesive, and the like. Further, the mask adhesive layer may be protected by a protective member or the like until immediately before the pellicle is attached to the mask.

On the other hand, the pellicle film prepared in this step has an outer diameter larger than that of the pellicle frame. That is, when it is attached to the pellicle frame, at least a part of it protrudes. When the pellicle film has substantially the same size (outer diameter) as the pellicle frame, it becomes difficult to align the pellicle film and the pellicle frame. On the other hand, by making the size (outer diameter) of the pellicle film larger than that of the pellicle frame, the alignment between the pellicle film and the pellicle frame becomes easy, and the pellicle can be efficiently produced. The pellicle film may have a size that protrudes from the entire circumference when attached to the pellicle frame, or may have a size that only a part of the pellicle film protrudes.

The thickness of the pellicle film is appropriately set according to the intended use of the pellicle, but is usually preferably 1 μm or less. The thinner the pellicle film is, the higher the transmittance of the light (exposure light) irradiating the mask is likely to be.

Here, the material constituting the pellicle film is appropriately selected according to the type of exposure light and the like, and is not particularly limited as long as it is a film that can sufficiently transmit the exposure light and is difficult to be decomposed by the exposure light. Further, an antioxidant film or a heat radiating film may be laminated on one surface or both surfaces of the pellicle film, if necessary.

Examples of the material constituting the pellicle film include fluororesin such as amorphous fluoropolymer, nitrocellulose, cellulose acetate and the like, and amorphous fluoropolymer is particularly preferable. The amorphous fluoropolymer has high solubility in a non-aqueous solvent described later.

Here, "amorphous" means that a clear diffraction phenomenon is not shown by the X-ray diffraction method. The pellicle film made of an amorphous fluoropolymer has high transmittance to excimer laser light (general exposure light), and can be, for example, a film having a transmittance of 99% or more for light having a wavelength of 193 nm. Further, the pellicle film made of an amorphous fluoropolymer tends to become a self-supporting film when the thickness is 1 μm or less, and is very easy to handle. The self-supporting membrane means a membrane that does not wrinkle or loosen when attached to the pellicle frame.

Examples of amorphous fluoropolymers include perfluoroalicyclic polymers having a cyclic structure in the main chain and chained perfluoropolymers having no cyclic structure in the main chain.

上記構造式において、ｍは０または１であり、ｎは１０〜１×１０^４の範囲である。 Examples of the perfluoroalicyclic polymer having a cyclic structure in the main chain include a polymer having a cyclic perfluoroether group represented by the following chemical formula as a repeating unit. Other examples of perfluoroalicyclic polymers include polymers shown in JP-A-2000-275817 and the like.

In the above structural formula, m is 0 or 1, n is in the range of between 1:10 × 10 ^4.

Examples of perfluoroalicyclic polymers include Cytop (CYTOP, manufactured by Asahi Glass Co., Ltd.) and the like.

上記一般式において、Ｘ^１およびＸ^２はそれぞれ独立に、ＨまたはＦを表し、Ｘ^３はＨ、Ｆ、ＣＨ_３、またはＣＦ_３を表し、Ｘ^４およびＸ^５はそれぞれ独立に、Ｈ、Ｆ、またはＣＦ_３を表し、a、ｂおよびｃはそれぞれ独立に、０または１を表す。 On the other hand, an example of a chain perfluoropolymer having no cyclic structure in the main chain includes a polymer having a repeating unit represented by the following general formula. Other examples of the chain perfluoropolymer include the polymers shown in JP-A-2003-57803.

In the above general formula, X ¹ and X ² independently represent H or F, X ³ represents H, F, CH _3, or CF ₃ , and X ⁴ and X ⁵ independently represent H and F, respectively. , Or CF ₃ , and a, b, and c independently represent 0 or 1, respectively.

When a is 0, Rf is a linear or branched fluoroalkyl group having 4 to 100 carbon atoms in which at least a part of a hydrogen atom is replaced with a fluorine atom, or a linear or linear group having 4 to 100 carbon atoms. Represents a fluoroalkyl group that is branched and contains an ether bond in which at least a part of a hydrogen atom is replaced with a fluorine atom. On the other hand, when a is 1, Rf is a linear or branched chain having 3 to 99 carbon atoms in which at least a part of hydrogen atoms is replaced with a fluorine atom, or a direct group having 3 to 99 carbon atoms. Represents a fluoroalkyl group containing an ether bond in the form of a chain or branched chain in which at least a part of a hydrogen atom is replaced with a fluorine atom.

