JP2021107939A - Production method for composition for upper layer film formation, production method for photosensitive resin composition, pattern formation method, and manufacturing method for electronic device - Google Patents

Abstract

To provide a production method for a composition for upper layer film formation or a photosensitive resin composition, having excellent coatability; and to provide a pattern formation method, and a manufacturing method for an electronic device.SOLUTION: A production method for a composition for upper layer film formation or a photosensitive resin composition, includes a first filtration step of filtering solution containing a fluorine-containing resin, a step of preparing the composition for the upper layer film formation or the photosensitive resin composition by using the solution containing the fluorine-containing resin passing through the first filtration step, and the second filtration step of filtering the composition for the upper layer film formation or the photosensitive resin composition.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a composition for forming an upper layer film, a method for producing a photosensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.

An image forming method called chemical amplification is used as an image forming method of a resist. To explain the image formation method of positive chemical amplification as an example, the photoacid generator in the exposed area decomposes to generate acid in the exposure, and the generated acid is generated in the post-exposure bake (PEB: Post Exposure Bake). This is an image forming method in which an alkali-insoluble group is changed to an alkali-soluble group by using it as a reaction catalyst, and an exposed portion is removed by alkaline development.

When applying a chemically amplified resist to immersion exposure, a method of providing an upper layer film between the resist film and the lens is known. For example, Patent Document 1 discloses a pattern forming method using a composition for forming an upper layer film containing a predetermined component.

Japanese Unexamined Patent Publication No. 2016-200761

In the scan type immersion exposure, it is necessary to move the immersion liquid in accordance with the movement of the lens. However, if the scanning speed is increased in order to improve the throughput, the immersion liquid may not be able to follow the movement of the lens. In order to solve such a problem, when an upper layer film or a resist film is formed by using a composition for forming an upper layer film or a photosensitive resin composition containing a fluorine-containing resin having a predetermined repeating unit, the immersion liquid is used. It has been proposed that the speed at which the lens can be followed can be improved.
On the other hand, the present inventors have found that there is room for improvement in the coatability of the upper layer film forming composition or the photosensitive resin composition. Specifically, it was found that the film thickness formed by applying the above-mentioned upper layer film forming composition or photosensitive resin composition onto a substrate tends to vary. In particular, such a tendency was remarkable near the outer peripheral portion of the film.

An object of the present invention is to provide a method for producing a composition for forming an upper layer film or a photosensitive resin composition having excellent coatability.
Another object of the present invention is to provide a pattern forming method and a method for manufacturing an electronic device.

As a result of diligent studies on the above problems, the present inventor has found that a desired effect can be obtained by carrying out a predetermined filtration treatment.
That is, the above problem can be solved by the means shown below.

(1) A first filtration step of filtering a solution containing a fluorine-containing resin, a step of preparing a photosensitive resin composition using a solution containing a fluorine-containing resin that has undergone the first filtration step, and the above-mentioned photosensitive. A method for producing a photosensitive resin composition, which comprises a second filtration step of filtering the resin composition, wherein the fluorine-containing resin is a repeating unit represented by the general formula (1) described later and the general formula (2). A method for producing a photosensitive resin composition, which comprises at least one selected from the group consisting of repeating units represented by.
(2) The fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (3) described later and a repeating unit represented by the general formula (4) (1). The method for producing a photosensitive resin composition according to.
(3) The method for producing a photosensitive resin composition according to (1) or (2), wherein the pore size of the filter used for filtration in the first filtration step is 0.5 μm or less.
(4) The first filtration step is a step 1 in which the solution containing the fluorine-containing resin is filtered using the first filter, and the fluorine-containing resin that has undergone the step 1 using the second filter. The method for producing a photosensitive resin composition according to any one of (1) to (3), which comprises the step 2 of filtering the containing solution.
(5) The photosensitive resin composition according to (4), wherein the first filtration step further comprises a step 3 of filtering the solution containing the fluorine-containing resin that has undergone the step 2 using a third filter. Manufacturing method of things.
(6) Any of (1) to (5), wherein the first filtration step includes a circulation filtration step in which a solution containing a fluorine-containing resin that has passed through the filter is further guided to the same filter and circulated in the system. The method for producing a photosensitive resin composition according to.
(7) A step of forming a resist film using the photosensitive resin composition obtained by the production method according to any one of (1) to (6), a step of exposing the resist film, and a step of exposing the resist film. A pattern forming method including a step of developing a resist film.
(8) A method for manufacturing an electronic device, including the pattern forming method according to (7).
(9) A first filtration step of filtering a solution containing a fluorine-containing resin, a step of preparing a composition for forming an upper layer film using a solution containing a fluorine-containing resin that has undergone the first filtration step, and the upper layer. A method for producing an upper layer film-forming composition, which comprises a second filtration step of filtering the film-forming composition, wherein the fluorine-containing resin is a repeating unit and a general formula represented by the general formula (1) described later. A method for producing a composition for forming an upper layer film, which comprises at least one selected from the group consisting of the repeating units represented by (2).
(10) The fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (3) described later and a repeating unit represented by the general formula (4) (9). The method for producing a composition for forming an upper layer film according to.
(11) The method for producing an upper layer film forming composition according to (9) or (10), wherein the pore size of the filter used for filtration in the first filtration step is 0.5 μm or less.
(12) In the first filtration step, the first filter is used to filter the solution containing the fluorine-containing resin, and the second filter is used to filter the fluorine-containing resin that has undergone the first step. The method for producing an upper layer film forming composition according to any one of (9) to (11), which comprises step 2 of filtering the containing solution.
(13) The upper layer film forming according to (12), wherein the first filtration step further includes a step 3 of filtering the solution containing the fluorine-containing resin that has undergone the step 2 using a third filter. Method for producing the composition.
(14) Any of (9) to (13), wherein the first filtration step includes a circulation filtration step in which the solution containing the fluorine-containing resin that has passed through the filter is further guided to the same filter and circulated in the system. The method for producing an upper layer film forming composition according to.
(15) A step of forming an upper layer film on a resist film using the composition for forming an upper layer film obtained by the production method according to any one of (9) to (14), exposing the resist film. A pattern forming method comprising a step and a step of developing the exposed resist film.
(16) A method for manufacturing an electronic device, including the pattern forming method according to (15).

According to the present invention, it is possible to provide a method for producing a composition for forming an upper layer film or a photosensitive resin composition having excellent coatability.
Further, according to the present invention, it is possible to provide a pattern forming method and a method for manufacturing an electronic device.

The schematic diagram of one aspect of the apparatus used for the 1st filtration step which will be described later. The schematic diagram of one aspect of the apparatus used for the 1st filtration step which will be described later. The schematic diagram of one aspect of the apparatus used for the 1st filtration step which will be described later. The schematic diagram of one aspect of the apparatus used for the 1st filtration step which will be described later.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "active ray" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, or the like. .. Further, the term "light" as used herein means an active ray or radiation. Further, unless otherwise specified, the term "exposure" in the present specification means not only exposure with far ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also electron beams or ion beams. Drawing with particle beams such as, etc. is also included in the exposure.
In the present specification, the "hole diameter" of the filter is the manufacturer's nominal diameter value or a value based on the nominal diameter value.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (Mw / Mn) are measured by GPC (solvent: THF) by a GPC (Gel Permeation Chromatography) apparatus (HLC-8120 GPC manufactured by Toso). (Tetrahydrofuran), flow rate (sample injection amount): 10 μl, column: TSK gel multipore HXL-M (× 4) manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detector: differential refractometer It is defined as a polystyrene conversion value by (RI) detector).
The binding direction of the divalent group (for example, -COO-) described in the present specification is not particularly limited. For example, when L in the general formula (1) described later is -COO-, if the _{position bonded to the R 2} side is * 1 and the position bonded to the R ₃ side is * 2, L is It may be * 1-O-CO- * 2 or * 1-CO-O- * 2.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

For forming an upper layer film containing a fluorine-containing resin (hereinafter, also simply referred to as “fluorine-containing resin”) having a repeating unit represented by the general formula (1) or (2) described later, which is obtained by the production method of the present invention. The coating property of the composition or the photosensitive resin composition is good.
The present inventor has found that the coatability of the upper layer film forming composition or the photosensitive resin composition is greatly affected by the fluorine-containing resin. Specifically, since the fluorine-containing resin has a high cohesive force, polymer aggregates are likely to be generated, and such polymer aggregates affect the coatability of the upper layer film forming composition or the photosensitive resin composition. The present inventor knows that this is caused by. Therefore, the present inventor has attempted to prepare a composition for forming an upper layer film or a photosensitive resin composition having a small content of the polymer aggregates.
The present inventor applies a solution containing a fluorine-containing resin to a first filtration step before preparing a composition for forming an upper layer film or a photosensitive resin composition, and uses the obtained filtrate for forming an upper layer film. We have found a production method of the present invention for preparing a composition or a photosensitive resin composition. According to the above method, it is considered that the polymer aggregates can be removed more effectively than the method of simply filtering the prepared upper layer film forming composition or the photosensitive resin composition. As a result, the upper layer film forming composition or the photosensitive resin composition obtained by using the above method has excellent coatability.
That is, the production method of the present invention grasps the problems when a predetermined fluorine-containing resin is used as described above, and selects the fluorine-containing resin as the target to be filtered, so that the coating property can be applied more efficiently. It is possible to obtain an excellent composition for forming an upper layer film or a photosensitive resin composition.

[First Embodiment (Method for producing a composition for forming an upper layer film)]
The first embodiment of the present invention relates to a method for producing a composition for forming an upper layer film.
The method for producing the composition for forming an upper layer film of the present invention includes the following steps.
First filtration step: First filtration step of filtering a solution containing a fluorine-containing resin Preparation step: A step of preparing a composition for forming an upper layer film using a solution containing a fluorine-containing resin that has undergone the first filtration step. Second Filtration Step: Second Filtration Step for Filtering the Upper Layer Film Forming Composition Each step will be described in detail below.

<First filtration process>
The first filtration step is a step of filtering a solution containing a fluorine-containing resin. The fluorine-containing resin has at least one selected from the group consisting of repeating units represented by the general formulas (1) and (2) described later. The details of the fluorine-containing resin and the general formulas (1) and (2) are shown in the latter part.

The pore size of the filter used in the method for producing the composition for forming an upper layer film of the present invention is excellent in efficiency in consideration of the balance between the time required for filtration and the ability to remove polymer aggregates from the solution (hereinafter,). From the viewpoint of "excellent filtration efficiency"), 0.5 μm or less is preferable, 0.001 to 0.5 μm is more preferable, and 0.001 to 0.2 μm is further preferable.

The material of the filter used in the method for producing the composition for forming an upper layer film of the present invention is not particularly limited, and specific examples thereof include polyolefin resin (polyethylene and polypropylene, etc.), polyamide resin (nylon, etc.), and Fluororesin-containing resin can be mentioned. Among them, polyethylene or nylon is preferable as the material of the filter.

The first filtration step in the method for producing the composition for forming an upper layer film of the present invention preferably includes steps 1 and 2, and more preferably steps 1 to 3, from the viewpoint of excellent filtration efficiency.
Step 1: A step of filtering a solution containing a fluorine-containing resin using a first filter Step 2: A step of filtering a solution containing a fluorine-containing resin that has undergone the above step 1 using a second filter Step 3: Third Step 3 and subsequent steps of filtering the solution containing the fluorine-containing resin that has undergone the above step 2 may be carried out by using a different filter to further filter the solution containing the fluorine-containing resin. good.

The step 1 is a step of filtering the solution containing the fluorine-containing resin using the first filter. As the first filter, the filter as described above can be preferably used.

The step 2 is a step of further filtering the solution containing the fluorine-containing resin filtered using the first filter using a second filter different from the first filter.
Here, the second filter may have a different pore diameter from the first filter, or may have a different material from the first filter.

From the viewpoint of excellent filtration efficiency, the pore size of the second filter is preferably smaller than the pore size of the first filter.
Specifically, the pore size of the second filter is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, from the viewpoint of excellent filtration efficiency.
The difference between the pore diameter of the second filter and the pore diameter of the first filter is preferably 0.001 to 0.1 μm.

The material of the second filter is preferably a material different from that of the first filter. For example, it is preferable that the first filter is made of a polyolefin resin and the second filter is made of a polyamide resin.
Polyolefin resin filters usually remove impurities by their pore size. On the other hand, the polyamide resin filter has an adsorption action on the amide portion of the resin, and it is said that the adsorption action also contributes to the removal of impurities. By using filters with different characteristics together, polymer aggregates can be removed more efficiently.

In step 3, the solution containing the fluorine-containing resin filtered using the first filter and the second filter is further filtered using a third filter different from the first filter and the second filter. It is a process to do.
Here, the third filter may have a different pore diameter from the first filter and the second filter, or may have a different material from the first filter and the second filter.

From the viewpoint of excellent filtration efficiency, the pore size of the third filter is preferably smaller than the pore size of the first filter, and more preferably smaller than the pore size of either the first filter or the second filter.
Specifically, the pore size of the third filter is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm.
The difference between the pore diameter of the third filter and the pore diameter of the first filter is preferably 0.001 to 0.1 μm.
The material of the third filter may be, for example, the same as the material of the first filter.
As described above, after step 3, a step of further filtering the solution containing the fluorine-containing resin may be carried out by using a different filter.

It is also preferable that the first filtration step includes a circulation filtration step in which the solution containing the fluorine-containing resin that has passed through the filter is further guided to the same filter and circulated in the system.
Specifically, for example, the first filtration step may include a circulation filtration step in which the solution containing the fluorine-containing resin that has undergone step 1 is further guided to the same first filter and circulated in the system. Further, the first filtration step may include a circulation filtration step in which the solution containing the fluorine-containing resin that has undergone the step 2 is further guided to the first filter or the second filter and circulated in the system. The first filtration step may include a circulation filtration step in which the solution containing the fluorine-containing resin that has undergone step 3 is further guided to a first filter, a second filter, or a third filter and circulated in the system. good.
A plurality of circulation filtration steps may be used in combination during the first filtration step. For example, the solution containing the fluorine-containing resin that has undergone step 3 is further guided to the first filter, and in the circulation filtration step of circulating in the system, at the same time, the solution containing the fluorine-containing resin that has undergone step 2 is further added to the first filter. It may have a circulation filtration step which leads to a second filter and circulates in the system.
The number of circulations can be appropriately adjusted from the viewpoint of the removal rate of polymer aggregates and productivity, and is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15, and even more preferably 4 to 10.
In addition, in the case of carrying out the circulation filtration step, the number of circulations is [the total amount of filtration by any one of the filters used in the circulation filtration step of the solution containing fluorine-containing resin / the circulation filtration step. Amount of solution containing a fluorine-containing resin].

Hereinafter, an example of the embodiment of the first filtration step will be described with reference to the drawings. 1 to 4 are schematic views of the apparatus used in the first filtration step.

The apparatus of FIG. 1 is an apparatus used for the first filtration step of the embodiment in which only step 1 is carried out and the circulation filtration step is not carried out.
In the device of FIG. 1, the tank 1, the pump 2, and the column 100 in which the first filter is installed are connected by the flow paths 5 to 7. Further, a flow meter 3 and a filling port 8 are installed in the flow path 7. By driving the pump 2, the solution containing the fluorine-containing resin filled in the tank 1 passes through the column 100 in which the first filter is installed, and the solution containing the fluorine-containing resin that has passed through the column 100 is filled with the treatment liquid. The container 4 is to be filled.

The apparatus of FIG. 2 is an apparatus used for the first filtration step of the embodiment in which steps 1 to 3 are carried out and the circulation filtration step is not carried out.
In the apparatus of FIG. 2, the tank 1, the pump 2, the column 100 in which the first filter is installed, the column 200 in which the second filter is installed, and the column 300 in which the third filter is installed are in the flow path. It is connected by 5, 6, 7, 9, and 10. Further, a flow meter 3 and a filling port 8 are installed in the flow path 7. By driving the pump 2, the solution containing the fluorine-containing resin filled in the tank 1 passes through the column 100, the column 200, and the column 300, and the solution containing the fluorine-containing resin that has passed through the column 300 is filled with the treatment liquid. The container 4 is to be filled.

The apparatus of FIG. 3 is an apparatus used for the first filtration step of the embodiment in which the step 1 is carried out and the circulation filtration step is carried out.
In the device of FIG. 3, the tank 1, the pump 2, and the column 100 in which the first filter is installed are connected by the flow paths 5 to 7.
Further, the flow path 7 is also connected to the tank 1, and by driving the pump 2, the solution containing the fluorine-containing resin contained in the tank 1 is circulated in the system. .. Further, a filling port 8 is installed in the flow path 7, and a solution containing a fluorine-containing resin that has undergone a predetermined circulation filtration step is filled in the treatment liquid filling container 4.
Here, the filling port 8 is often closed at the start of driving the pump so that a predetermined number of circulations can be achieved.
The number of circulations can be calculated using the flow meter 3 installed in the flow path 7.

The apparatus of FIG. 4 is an apparatus used for the first filtration step of the embodiment in which steps 1 to 3 are carried out and the circulation filtration step is carried out.
In the apparatus of FIG. 4, the tank 1, the pump 2, the column 100 in which the first filter is installed, the column 200 in which the second filter is installed, and the column 300 in which the third filter is installed are in the flow path. It is connected by 5, 6, 7, 9, and 10.
Further, the flow path 7 is also connected to the tank 1, and by driving the pump 2, the solution containing the fluorine-containing resin contained in the tank 1 is circulated in the system. .. Further, a filling port 8 is installed in the flow path 7, and a solution containing a fluorine-containing resin that has undergone a predetermined circulation filtration step is filled in the treatment liquid filling container 4.
Here, the filling port 8 is often closed at the start of driving the pump so that a predetermined number of circulations can be achieved.
The number of circulations can be calculated using the flow meter 3 installed in the flow path 7.

The solvent contained in the solution containing the fluorine-containing resin is not particularly limited as long as it can dissolve the fluorine-containing resin, but the solvent used in the composition for forming the upper layer film is preferable. Of these, diisoamyl ether is more preferable. The solvent used in the composition for forming the upper layer film will be described later.
The content of the fluorine-containing resin in the solution containing the fluorine-containing resin used in the first filtration step is 0.1 to 30 with respect to the total mass of the solution containing the fluorine-containing resin from the viewpoint of excellent filtration efficiency. It is preferably by mass%, more preferably 1 to 20% by mass.

<Preparation process>
A composition for forming an upper layer film is prepared using a solution containing a fluorine-containing resin that has undergone the first filtration step.
The method for preparing the composition for forming an upper layer film is not particularly limited as long as a solution containing a fluorine-containing resin that has undergone the first filtration step is used, and a solution containing the fluorine-containing resin that has undergone the first filtration step and a predetermined component are used. By mixing, a composition for forming an upper layer film is prepared.
Details of the composition for forming an upper layer film will be described later.