The method for producing the pellicle film is not particularly limited, and the pellicle film may be produced by forming a pellicle film on various substrates by a spin coating method or the like and peeling the pellicle film from the substrate. At this time, the method of peeling the substrate is not particularly limited, and a method of physically peeling the substrate may be used, or a method of melting and removing the substrate by etching or the like may be used.

Here, the method of sticking the above-mentioned pellicle film and the pellicle frame is not particularly limited, and various adhesives are applied on the pellicle frame with a dispenser or the like, prebaked as necessary, and then the pellicle film is adhered (adhesive). It may be placed on a film adhesive layer). After the pellicle film is placed, the film adhesive may be cured by heating, irradiating with active light, or the like, if necessary. Examples of the film adhesive include an acrylic resin adhesive, an epoxy resin adhesive, a silicone resin adhesive, a polyimide resin adhesive, a fluorine-containing silicone adhesive and the like.

(B) Trimming step In the (b) trimming step of the method for producing a pellicle of the present invention, a portion of the pellicle film pasted by the above-mentioned (a) pasting step is removed from the outer periphery of the pellicle frame (in the present specification). Also called "trimming").

The trimming method is not particularly limited, and for example, an unnecessary portion of the pellicle film can be cut with a cutter, a knife, a laser, or the like. Further, the method using an organic solvent may be used.

(C) Solvent coating step In the (c) solvent coating step of the method for producing a pellicle of the present invention, the compound represented by the following general formula (1) and / / are attached to the end of the pellicle frame after the above (b) trimming step. Alternatively, a non-aqueous solvent containing the compound represented by the following general formula (2) is applied. The non-aqueous solvent may contain only one of the compound represented by the following general formula (1) and the compound represented by the following general formula (2), or may contain both. It is preferable to include a compound represented by the following general formula (1). Further, a non-aqueous solvent other than these structures may be further contained.

The total amount of the compound represented by the following general formula (1) and the compound represented by the following general formula (2) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the non-aqueous solvent applied in this step. 30 to 70 parts by mass is more preferable, and 30 to 50 parts by mass is further preferable. When the total amount of the compound represented by the following general formula (1) and the compound represented by the following general formula (2) is 10 parts by mass or more, foreign substances derived from the pellicle membrane adhering to the pellicle frame can be easily dissolved even at room temperature. .. On the other hand, when the amount is 70 parts by mass or less, the non-aqueous solvent is less likely to remain on the pellicle, outgas is less likely to be generated, and the non-aqueous solvent is less likely to remain on the pellicle surface.

上記一般式（１）において、Ｘ^１〜Ｘ^６は、フッ素原子、水素原子、フッ素原子を有するアルキル基、アルキル基、アルケニル基、またはアルキニル基のいずれかを表し、Ｘ^１〜Ｘ^６のうち、４つ以上がフッ素原子である。

上記一般式（２）において、Ｙ^１〜Ｙ^６は、フッ素原子、水素原子、フッ素原子を有するアルキル基、アルキル基、アルケニル基、またはアルキニル基のいずれかを表し、Ｙ^１〜Ｙ^６のうち、３つ以下がフッ素原子である（ただし、Ｙ^１〜Ｙ^６のうち１つ以下がフッ素原子である場合、Ｙ^１〜Ｙ^６のうち少なくとも１つがフッ素原子を有するアルキル基である。

In the above general formula (1), X ^{1 to} X ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group, and among X ^{1 to} X ⁶ , Four or more are fluorine atoms.

In the above general formula (2), Y ^{1 to} Y ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group, and among Y ^{1 to} Y ⁶ , three following is a fluorine atom (provided that when the following one of Y ¹ to Y ⁶ is a fluorine atom, an alkyl group having at least one fluorine atom in Y ¹ to Y ^6.

The alkyl group having a fluorine atom preferably has 4 or less carbon atoms, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, and 3 , 3,3-Trifluoropropyl group, perfluoropropyl group, 2,2,2,2', 2', 2'-hexafluoroisopropyl group, perfluoroisopropyl group, perfluorobutyl group and the like.