<Second filtration process>
The method for producing an upper layer film forming composition of the present invention includes a second filtration step of further filtering the prepared upper layer film forming composition.
Also in the second filtration step, a filter similar to the filter that can be used in the first filtration step can be preferably used.
Similar to the first filtration step, the second filtration step may include a plurality of steps using a plurality of filters, or may include a circulation filtration step.
The pore size of the filter used in the second filtration step is preferably 0.5 μm or less, more preferably 0.001 to 0.5 μm, and even more preferably 0.001 to 0.1 μm in terms of excellent filtration efficiency.

In each step, the solution containing the fluorine-containing resin or the composition for forming the upper layer film is degassed before and / or after the solution containing the fluorine-containing resin or the composition for forming the upper layer film is subjected to filtration. Etc. may be performed.
The upper layer film forming composition produced by using the method for producing an upper layer film forming composition of the present invention has excellent coatability and can form an upper layer film having a uniform film thickness.

[Second embodiment (method for producing a photosensitive resin composition)]
The second embodiment of the present invention relates to a method for producing a photosensitive resin composition.
The method for producing a photosensitive resin composition of the present invention includes the following steps.
First filtration step: First filtration step of filtering a solution containing a fluorine-containing resin Preparation step: A step of preparing a photosensitive resin composition using a solution containing a fluorine-containing resin that has undergone the first filtration step. Filtration step: Second filtration step for filtering the photosensitive resin composition The following describes each step in detail.

<First filtration process>
The first filtration step is a step of filtering a solution containing a fluorine-containing resin. The fluorine-containing resin has at least one selected from the group consisting of repeating units represented by the general formulas (1) and (2) described later. The details of the fluorine-containing resin and the general formulas (1) and (2) are shown in the latter part.

The suitable pore size of the filter used in the method for producing the photosensitive resin composition of the present invention is the same as the preferable range of the pore size of the filter used in the method for producing the composition for forming an upper layer film.
The suitable material of the filter used in the method for producing the photosensitive resin composition of the present invention is the same as the suitable material for the filter used in the method for producing the composition for forming an upper layer film.

The first filtration step in the method for producing a photosensitive resin composition of the present invention preferably includes steps 1 and 2, and more preferably steps 1 to 3, from the viewpoint of excellent filtration efficiency.
Step 1: Filter the solution containing the fluorine-containing resin using the first filter Step 2: Filter the solution containing the fluorine-containing resin that has undergone the step 1 using the second filter Step 3: Step of filtering the solution containing the fluorine-containing resin that has undergone the step 2 using a third filter Further, after step 3, a step of further filtering the solution containing the fluorine-containing resin using a different filter is carried out. You may.

Steps 1 to 3 in the first filtration step included in the method for producing a photosensitive resin composition of the present invention are the same as steps 1 to 3 in the first filtration step included in the method for producing a composition for forming an upper layer film described above. The same applies to suitable conditions.
Further, as in the circulation filtration step in the first filtration step included in the method for producing the composition for forming an upper layer film of the present invention, the circulation is also carried out in the first filtration step included in the method for producing the photosensitive resin composition of the present invention. A filtration step may be performed.

The solvent contained in the solution containing the fluorine-containing resin is not particularly limited as long as it can dissolve the fluorine-containing resin, but the solvent used in the photosensitive resin composition is preferable. Of these, PGMEA (propylene glycol monomethyl ether acetate) is more preferable. The solvent used in the photosensitive resin composition will be described later.
The content of the fluorine-containing resin in the solution containing the fluorine-containing resin used in the first filtration step is 0.1 to 30 mass with respect to the total mass of the solution containing the fluorine-containing resin from the viewpoint of excellent filtration efficiency. % Is preferable, and 1 to 20% by mass is more preferable.

<Preparation process>
A photosensitive resin composition is prepared using a solution containing a fluorine-containing resin that has undergone the first filtration step.
The method for preparing the photosensitive resin composition is not particularly limited as long as a solution containing the fluorine-containing resin that has undergone the first filtration step is used, and the solution containing the fluorine-containing resin that has undergone the first filtration step and a predetermined component are mixed. The photosensitive resin composition is prepared by the above.
Details of the photosensitive resin composition will be described later.

<Second filtration process>
The method for producing a photosensitive resin composition of the present invention includes a second filtration step of further filtering the prepared photosensitive resin composition.
Also in the second filtration step, a filter similar to the filter that can be used in the first filtration step can be preferably used.
Similar to the first filtration step, the second filtration step may include a plurality of steps using a plurality of filters, or may include a circulation filtration step.
The pore size of the filter used in the second filtration step is preferably 0.5 μm or less, more preferably 0.001 to 0.5 μm, and even more preferably 0.001 to 0.1 μm in terms of excellent filtration efficiency.

In each step, the solution containing the fluorine-containing resin or the photosensitive resin composition is degassed before and / or after the solution containing the fluorine-containing resin or the photosensitive resin composition is subjected to filtration. You may go.
The photosensitive resin composition produced by using the method for producing a photosensitive resin composition of the present invention has excellent coatability and can form a resist film having a uniform film thickness.

[Solution containing fluorine-containing resin]
Next, the above-mentioned solution containing the fluorine-containing resin (hereinafter, also simply referred to as “specific solution”) will be described.
In the following, first, the fluorine-containing resin will be described in detail.

<Fluorine-containing resin having a repeating unit represented by the general formula (1) or (2)>
The fluorine-containing resin has at least one selected from the group consisting of repeating units represented by the following general formulas (1) and (2). The repeating unit represented by the following general formula (1) or (2) is a case of immersion exposure using an upper layer film formed by using a composition for forming an upper layer film containing a fluorine-containing resin, and a fluorine-containing repeating unit. When a resist film formed by using a photosensitive resin composition containing a resin is used for immersion exposure, it contributes to improvement of scanning speed and suppression of development defects.
Unless otherwise specified, the preferable conditions referred to in the description of the following general formula (1) or (2) are defined from the viewpoint of excellent scanning speed and ability to suppress development defects.

In the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom. Among them, as R ₁ , from the viewpoint of the copolymerizability of the monomer, a halogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, a fluorine atom or a methyl group is more preferable, and a methyl group is further preferable. ..

In the general formula (1), R ₂ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom.
R number of carbon atoms of the alkylene group represented by _2, preferably 1 to 15, more preferably 1 to 10, 2 to 4 is more preferred.
Alkylene group represented by R ₂ may be linear, may be branched, or may have a cyclic structure. The ring structure may be a monocyclic structure or a polycyclic structure, and a polycyclic structure is preferable. It is also preferable that a part of the ring structure is substituted with an oxygen atom to have -COO-.
Among them, an alkylene group represented by R ₂ is a linear or branched chain is preferred.
Alkylene group represented by R ₂ may have an oxygen atom, the alkylene group, also preferred to have a -COO-.
Alkylene group represented by R _2, as a substituent group, preferably has a fluorine atom. When the alkylene group has a fluorine atom, the number of fluorine atoms is preferably 1 to 10, more preferably 2 to 5.
As R ₂ , for example, -CH _2- , -C (C ₂ H ₅ ) H-, -C (C ₄ H ₉ ) HCH ₂ C (CF ₃ ) _2- , -C (CH ₃ ) ₂ Examples thereof include C (CF ₃ ) _2- , -C (CH _{2 OCOC 2} F ₅ ) HCH _2-.

In the general formula (1), R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom. When R ₃ is a hydrogen atom, -L-R ₃ represents -OH or -COOH.
The R _3, an alkyl group is preferable.
The _{number of carbon atoms of the alkyl group represented by R 3} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.
The _{alkyl group represented by R 3} may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, the alkyl group represented by R _3, linear or branched are preferred, linear is preferred.
The _{alkyl group represented by R 3} preferably has a fluorine atom as a substituent. When the alkyl group has a fluorine atom, the number of fluorine atoms is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.

In the general formula (1), L represents −O− or −COO−.
Above all, -COO- is preferable as L.
When L represents a -COO-, as the _{R 3,} an alkyl group is preferable. If L represents -O-, preferably a hydrogen atom _{R 3.}

In the general formula (1), at least one of _{R 2} and R _{3 has a fluorine atom.}

In the general formula (2), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom.
As R ₄ , an alkyl group is preferable.
R number of the alkyl group represented by ₄ carbon is preferably 1 to 10, more preferably 1 to 5, 2 is more preferable.
The _{alkyl group represented by R 4} may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, the alkyl group represented by R _4, and is preferably linear.
The _{alkyl group represented by R 4} preferably has a fluorine atom as a substituent.

In the general formula (2), R ₅ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom.
The alkylene group represented by R ₅ is 1 to 10, more preferably 3 to 8, 5 to 6 is more preferred.
The _{alkylene group represented by R 5} may be linear, branched or chain-like, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, an alkylene group represented by R ₅ is a branched chain is preferred.
The _{alkylene group represented by R 5} may have an oxygen atom, and preferably has —O— in the alkylene group.
The _{alkylene group represented by R 5} preferably has a fluorine atom as a substituent. When the alkylene group has a fluorine atom, the number of fluorine atoms is preferably 1 to 10, more preferably 2 to 8, and even more preferably 6.

In the general formula (2), R ₆ represents an alkyl group which may have a hydrogen atom or a fluorine atom.
Among them, as R _6, from the viewpoint of solubility in a developing solution is preferably a hydrogen atom.
The _{number of carbon atoms of the alkyl group represented by R 6} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.
The _{alkyl group represented by R 6} may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
The _{alkyl group represented by R 6} preferably has a fluorine atom as a substituent.

In the general formula (2), L represents −O− or −COO−.
Above all, -O- is preferable as L.

At _{least one of R 4 to} R ₆ has a fluorine atom.

<Fluorine-containing resin having a repeating unit represented by the general formula (3) or (4)>
The fluorine-containing resin preferably has at least one selected from the group consisting of repeating units represented by the following general formulas (3) and (4).
Unless otherwise specified, the preferable conditions referred to in the description of the following general formulas (3) and (4) are defined from the viewpoint of excellent scanning speed and ability to suppress development defects.

The repeating unit represented by the general formula (3) is a preferred embodiment of the repeating unit represented by the general formula (1).

In the general formula (3), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom.
R ₁ in the general formula (3), corresponds to R ₁ in the general formula (1), the preferred conditions are also the same.

In the general formula (3), R ₇ represents an alkylene group having a fluorine atom, which may have an oxygen atom.
The carbon number of the alkylene group represented by R ₇ is preferably 1 to 15, more preferably 1 to 10, further preferably 2 to 4, and particularly preferably 4.
The _{alkylene group represented by R 7} may be linear, branched or chain-like, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, the _{alkylene group represented by R 7} is preferably linear or branched, and more preferably branched.
The number of fluorine atoms contained in the alkylene group represented by R ₇ is preferably 1 to 10, more preferably 2 to 3, and even more preferably 2.

In the general formula (3), R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom.
The R _3, an alkyl group is preferable.
The _{number of carbon atoms of the alkyl group represented by R 3} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.
The _{alkyl group represented by R 3} may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, the alkyl group represented by R _3, linear or branched are preferred, linear is preferred.
The _{alkyl group represented by R 3} may have a fluorine atom as a substituent. When the alkyl group has a fluorine atom, the number of fluorine atoms is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.

The repeating unit represented by the general formula (4) is a preferred embodiment of the repeating unit represented by the general formula (2).

In the general formula (4), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom.
R ₄ in the general formula (4) in the general formula (2) corresponds to the R ₄ in a suitable condition as well.

In the general formula (4), R ₈ represents an alkylene group which may have an oxygen atom.
The carbon number of the alkylene group represented by R ₈ is preferably 1 to 7, more preferably 1 to 5, and even more preferably 3.
The _{alkylene group represented by R 8} may be linear, branched or chain-like, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among them, the alkylene group represented by _{R 8 is preferably linear.}
The _{alkylene group represented by R 8} may have an oxygen atom, and preferably has —O— in the alkylene group.

R ₉ and R ₁₀ each independently represent an alkyl group which may have a fluorine atom.
The _{number of carbon atoms of the alkyl group represented by R 9} and R ₁₀ is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
The _{alkyl groups represented by R 9} and R ₁₀ may be linear, branched, or have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Of these, the alkyl groups represented by _{R 9} and R _{10 are preferably linear.}
The _{alkyl group represented by R 9} and R ₁₀ preferably has a fluorine atom as a substituent. When the alkyl group has a fluorine atom, the number of fluorine atoms is preferably 1 to 10, more preferably 2 to 3, and even more preferably 3.
At _{least one of R 9} and R ₁₀ has a fluorine atom.

In the general formula (4), R ₁₁ represents an alkyl group which may have a hydrogen atom or a fluorine atom.
Among them, as R _11, a hydrogen atom is preferred from the viewpoint of solubility in a developing solution.
The _{number of carbon atoms of the alkyl group represented by R 11} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 2.
The _{alkyl group represented by R 11} may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
The _{alkyl group represented by R 11} preferably has a fluorine atom as a substituent.

The fluorine-containing resin may have only one type of repeating units represented by the above-mentioned general formulas (1) to (4), or may have two or more types.
The total content of the repeating units represented by the general formula (1) (including the general formula (3)) and the general formula (2) (including the general formula (4)) in the fluorine-containing resin is fluorine. It is preferably 45 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 80 to 100 mol%, based on all the repeating units of the contained resin.

The fluorine-containing resin may have a repeating unit other than the repeating units represented by the above-mentioned general formulas (1) to (4).
The other repeating units will be described in detail below.

The fluorine-containing resin may have a repeating unit having a _{CH 3-part structure in the side chain portion.} Specific examples thereof include a repeating unit represented by the general formula (II) and a repeating unit represented by the following general formula (III).

Hereinafter, the repeating unit represented by the general formula (II) will be described in detail.

In the above general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, and R ₂ is an organic group stable to an acid having one or more CH _{3 partial structures.} show. Here, more specifically, the organic group stable to an acid is preferably an organic group having no "group decomposed by the action of an acid to produce a polar group".

The alkyl group of X _b1 preferably has 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
X _b1 is preferably a hydrogen atom or a methyl group.

The R _2, has one or more CH ₃ moiety, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group. The cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group described above may further have an alkyl group as a substituent.
R ₂ has one or more CH ₃ moiety, the alkyl group or alkyl-substituted cycloalkyl groups are preferred.
The number is preferably 2 to 10 CH ₃ partial structure having a stable organic radical in the acid having one or more CH ₃ partial structure as R _2, 2 to 8 is more preferable.

As the alkyl group having one or more CH _{3 partial structures in R 2} , a branched-chain alkyl group having 3 to 20 carbon atoms is preferable. Specific examples of the alkyl group include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, and a 3-methyl-4- Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group , Or 2,3,5,7-tetramethyl-4-heptyl group is preferable, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl -4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group , Or 2,3,5,7-tetramethyl-4-heptyl group is more preferable.

In R _2, a cycloalkyl group having one or more CH ₃ partial structure, may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo structure, a bicyclo structure, a tricyclo structure, a tetracyclo structure and the like having 5 or more carbon atoms. The cycloalkyl group preferably has 6 to 30 carbon atoms, more preferably 7 to 25 carbon atoms. Examples of the cycloalkyl group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a sedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecanyl group. A group or cyclododecanyl group is preferable, and an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group or tricyclodecanyl group is more preferable, and a norbornyl group, cyclopentyl group or cyclohexyl group is preferable. Is even more preferable.
In R _2, the alkenyl group having one or more CH ₃ partial structure is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, branched-chain alkenyl group is more preferable.
In R _2, the aryl group having one or more CH ₃ partial structure is preferably an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, and, like naphthyl groups. Of these, a phenyl group is preferable.
In R _2, the aralkyl group having one or more CH ₃ partial structure, preferably an aralkyl group having 7 to 12 carbon atoms, for example, benzyl group, phenethyl group, and include naphthylmethyl group.

In R _2, examples of the hydrocarbon group having two or more CH ₃ partial structure include an isopropyl group, an isobutyl group, t- butyl group, 3-pentyl, 2-methyl-3-butyl group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2, 4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3, Examples thereof include a 5-dimethylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-t-butylcyclohexyl group, and an isobornyl group. Among them, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3, 5-Dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7 -Tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4-t-butylcyclohexyl group, or isobornyl group are preferable.

A specific example of the repeating unit represented by the general formula (II) is shown below.

The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-degradable) repeating unit, and specifically, a group that is decomposed by the action of an acid to produce a polar group. It is preferable that the repeating unit does not have.

Hereinafter, the repeating unit represented by the general formula (III) will be described in detail.

In the above general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, and R ₃ is an organic group stable to an acid having one or more CH _{3 partial structures.} show. n represents an integer of 1 to 5.

A hydrogen atom is preferable as _{X b2.}
When X _b2 is an alkyl group, the alkyl group preferably has 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.

R ₃ is preferably an organic group that does not have the "group that decomposes by the action of an acid to produce a polar group" described in the resin (A) described later.

Examples of R ₃ include alkyl groups having one or more CH _{3 partial structures.}
The number 1 to 10 are preferable CH ₃ partial structure having a stable organic radical in the acid having one or more CH ₃ partial structure as R _3, and more preferably 1 to 8, 1 to 4 is more preferred.

In R _3, the alkyl group having one or more CH ₃ partial structure, preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of the alkyl group include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, and a 3-methyl-4- Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group , Or 2,3,5,7-tetramethyl-4-heptyl group is preferable, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl -4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group , Or 2,3,5,7-tetramethyl-4-heptyl group is more preferable.

In R _3, specific examples of the alkyl group having two or more CH ₃ partial structure, an isopropyl group, an isobutyl group, t- butyl group, 3-pentyl, 2,3-dimethylbutyl group, 2-methyl - 3-Butyl group, 3-Hexyl group, 2-Methyl-3-pentyl group, 3-Methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, Isooctyl group, 2,4,4-trimethylpentyl group Groups include 2-ethylhexyl groups, 2,6-dimethylheptyl groups, 1,5-dimethyl-3-heptyl groups, and 2,3,5,7-tetramethyl-4-heptyl groups. Among them, isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2, 4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, or A 2,6-dimethylheptyl group is preferred. It is also preferred carbon number of the alkyl group having two or more CH ₃ partial structure is 5-20.

n represents an integer of 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

Hereinafter, preferred specific examples of the repeating unit represented by the general formula (III) will be shown.

The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-degradable) repeating unit, and specifically, a group that is decomposed by the action of an acid to produce a polar group. It is preferable that the repeating unit does not have.

The content of the repeating unit represented by the general formula (II) is not particularly limited, but is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, based on all the repeating units of the fluorine-containing resin.
The content of the repeating unit represented by the general formula (III) is not particularly limited, but is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, based on all the repeating units of the fluorine-containing resin.

The fluorine-containing resin may further have a repeating unit represented by the following general formula (III).