The alkyl group preferably has 6 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group and the like. Is done.

The alkenyl group preferably has 4 or less carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-propenyl group, a 1-methylvinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1-. It contains a methyl-1-propynyl group, a 1-ethylvinyl group, a 1-methylallyl group and the like.

The alkynyl group preferably has 4 or less carbon atoms, and examples thereof include an ethynyl group, a 1-propynyl group, a propargyl group, a 1-butynyl group, and a 2-butynyl group.

Specific examples of the compound represented by the general formula (1) include hexafluorobenzene, pentafluorobenzene, 2,3,4,5,6-pentafluorotoluene, and 2,3,4,5,6-penta. Fluoroethylbenzene, perfluorotoluene, 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 2,3,4,5 -Tetrafluorotoluene, 2,3,4,5-tetrafluoroethylbenzene, 2,3,4,6-tetrafluorotoluene, 2,3,4,6-tetrafluoroethylbenzene, 2,3,5,6-tetra Fluorotoluene, 2,3,5,6-tetrafluoroethylbenzene, 2,3,4,5-tetrafluoro-1-trifluoromethylbenzene, 2,3,4,6-tetrafluoro-1-trifluoromethylbenzene , 2,3,5,6-tetrafluoro-1-trifluoromethylbenzene, 2,3,4,5,6-pentafluoro-pentafluoroethylbenzene and the like are included. The non-aqueous solvent may contain only one kind of the compound represented by the above general formula (1), or may contain two or more kinds.

Among these, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene, and perfluorotoluene are easy to obtain and remove foreign substances derived from the pellicle film. And 2,3,4,5,6-pentafluoro-pentafluoroethylbenzene are preferred.

On the other hand, specific examples of the compound represented by the above general formula (2) include 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 2,3-difluorotoluene, and 2,4. -Difluorotoluene, 2,5-difluorotoluene, 2,6-difluorotoluene, 2,3-difluoroethylbenzene, 2,4-difluoroethylbenzene, 2,5-difluoroethylbenzene, 2,6-difluoroethylbenzene, 2,3- Difluoro-1-trifluoromethylbenzene, 2,4-difluoro-1-trifluoromethylbenzene, 2,-difluoro-1-trifluoromethylbenzene, 2,6-difluoro-1-trifluoromethylbenzene, 1,2 , 3-Trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 2,4,6-trifluorotoluene, 2,4,6-trifluoroethylbenzene, 2,4 , 6-Trifluoro-1-trifluoromethylbenzene, benzotrifluoride, 2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 2-methylbenzotrifluoride, 3-methylbenzotrifluo Lido, 4-methylbenzotrifluoride, 1,2-bis (trifluoromethyl) benzene, 1,3-bis (trifluoromethyl) benzene, 1,4-bis (trifluoromethyl) benzene and the like are included. The non-aqueous solvent may contain only one kind of the compound represented by the above general formula (2), or may contain two or more kinds.

Among the above, hexafluorobenzene is particularly preferable in that foreign substances derived from the pellicle film can be easily removed, and it is preferable that hexafluorobenzene is contained in an amount of 30 to 50 parts by mass with respect to the total amount of the non-aqueous solvent, and 30 to 50 parts by mass. It is more preferable to include a part.

The other solvent contained in the non-aqueous solvent is not particularly limited as long as it is a non-aqueous solvent compatible with the compound represented by the above general formula (1) or the compound represented by the general formula (2). .. Examples include various fluorosolvents. The non-aqueous solvent may contain only one kind of other solvent, or may contain two or more kinds.

Examples of other solvents include perfluoroalkylamines such as CH ₃ CCl ₂ F, CF ₃ CF ₂ CHCl ₂ , CClF ₂ CF ₂ CHClF, perfluorohexane, perfluorotributylamine, and perfluoro (2-butyl tetrahydrofuran). , Methoxy-nonafluorobutane, fluorinated alcohols, ClCF ₂ CFClCF ₂ CFCl ₂ , tridecafluorooctane, decafluoro-3-methoxy-4 (trifluoromethyl) pentane and the like.

Here, the method of applying the non-aqueous solvent in this step is not particularly limited, and is not particularly limited as long as the foreign matter derived from the pellicle film can be removed. As an example of the method of applying the non-aqueous solvent only to a desired region, application with a dispenser or the like can be given. In particular, the needle type dispenser is preferable because a small amount of non-aqueous solvent can be applied only to a desired region.

At this time, it is preferable to apply the non-aqueous solvent with the sticking surface of the pellicle film and the pellicle frame in the direction of gravity. Further, the non-aqueous solvent is preferably applied to the end portion (outer peripheral side) of the pellicle frame, and when the pellicle frame has the above-mentioned chamfered portion, it is preferably applied to the chamfered portion and the side surface. When a non-aqueous solvent adheres to the sticking surface between the pellicle film and the pellicle frame, the pellicle film in the region may be dissolved, the adhesive strength between the pellicle film and the pellicle frame may decrease, or the pellicle film may have holes. is there.

The non-aqueous solvent may be applied all around the circumference of the pellicle frame, or may be applied only to a necessary area. Further, the non-aqueous solvent may be applied only once, or may be applied in two or more times.

After applying the non-aqueous solvent, the non-aqueous solvent may be volatilized at room temperature, or may be volatilized by heating or the like. It is preferable to sufficiently remove the non-aqueous solvent before storing in a case or the like. This makes it easier to suppress the generation of outgas when the pellicle is attached to the mask and exposed.

The present invention will be described in detail based on examples, but the present invention is not limited to these examples.

[Non-aqueous solvent]
In each Example and Comparative Example, the following non-aqueous solvents were used alone or in combination in the solvent coating step.
・ Perfluorobenzene (manufactured by Tokyo Kasei Co., Ltd.)
・ AC6000 (3M, Tridecafluorooctane)
-FC43 (3M, Tris (perfluorobutyl) amine)
-FC75 (3M, perfluoro (butyl tetrahydrofuran))
・ Perfluorononane (manufactured by Tokyo Kasei Co., Ltd.)
・ Perfluoro (1,3-dimethylcyclohexane) (manufactured by Tokyo Kasei Co., Ltd.)

[Example 1]
-Attachment process (preparation of pellicle film and attachment of pellicle film to pellicle frame)
A pellicle film was formed on a glass substrate by spin coating a Cytop solution (trade name "CYTOP", manufactured by AGC Inc., concentration 9% by mass). Next, an adhesive was applied to a temporary frame (made of plastic) for peeling whose inner diameter was larger than the outer diameter of the pellicle described later, and was attached to the pellicle film. Then, the pellicle film was peeled off from the glass substrate to make the pellicle film self-supporting.

On the other hand, an adhesive (trade name "CYAF", manufactured by AGC Inc.) was applied to a pellicle frame made of anodized aluminum (outer dimensions: 149 mm × 122 mm, frame height: 5.8 mm, frame width: 2 mm). As the pellicle frame, a frame having a C chamfered along the outer circumference of the sticking surface of the pellicle film was used. Then, the pellicle frame (adhesive) was uniformly pressed against the self-supporting pellicle film so as not to wrinkle, and the adhesive was cured by irradiation with ultraviolet light.

・ Trimming process (trimming of pellicle film)
The unnecessary pellicle film protruding from the pellicle frame was cut off with a blade along the frame.

・ Solvent application process (removal of foreign matter)
When the pellicle after trimming the pellicle film was visually confirmed, debris (foreign matter derived from the pellicle film) after being cut with a blade was attached to the chamfered portion (C surface) of the pellicle frame. Therefore, perfluorobenzene (manufactured by Tokyo Kasei Co., Ltd.) was applied to the chamfered portion (C surface) of the pellicle frame with a needle-type dispenser (needle diameter: 0.312 μm, dropping rate: 0.12 (mL / min)). , This was dried.

[Examples 2 and 3 and Comparative Examples 1 to 5]
As shown in Table 1, a pellicle was prepared in the same manner as in Example 1 except that the type of the non-aqueous solvent in the solvent coating step was changed as shown in Table 1.

[Evaluation]
The pellicle produced in Examples and Comparative Examples was evaluated as follows.