In general formula (III)
R ₄ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, or a group having a cyclic siloxane structure.
L ₆ represents a single bond or a divalent linking group.

In the formula (III), the alkyl group of _{R 4} is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.
The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.
The _{divalent linking group of L 6} is preferably an alkylene group (preferably 1 to 5 carbon atoms) or an oxy group.

The fluorine-containing resin may have a lactone group, an ester group, an acid anhydride, or a group similar to the acid-degradable group in the resin (A) described later.
The fluorine-containing resin may further have a repeating unit represented by the following general formula (VIII).

In the above general formula (VIII)
Z ₂ represents −O− or −N (R ₄₁ ) −. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or -OSO _2- R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group, or a camphor residue. The alkyl groups of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

A specific example of the repeating unit represented by the above general formula (VIII) is shown below.

The fluorine-containing resin preferably contains a repeating unit (d) derived from a monomer having an alkali-soluble group. Thereby, the solubility in liquid immersion and the solubility in the coating solvent can be controlled. Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, sulfonylamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imide groups, Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, or tris (alkylsulfonyl) methylene group Examples include groups having.
As the monomer having an alkali-soluble group, a monomer having an acid dissociation constant pKa of 4 or more is preferable, a monomer having a pKa of 4 to 13 is more preferable, and a monomer having a pKa of 8 to 13 is further preferable. By containing a monomer having a pKa of 4 or more, swelling during negative and positive development is suppressed, and not only good developability for an organic developer but also good development even when an alkaline developer is used. Sex is obtained.

The acid dissociation constant pKa is as described in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.), and the value of pKa of the monomer containing an alkali-soluble group is, for example, infinite. It can be measured at 25 ° C. using a diluting solvent, and Hammett's substituent constant and values based on a database of known literature values can also be calculated by using the following software package 1. All the pKa values described herein indicate values calculated using this software package.

Software Package 1: AdvancedChemistryDevelopment (ACD / Labs) Software V8.14forSolaris (1994-2007ACD / Labs)

The monomer having a pKa of 4 or more is not particularly limited, and examples thereof include a monomer having an acid group (alkali-soluble group) such _{as a phenolic hydroxyl group, a sulfonamide group, -COCH 2 CO-, and a carboxylic acid group.}

The total amount of repeating units derived from the monomer having an alkali-soluble group in the fluorine-containing resin is preferably 0 to 90 mol%, more preferably 0 to 80 mol%, and 0 to 0, based on all the repeating units of the fluorine-containing resin. 70 mol% is more preferred.

The monomer having an alkali-soluble group may contain only one acid group or two or more acid groups. The repeating unit derived from this monomer preferably has 2 or more acid groups per repeating unit, more preferably 2 to 5 acid groups, and further preferably 2 to 3 acid groups. preferable.

Specific examples of the repeating unit derived from the monomer having an alkali-soluble group include, but are not limited to, the examples described in paragraphs [0278] to [0287] of JP-A-2008-309878.

The fluorine-containing resin is preferably solid at room temperature (25 ° C.). The glass transition temperature (Tg) of the fluorine-containing resin is preferably 50 to 250 ° C., more preferably 70 to 250 ° C., further preferably 80 to 250 ° C., particularly preferably 90 to 250 ° C., and most preferably 100 to 250 ° C.
The fluorine-containing resin preferably has a repeating unit having a monocyclic or polycyclic cycloalkyl group. The monocyclic or polycyclic cycloalkyl group may be contained in either the main chain or the side chain of the repeating unit. Of these, a repeating unit having both a monocyclic or polycyclic cycloalkyl group and a CH _3- part structure is preferable, and a repeating unit having both a monocyclic or polycyclic cycloalkyl group and a CH _3- part structure in the side chain is more preferable. preferable.

The term "solid" at 25 ° C means that the melting point is 25 ° C or higher.
The glass transition temperature (Tg) can be measured by differential scanning calorimetry. For example, the specific volume of the sample changed when the sample was heated once, cooled, and then heated again at 5 ° C./min. It can be measured by analyzing the value.

The fluorine-containing resin is preferably insoluble in an immersion liquid (preferably water) and soluble in an organic developer. From the viewpoint that development and peeling can be performed using an alkaline developer, the fluorine-containing resin is preferably soluble in the alkaline developer.

The content of fluorine atoms in the fluorine-containing resin is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, based on the molecular weight of the fluorine-containing resin.

The weight average molecular weight of the fluorine-containing resin in terms of standard polystyrene by GPC is preferably 2000 to 20000, more preferably 2000 to 12000. The dispersity (Mw / Mn, also referred to as molecular weight distribution) of the fluorine-containing resin is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 1.95.

From the viewpoint of reducing elution of the fluorine-containing resin into the liquid immersion liquid, the amount of residual monomer is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass.

The blending amount of the fluorine-containing resin in the specific solution is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total solid content.

The method for synthesizing the fluorine-containing resin is not particularly limited, and a known method is adopted. For example, a monomer solution containing a polymerizable monomer (hereinafter, also referred to as “monomer solution”) and a solution containing a polymerization initiator (hereinafter, also referred to as “initiator solution”) are held in independent storage tanks for polymerization. A method of continuously or intermittently supplying the system to radical polymerization is preferable.
Examples of components that can be contained in the monomer solution other than the monomer include a solvent, a polymerization inhibitor, oxygen, and a chain transfer agent. Examples of the components that can be contained in the initiator solution other than the initiator include a solvent.

The specific solution may contain components other than the fluorine-containing resin.
For example, the specific solution may contain a solvent. Examples of the solvent include a solvent that can be contained in the composition for forming an upper layer film described later.

The method for preparing the specific solution is not particularly limited, and a known method is adopted.
For example, a fluorine-containing resin may be produced by polymerizing a predetermined monomer in a solvent, and the obtained solution containing the fluorine-containing resin may be used as a specific solution, or a separately produced fluorine-containing resin may be used as a predetermined solvent. A specific solution may be prepared by dissolving in.

[Composition for forming upper layer film]
Next, a composition for forming an upper layer film, which is prepared by using a solution containing a fluorine-containing resin that has undergone the above-mentioned first filtration step, will be described.
The composition for forming an upper layer film produced by the production method of the present invention is a composition for forming an upper layer film for a photoresist, which contains a fluorine-containing resin.
The fluorine-containing resin is as described above.
The content of the fluorine-containing resin in the composition for forming the upper layer film is not particularly limited, but is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, based on the total solid content.

<Solvent>
The composition for forming an upper layer film may contain a solvent.
In order to form a good pattern without dissolving the resist film, the upper layer film forming composition produced by the method for producing the upper layer film forming composition of the present invention may use a solvent that does not dissolve the resist film. It is preferable to use a solvent having a component different from that of the developer containing an organic solvent (organic developer).
From the viewpoint of uniformly applying the upper layer film, the solid content concentration of the upper layer film forming composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 1 to 10% by mass. ..

The solvent that can be used is not particularly limited as long as the fluorine-containing resin is not dissolved and the resist film is not dissolved. For example, an alcohol solvent, an ether solvent, an ester solvent, a fluorine solvent, or a hydrocarbon solvent is used. Solvents and the like are preferable, and non-fluorine-based alcohol-based solvents are more preferable. As a result, the insolubility with respect to the resist film is further improved, and when the composition for forming an upper layer film is applied onto the resist film, the upper layer film can be formed more uniformly without dissolving the resist film. The viscosity of the solvent is preferably 5 mPa · s or less, more preferably 3 mPa · s or less, further preferably 2 mPa · s or less, and particularly preferably 1 mPa · s or less.

As the alcohol solvent, a monohydric alcohol is preferable from the viewpoint of coatability, and a monohydric alcohol having 4 to 8 carbon atoms is more preferable. Examples of the monohydric alcohol having 4 to 8 carbon atoms include linear, branched or cyclic alcohols, and among them, linear or branched alcohols are preferable. Specific examples of such alcoholic solvents include 1-butanol, 2-butanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2. -Pentanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, Alcohols such as 3-heptanol, 3-octanol, and 4-octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol; and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, Examples thereof include triethylene glycol monoethyl ether and glycol ethers such as methoxymethylbutanol. Of these, alcohol or glycol ether is preferable, and 1-butanol, 1-hexanol, 1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 4-methyl-1-pentanol, or , 4-Methyl-2-pentanol is more preferred.
Specific examples of the ether solvent include dioxane, tetrahydrofuran, and diisoamyl ether in addition to the glycol ether solvent. Among the ether solvents, an ether solvent having a branched structure is preferable, and diisoamyl ether is more preferable.
Specific examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butylate, and the like. Isobutyl butylate, butyl butylate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate. Can be mentioned. Among the ester-based solvents, an ester-based solvent having a branched structure is preferable.

Specific examples of the fluorosolvent include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,5,5-octafluoro-1-pen. Tanol, 2,2,3,3,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol , 2,2,3,3,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,5,5,6,6,7,7 -Dodecafluoro-1,8-octanediol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanol, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, Examples thereof include perfluorotributylamine and perfluorotetrapentylamine. Among the fluorinated solvents, fluorinated alcohol or fluorinated hydrocarbon solvent is preferable.
Specific examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; and n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3 Examples include aliphatic hydrocarbon solvents such as −methylheptane, 3,3-dimethylhexane, and 2,3,4-trimethylpentane.

These solvents may be used alone or in combination of two or more.
Further, as described above, it is also preferable to use the same solvent as the solvent contained in the specific solution.
When a solvent other than the above is mixed, the mixing ratio is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% by mass with respect to the total amount of the solvent for forming the upper layer film. Is even more preferable. By mixing a solvent other than the above, the solubility in the resist film, the solubility of the polymer in the composition for forming the upper layer film, the dissolution characteristics from the resist film, and the like can be appropriately adjusted.