(Solubility of foreign matter at room temperature)
The solubility of foreign substances in the non-aqueous solvent used in Examples and Comparative Examples at room temperature was confirmed as follows. First, the pellicle membranes used in Examples and Comparative Examples were prepared, and 1 μL to 2 μL of a non-aqueous solvent was added dropwise to the pellicle membrane. Then, after 5 seconds, it was visually confirmed whether or not a hole was opened. The evaluation was based on the following criteria.
◯: Dissolved at room temperature Δ: A small amount dissolved at room temperature ×: Not dissolved at room temperature

(Outgas and liquid sauce)
Each pellicle was installed in a chamber (manufactured by GF Science). After installation, the mixture was heated at 50 ° C. for 4 hours, and the generated gas component was adsorbed on a TENAX collection tube and analyzed by TD-GCMS (manufactured by Shimadzu Corporation). At the same time, the liquid adhering to the pellicle frame of the pellicle (hereinafter, also referred to as “liquid sauce”) was visually confirmed. It was evaluated according to the following criteria.
⊚: No peak derived from non-aqueous solvent was detected by TD-GCMS and no liquid dripping. 〇: No peak derived from non-aqueous solvent was detected by TD-GCMS, but liquid dripping was present. ×: TD-GCMS A peak derived from a non-aqueous solvent was detected in

(Foreign matter remaining)
After the solvent was applied in the above-mentioned solvent application step, the pellicle was irradiated with light using Senalite (high-intensity halogen certification device, manufactured by Senna and Burns), and the presence or absence of foreign matter was visually confirmed. At the same time, the dissolution state of the foreign matter was confirmed by observing with an optical microscope even at 100 times.

As shown in Table 1, FIGS. 2A and 2B, when a non-aqueous solvent containing the compound (perfluorobenzene) represented by the above general formula (1) is applied in the solvent application step (Examples 1 to 3). ), The foreign matter could be sufficiently removed. Further, when these non-aqueous solvents were used, no outgas was generated and no liquid dripping occurred.

On the other hand, as shown in Table 1, FIG. 2C and FIG. 2D, the compound represented by the above general formula (1) or the compound represented by the general formula (2) (perfluorobenzene) is not contained. When an aqueous solvent was used, foreign matter was likely to remain (Comparative Examples 1 to 5).

According to the method for producing a pellicle of the present invention, it is possible to remove foreign substances generated after the pellicle film is attached to the pellicle frame, which is very useful for producing a pellicle, and eventually a semiconductor device.

11 Pellicle frame 11A Chamfered part 11B Side surface

Claims (5)

A method for manufacturing a pellicle having a pellicle film and a pellicle frame to which the pellicle film is attached.
A sticking step of sticking a pellicle film having an outer diameter larger than that of the pellicle frame to the pellicle frame,
A trimming step of trimming the pellicle film protruding from the outer circumference of the pellicle frame, and
A solvent coating step of applying a non-aqueous solvent containing a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) to the end of the pellicle frame after the trimming step. ,

(In the general formula (1), X ^{1 to} X ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group.
Of X ^{1 to} X ⁶ , 4 or more are fluorine atoms)

(In the general formula (2), Y ^{1 to} Y ⁶ represent any of a fluorine atom, a hydrogen atom, an alkyl group having a fluorine atom, an alkyl group, an alkenyl group, or an alkynyl group.
If 3 or less of Y ^{1 to} Y ⁶ are fluorine atoms (provided that 1 or less of Y ^{1 to} Y ⁶ are fluorine atoms, then at least one of Y ^{1 to} Y ⁶ has a fluorine atom. Alkyl group)))
A method for manufacturing a pellicle. The non-aqueous solvent applied in the solvent application step contains a compound represented by the general formula (1).
The method for producing a pellicle according to claim 1. The non-aqueous solvents to be applied in the solvent coating step are tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, 2,3,4,5,6-pentafluorotoluene, perfluorotoluene and 2,3,4,5. , Contains any compound selected from the group consisting of 6-pentafluoro-pentafluoroethylbenzene,
The method for producing a pellicle according to claim 1 or 2. The non-aqueous solvent applied in the solvent application step contains 30 to 50% by mass of hexafluorobenzene.
The method for producing a pellicle according to any one of claims 1 to 3. The pellicle frame has a chamfered portion at the outer peripheral end of the surface to which the pellicle film is attached.
In the solvent coating step, the non-aqueous solvent is applied to the chamfered portion.
The method for producing a pellicle according to any one of claims 1 to 4.

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