The composition for forming an upper layer film is further selected from the group consisting of (A1) a basic compound or a base generator, and (A2) an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond. It is preferable to contain at least one compound selected from the group consisting of compounds having a bond or a group.

<(A1) Basic compound or base generator>
It is also preferable that the composition for forming an upper layer film further contains at least one of a basic compound and a base generator (hereinafter, these are also collectively referred to as “additive” or “compound (A1)”).

(Basic compound)
The basic compound contained in the composition for forming an upper layer film is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound. Further, the basic compound contained in the photosensitive resin composition can be used in the same manner.
Further, for example, compounds classified into the following (1) to (7) can be used.

(1) Compound represented by the general formula (BS-1)

In the general formula (BS-1),
R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. The organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

The number of carbon atoms of the alkyl group as R is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 12.
The number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15.

The number of carbon atoms of the aryl group as R is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.
The carbon number of the aralkyl group as R is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 11. Specific examples thereof include a benzyl group.

The hydrogen atom of the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R may be substituted with a substituent. Specific examples of this substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-isopropylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, and tri. Isodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N Included are −dibutylaniline, N, N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

Moreover, as a preferable basic compound represented by the general formula (BS-1), a basic compound which is an alkyl group in which at least one R is substituted with a hydroxy group can be mentioned. Specific examples thereof include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed in the alkyl group as R. As the oxyalkylene chain, −CH ₂ CH ₂ O− is preferable. Specific examples include tris (methoxyethoxyethyl) amine and the compounds exemplified in column 3 of US6040112 after the 60th line.

Specific examples of the basic compound represented by the general formula (BS-1) are shown below.

(2) Compound having a nitrogen-containing heterocyclic structure This nitrogen-containing heterocycle may or may not have aromaticity. Moreover, it may have a plurality of nitrogen atoms. Furthermore, it may contain a heteroatom other than nitrogen. Specific examples include compounds having an imidazole structure (2-phenylbenzimidazole and 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2). , 6,6-Pentamethyl-4-piperidyl) sebacate, etc.], compounds having a pyridine structure (4-dimethylaminopyridine, etc.), and compounds having an antipyrine structure (antipyrine, hydroxyantipyrine, etc.) can be mentioned.

Further, a compound having two or more rings is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] nona-5-ene and 1,8-diazabicyclo [5.4.0] -undeca-7-ene.

(3) Amine Compound Having a Phenoxy Group The amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group includes, for example, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an asyloxy group, an aryloxy group and the like. It may have a substituent.

This compound preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene chains, -CH ₂ CH ₂ O- is preferable.

Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. Examples of the compounds (C1-1) to (C3-3) can be mentioned.

The amine compound having a phenoxy group is, for example, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether. Is added and then extracted with an organic solvent such as ethyl acetate or chloroform. Further, the amine compound having a phenoxy group is obtained by heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal to make a strong reaction such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium. It can also be obtained by adding an aqueous solution of the base and then extracting with an organic solvent such as ethyl acetate or chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be appropriately used. Specific examples of ammonium salt anions include halides, sulfonates, borates, and phosphates. Of these, halides or sulfonates are preferable.

As the halide, chloride, bromide, or iodide is preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is preferable. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms.

The alkyl group contained in the alkyl sulfonate may have a substituent. Specific examples of this substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of alkyl sulfonates include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate.

Specific examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As the substituent, a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, or a cyclohexyl group is preferable. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

The ammonium salt may be hydroxyd or carboxylate. In this case, the ammonium salt may be a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or tetra- (n-butyl) ammonium hydroxide). preferable.

Examples of preferred basic compounds include guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholin, and aminoalkylmorpholin. Can be mentioned. These may have additional substituents.
Specific examples of the preferred substituent include an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group and a nitro group. Examples include hydroxyl groups and cyano groups.

Specific examples of particularly preferable basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, and the like. 2-Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2 -Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 3-amino Ethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidin, piperazin, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 tetramethylpiperidin , 4-Piperidinopiperidin, 2-iminopiperidin, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine , 2- (Aminomethyl) -5 methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazolin, 3-pyrazolin, N-aminomorpholine, and N- (2-amino Ethyl) morpholine can be mentioned.

(5) A compound having a proton-accepting functional group and decomposing by irradiation with active light or radiation to reduce or eliminate the proton-accepting property, or to generate a compound in which the proton-accepting property is changed to acidic. (PA)
The composition for forming an upper layer film has a proton-accepting functional group as a basic compound, and is decomposed by irradiation with active light or radiation to reduce, eliminate, or have a proton-accepting property. It may further contain a compound (hereinafter, also referred to as compound (PA)) that generates a compound that has changed from to acidic to acidic.

A proton-accepting functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. It means a functional group having a nitrogen atom having an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.

Examples of preferable partial structures of the proton acceptor functional group include a crown ether structure, an aza-crown ether structure, a 1-3-grade amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (PA) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. Specifically, it means that when a proton adduct is formed from a compound (PA) having a proton-accepting functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.

Proton acceptability can be confirmed by measuring pH. The acid dissociation constant pKa of the compound generated by decomposing the compound (PA) by irradiation with active light or radiation is preferably pKa <-1, more preferably -13 <pKa <-1, and -13 <pKa <-3. Is even more preferable.

The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition by irradiation with active light or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with a proton-accepting functional group, the proton-accepting property is reduced, eliminated, or proton-accepting property as compared with the compound (PA). It is a compound that has changed from to acidic.

In the general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H, or -X ₁ NHX ₂ Rf. Here, Rf represents an alkyl group, a cycloalkyl group, or an aryl group, and X ₁ and X ₂ independently _{represent -SO 2-} or -CO-, respectively.
A represents a single bond or a divalent linking group.
X represents −SO _2- or −CO−.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. Rx and Ry may be bonded to each other to form a ring, and Rx and R may be bonded to each other to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

The general formula (PA-1) will be described in more detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. Among them, an alkylene group having at least one fluorine atom is preferable, the number of carbon atoms is preferably 2 to 6, and more preferably 2 to 4. The alkylene group may have a linking group such as an oxygen atom or a sulfur atom. As the alkylene group, an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is preferable, a carbon atom bonded to the Q moiety preferably has a fluorine atom, and a perfluoroalkylene group is further preferable. A perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group is particularly preferable.

The monovalent organic group in Rx preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.

The alkyl group in Rx may have a substituent. Of these, linear and branched alkyl groups having 1 to 20 carbon atoms are preferable, and the alkyl chain may have an oxygen atom, a sulfur atom, or a nitrogen atom.

As the divalent organic group in Ry, an alkylene group is preferable.
As the ring in which Rx and Ry may be bonded to each other, a 5- to 10-membered ring containing a nitrogen atom is preferable, and a 6-membered ring is more preferable.

Examples of the alkyl group having a substituent include a linear or branched alkyl group substituted with a cycloalkyl group (for example, an adamantyl methyl group, an adamantyl ethyl group, a cyclohexyl ethyl group, and a camphor residue. (Basics, etc.).

As the cycloalkyl group in Rx, a cycloalkyl group having 3 to 20 carbon atoms is preferable. The cycloalkyl group may have an oxygen atom in the ring.
As the aryl group in Rx, an aryl group having 6 to 14 carbon atoms is preferable.

As the aralkyl group in Rx, an aralkyl group having 7 to 20 carbon atoms is preferable.
Examples of alkenyl groups in Rx include groups having a double bond at any position of the alkyl group listed as Rx.

The proton-accepting functional group in R is as described above, and includes groups having an aza-crown ether group, a 1-3-amine group, and a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole. Be done.

The alkyl group containing a proton acceptor functional group or an ammonium group in R, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group are the above Rx. It is a group similar to the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group mentioned above.

Examples of the substituent that each of the above groups may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably having 3 to 10 carbon atoms). 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 10 carbon atoms). Examples thereof include 2 to 20 carbon atoms) and an aminoacyl group (preferably 2 to 20 carbon atoms). As for the cyclic structure of the aryl group, the cycloalkyl group and the like, and the aminoacyl group, an alkyl group (preferably 1 to 20 carbon atoms) can be further mentioned as the substituent.

When B is −N (Rx) Ry−, it is preferable that R and Rx are bonded to each other to form a ring. By forming a ring, the stability is improved, and the storage stability of the composition using the ring is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and it may be a single ring or a polycycle, and the ring may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

Examples of monocycles include 4-membered rings, 5-membered rings, 6-membered rings, 7-membered rings, and 8-membered rings containing a nitrogen atom. Examples of polycycles include structures consisting of a combination of two or three or more monocyclic structures. The monocyclic or polycyclic ring may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 3 to 10 carbon atoms). 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 15 carbon atoms), an acyloxy group (preferably 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably 2 to 15 carbon atoms). 2 to 15 carbon atoms) or an aminoacyl group (preferably 2 to 20 carbon atoms) is preferable. The cyclic structure of an aryl group, a cycloalkyl group, or the like may further have an alkyl group (preferably 1 to 15 carbon atoms) as a substituent. The aminoacyl group may further have an alkyl group (preferably 1 to 15 carbon atoms) as a substituent.

_{As Rf in −X 1} NHX ₂ Rf represented by Q, an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms is preferable, and a perfluoroalkyl group having 1 to 6 carbon atoms is more preferable. Further, as X ₁ and X ₂ , it is preferable that at least one of them is −SO ₂ −, and it is more preferable that _{both X 1} and X ₂ are − SO _{2 −.}

Among the compounds represented by the general formula (PA-1), a compound having a Q-site of sulfonic acid can be synthesized by using a general sulfonamide reaction. For example, a method in which one sulfonyl halide portion of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide moiety is hydrolyzed, or a cyclic sulfonic acid anhydride. Can be obtained by reacting with an amine compound to open the ring.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion moiety.
As the compound (PA), compounds represented by the following general formulas (4) to (6) are preferable.

In the general formulas (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ are synonymous with each of the general formulas (PA-1).
C ⁺ indicates a counter cation.

As the counter cation, an onium cation is preferable. ^{More specifically, the sulfonium cation described as S +} (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ^{) in the general formula (ZI) and I +} in the general formula (ZII) described in the photoacid generator described later. Preferred examples include the iodonium cation described as (R ₂₀₄ ) and (R _205).

Specific examples of the compound (PA) include, but are not limited to, the compounds described in paragraphs [0743] to [0750] of JP2013-83966A.

Further, a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected. For example, an ionic compound having a proton acceptor moiety in the cation portion may be used. More specifically, a compound represented by the following general formula (7) can be mentioned.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2 and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.

As X ⁻ , a specific example similar to ^{X −} in the general formula (ZI) described later can be mentioned.
The aryl group of R and R _N, is preferably a phenyl group.

Proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

In the composition for forming an upper layer film, the blending amount of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content.

(6) Guanidine Compound The composition for forming an upper layer film may further contain a guanidine compound having a structure represented by the following formula (hereinafter, also referred to as “guanidine compound (A)”).

The guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by the three nitrogens.
The basicity of the guanidine compound (A) is preferably 7.0 to 20.0 in that the pKa of the conjugate acid is 6.0 or more, the neutralization reactivity with the acid is high, and the roughness property is excellent. It is preferably 8.0 to 16.0, and more preferably 8.0 to 16.0.

Due to such strong basicity, it is possible to suppress the diffusivity of acid and contribute to the formation of an excellent pattern shape.

As used herein, logP is a logarithmic value of n-octanol / water partition coefficient (P) and is an effective parameter capable of characterizing the hydrophilicity / hydrophobicity of a wide range of compounds. Generally, the partition coefficient is obtained by calculation regardless of the experiment, and in the present specification, CSChemDrawUltraVer. The value calculated by 8.0 softpackage (Crippen's fragmentation method) is shown.

Further, the logP of the guanidine compound (A) is preferably 10 or less. When it is equal to or less than the above value, it can be uniformly contained in the resist film.

The logP of the guanidine compound (A) is preferably 2 to 10, more preferably 3 to 8, and even more preferably 4 to 8.

Further, the guanidine compound (A) preferably has no nitrogen atom other than the guanidine structure.

Specific examples of the guanidine compound include, but are not limited to, the compounds described in paragraphs [0765] to [0768] of JP2013-83966A.

(7) Low-molecular-weight compound having a nitrogen atom and having a group desorbed by the action of an acid The composition for forming an upper layer film is a low-molecular-weight compound having a nitrogen atom and having a group desorbed by the action of an acid (7). Hereinafter, it may also include "low molecular weight compound (D)" or "compound (D)"). The small molecule compound (D) preferably has basicity after the group to be eliminated by the action of an acid is eliminated.

The group desorbed by the action of an acid is not particularly limited, but an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group is preferable, and a carbamate group or a hemiami. A nal ether group is more preferred.

The molecular weight of the small molecule compound (D) having a group eliminated by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.

As the compound (D), an amine derivative having a group eliminated by the action of an acid on a nitrogen atom is preferable.

Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In the general formula (d-1)
R'independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R'may be coupled to each other to form a ring.

As R', a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. ..
A specific example of the structure represented by the general formula (d-1) is shown below.

The compound (D) can be configured by arbitrarily combining the above-mentioned basic compound and the structure represented by the general formula (d-1).

It is particularly preferable that the compound (D) has a structure represented by the following general formula (A).

The compound (D) may be a compound corresponding to the above-mentioned basic compound as long as it is a small molecule compound having a group desorbed by the action of an acid.

In the general formula (A), _Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Also, when n = 2, the two R _a may be the same or different, two R _a attached to each other to form a divalent heterocyclic hydrocarbon group (preferably 20 or less carbon atoms), Alternatively, the derivative may be formed.

R _b independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. However, in -C (R _b ) (R _b ) (R _b ), when one or more R _b is a hydrogen atom _{, at least one of the remaining R b} is a cyclopropyl group, a 1-alkoxyalkyl group, or , Aryl group.

At least two R _bs may be bonded to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

In the general formula (A), the _{alkyl group, cycloalkyl group, aryl group, or aralkyl group represented by Ra} and R _b is a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group. It may be substituted with a functional group such as, an alkoxy group, or a halogen atom. The same applies to the alkoxyalkyl group represented by _{R b.}

The _{alkyl group, cycloalkyl group, aryl group, or aralkyl group of Ra} and / or R _b (these alkyl group, cycloalkyl group, aryl group, or aralkyl group is the functional group, alkoxy group, halogen. It may be replaced with an atom)
For example, groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, and derived from these alkanes. A group in which the group to be used is substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptan, cyclooctane, norbornan, adamantan, and noradamantan, and groups derived from these cycloalkanes are, for example, methyl group, ethyl group, n. Substituted with one or more of linear or branched alkyl groups such as -propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, or t-butyl group. Butyl group
Groups derived from aromatic compounds such as benzene, naphthalene, and anthracene, and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-. A group substituted with one or more of linear or branched alkyl groups such as a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a t-butyl group.
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indole, quinoline, perhydroquinoline, indazole, and benzimidazole, and groups derived from these heterocyclic compounds. A group substituted with one or more of a linear or branched alkyl group or a group derived from an aromatic compound,
A group derived from a linear or branched alcan, and a group obtained by substituting one or more of a group derived from an aromatic compound such as a phenyl group, a naphthyl group, and an anthracenyl group with a group derived from a cycloalcan, and a group. Examples thereof include groups in which the above-mentioned substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group.

Further, examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) formed by bonding _{Ra to each other or a derivative thereof include pyrrolidine, piperidine, morpholin, 1,} 4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazin, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H -1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazole [1,2-a] pyridine, (1S, 4S)-(+) ) -2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] deck-5-ene, indol, indolin, 1,2,3,4- Groups derived from heterocyclic compounds such as tetrahydroquinoxalin, perhydroquinolin, and 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds are linear or branched. Alcan-derived group, cycloalcan-derived group, aromatic compound-derived group, heterocyclic compound-derived group, hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, or , A group substituted with one or more functional groups such as an oxo group.

Specific examples of the compound (D) include, but are not limited to, the compounds described in paragraphs [0786] to [0788] of JP2013-83966A.

The compound represented by the general formula (A) can be synthesized based on JP-A-2007-298569, JP-A-2009-199021, and the like.
Compound (D) may be used alone or in combination of two or more.

Other usable compounds include compounds synthesized in Examples of JP-A-2002-363146, compounds described in paragraph 0108 of JP-A-2007-298569, and the like.
As the basic compound, a photosensitive basic compound may be used. Examples of the photosensitive basic compound include JP-A-2003-524799 and J. Am. Photopolym. Sci & Tech. Vol. 8, P.I. The compounds described in 543-553 (1995) and the like can be used.
As the basic compound, a compound called a so-called photodisintegrating base may be used. Examples of the photodisintegrating base include an onium salt of a carboxylic acid and an onium salt of a sulfonic acid whose α-position is not fluorinated. Specific examples of the photodisintegrating base include the groups described in paragraph 0145 of WO2014 / 133048A1, Japanese Patent Application Laid-Open No. 2008-158339, and Japanese Patent No. 399146.

(Content of basic compound)
The content of the basic compound in the upper layer film forming composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the upper layer film forming composition. 1 to 5% by mass is more preferable.

(Base generator)
Examples of the base generator (photobase generator) include JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, and JP-A-6-. Examples thereof include the compounds described in JP-A-194834, JP-A-8-146608, JP-A-10-83079, and European Patent No. 622682.
Further, the compounds described in JP-A-2010-243773 are also used as appropriate.
Specific examples of the photobase generator include 2-nitrobenzyl carbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4-methylphenylsulfonamide, and 1,1-dimethyl-2-. Phenylethyl-N-isopropylcarbamate can be mentioned.

(Content of base generator)
The content of the base generator in the upper layer film forming composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the upper layer film forming composition. 1 to 5% by mass is more preferable.

<(A2) Compound having a bond or group selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond>
A compound having at least one bond or group selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond (hereinafter, also referred to as compound (A2)) will be described below. do.

As described above, the compound (A2) is a compound containing at least one bond or group selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond. Since the oxygen atom or sulfur atom contained in these bonds or groups has an unshared electron pair, the acid can be trapped by the interaction with the acid diffused from the resist film.

The compound (A2) preferably has two or more bonds or groups selected from the above group, more preferably three or more, and even more preferably four or more. In this case, the bond or group selected from the ether bond, the thioether bond, the hydroxyl group, the thiol group, the carbonyl bond, and the ester bond contained in the compound (A2) may be the same or different from each other. You may.

The molecular weight of compound (A2) is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less, and particularly preferably 1500 or less.

The number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more.
The number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

The boiling point of compound (A2) is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and even more preferably 240 ° C. or higher.

Further, the compound (A2) is preferably a compound having an ether bond, preferably having 2 or more ether bonds, more preferably 3 or more, and further preferably 4 or more.
Among them, the compound (A2) preferably contains a repeating unit having an oxyalkylene structure represented by the following general formula (1).

During the ceremony
R ₁₁ represents an alkylene group which may have a substituent and represents
n represents an integer of 2 or more
* Represents the binding site.

_{The number of carbon atoms of the alkylene group represented by R 11} in the general formula (1) is not particularly limited, but 1 to 15 is preferable, 1 to 5 is more preferable, 2 or 3 is further preferable, and 2 is particularly preferable. When this alkylene group has a substituent, the substituent is not particularly limited, but for example, an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
n is preferably 2 to 20, and more preferably 10 or less because the focus margin (DOF: Depth of Focus) becomes larger.
The average value of n is preferably 20 or less, more preferably 2 to 10, further preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. Here, the "average value of n" means a value of n determined by measuring the weight average molecular weight of the compound (A2) by GPC and making the obtained weight average molecular weight consistent with the general formula. If n is not an integer, it shall be rounded off.
The plurality of R _11s may be the same or different.

Further, the compound having a partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) because the DOF becomes larger.

During the ceremony
R ₁₁ is the same as _{R 11} in general formula (1).
R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but 1 to 15 is preferable. R ₁₂ and R ₁₃ may be combined with each other to form a ring.
m represents an integer of 1 or more. m is preferably an integer of 1 to 20, and more preferably 10 or less because the DOF becomes larger.
The average value of m is preferably 20 or less, more preferably 1 to 10, further preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. Here, the "average value of m" is synonymous with the above-mentioned "average value of n".
When m is 2 or more, a plurality of R _11s may be the same or different.

The compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.

The compound (A2) may be a commercially available product or may be synthesized by a known method.

Specific examples of compound (A2) are shown below.

The content of the compound (A2) in the composition for forming an upper layer film is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content of the composition for forming an upper layer film. -20% by mass is more preferable, and 3 to 18% by mass is particularly preferable.

<Surfactant>
The composition for forming an upper layer film may further contain a surfactant.
The surfactant is not particularly limited, and if the composition for forming an upper layer film can be uniformly formed and dissolved in the solvent of the composition for forming an upper layer film, an anionic surfactant, a cationic surfactant, and , Nonionic surfactants can be used.
The amount of the surfactant added is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the composition for forming the upper layer film.
The surfactant may be used alone or in combination of two or more.

Examples of the surfactant include alkyl cationic surfactants, amide-type quaternary cationic surfactants, ester-type quaternary cationic surfactants, amine oxide-based surfactants, betaine-based surfactants, and alkoxys. Rate-based surfactants, fatty acid ester-based surfactants, amide-based surfactants, alcohol-based surfactants, ethylenediamine-based surfactants, and fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, Silicon-based surfactants and surfactants having both a fluorine atom and a silicon atom) are preferable.
Specific examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, and , Polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenol ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate. , And sorbitan fatty acid esters such as sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and poly. Surfactants such as oxyethylene sorbitan tristearate; and the commercially available surfactants listed below can be mentioned.
Examples of commercially available surfactants that can be used include Ftop EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431, and 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck F171. F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Surfron S-382, SC101, 102, 103, 104, 105, and 106 (Asahi Glass (Asahi Glass) (Manufactured by Toa Synthetic Chemical Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, and GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surfron S-393 (manufactured by Seimi Chemical Co., Ltd.), EFtop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351,352, EF801, EF802, and EF601 (manufactured by Gemco Co., Ltd.), PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA) Fluorescent surfactants such as FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, and 222D (manufactured by Neos Co., Ltd.) or silicon-based surfactants can be mentioned. Further, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

<Method of preparing composition for forming upper layer film>
The upper layer film forming composition produced by the method for producing an upper layer film forming composition of the present invention is preferably prepared by dissolving the above components in a solvent. As described above, as the source of the fluorine-containing resin, a solution containing the fluorine-containing resin that has undergone the first filtration step in the method for producing the composition for forming an upper layer film is used. The prepared upper layer film forming composition is subjected to the second filtration step described above.
The composition for forming an upper layer film preferably does not contain impurities such as metals. The content of the metal component contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and particularly preferably not substantially contained (below the detection limit of the measuring device). ..

[Photosensitive resin composition]
Next, the photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention will be described.
As described above, the photosensitive resin composition is prepared by using a solution containing a fluorine-containing resin that has undergone the first filtration step in the method for producing the photosensitive resin composition. That is, the photosensitive resin composition contains a fluorine-containing resin. The definition of the fluorine-containing resin is as described above.
The content of the fluorine-containing resin in the photosensitive resin composition is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total solid content.
Hereinafter, other components that may be contained in the photosensitive resin composition will be described in detail.

<Resin>
The photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention may be a negative type photosensitive resin composition or a positive type photosensitive resin composition. The photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention typically contains a resin whose polarity is increased by the action of an acid and its solubility in a developing solution containing an organic solvent is reduced. ..
A resin whose polarity is increased by the action of an acid and whose solubility in a developing solution containing an organic solvent is reduced (hereinafter, also referred to as “resin (A)”) is a main chain or side chain of the resin, or a main chain and a side chain. A resin having a group (hereinafter, also referred to as “acid-degradable group”) that decomposes by the action of an acid to generate a polar group (hereinafter, also referred to as “acid-degradable resin”) is preferable.
Further, the resin (A) is more preferably a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure (hereinafter, also referred to as "alicyclic hydrocarbon-based acid-degradable resin"). A resin having a monocyclic or polycyclic alicyclic hydrocarbon structure has high hydrophobicity, and it is considered that the developability when developing a region of a resist film having a weak light irradiation intensity with an organic developer is improved.

The photosensitive resin composition containing the resin (A) can be suitably used when irradiating ArF excimer laser light.

Typical examples of the polar group in the acid-degradable group include an acid group, specifically, a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, and the like. (Alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) ) An imide group, a tris (alkylcarbonyl) methylene group, a group having a tris (alkylsulfonyl) methylene group, and the like can be mentioned.
Preferred polar groups include a carboxylic acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonic acid group and the like.
A preferred group as a group that can be decomposed by an acid (acid-decomposable group) is a group in which the hydrogen atom of these polar groups is replaced with a group that desorbs an acid.
The groups eliminated with an acid include, for example, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) ( R ₀₂ ) (OR ₃₉ ) and the like can be mentioned.
In the formula, R _{36 to} R ₃₉ independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.
R _{01 to} R ₀₂ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
As the acid-degradable group, a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and a tertiary alkyl ester group is more preferable.

The resin (A) is selected from at least a group of repeating units having a partial structure represented by the following general formulas (pI) to (pV) and repeating units represented by the following general formulas (II-AB). It is preferable that the resin has one type.

In the general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z is required to form a cycloalkyl group with a carbon atom. Represents a group of atomic groups.
R _{12 to} R ₁₆ independently represent a linear or branched alkyl group or a cycloalkyl group having 1 to 4 carbon atoms. However, _{at least one of R 12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, _{at least one of R 17 to} R ₂₁ represents a cycloalkyl group. Further, _{either R 19} or R _{21 represents} a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group.
R _{22 to} R ₂₅ independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, _{at least one of R 22 to} R ₂₅ represents a cycloalkyl group. Further, R ₂₃ and R ₂₄ may be coupled to each other to form a ring.

In the general formula (II-AB),
R ₁₁ ′ and R ₁₂ ′ independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group.
Z'contains two bonded carbon atoms (CC) and represents an atomic group for forming an alicyclic structure.

Further, the general formula (II-AB) is preferably the following general formula (II-AB1) or general formula (II-AB2).

In formulas (II-AB1) and (II-AB2),
R _{13'~R 16} 'are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5, group decomposable by the action of an acid, -C (= O) -X- A'-R _{Represents 17} ', an alkyl group, or a cycloalkyl group. R _{l3'~R 16} may form a ring of at least two members to one of '.
Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure.
X represents an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} , or represents -NHSO ₂ NH-.
A'represents a single bond or a divalent linking group.
R ₁₇ ′ represents -COOH, -COOR ₅ , -CN, hydroxyl group, alkoxy group, -CO-NH-R ₆ , -CO-NH-SO _2- R ₆ , or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.

In the general formulas (pI) to (pV), the _{alkyl group in R 12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo structure, a bicyclo structure, a tricyclo structure, a tetracyclo structure and the like having 5 or more carbon atoms. The cycloalkyl group preferably has 6 to 30 carbon atoms, more preferably 7 to 25 carbon atoms. These cycloalkyl groups may have substituents.

Examples of the cycloalkyl group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a sedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecanyl group. A group or a cyclododecanyl group is preferable, and an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, or a tricyclodecanyl group is more preferable.

Further substituents of these alkyl groups and cycloalkyl groups include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (1 to 4 carbon atoms). The number of carbon atoms is 2 to 6). Examples of the substituent that the above-mentioned alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

The structures represented by the general formulas (pI) to (pV) in the above resin can be used for protection of polar groups. Examples of the polar group include various groups known in the art.

Specific examples thereof include a structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group is substituted with a structure represented by the general formulas (pI) to (pV). Of these, a structure in which the hydrogen atom of the carboxylic acid group or the sulfonic acid group is replaced with a structure represented by the general formulas (pI) to (pV) is preferable.

As the repeating unit having a polar group protected by the structures represented by the general formulas (pI) to (pV), the repeating unit represented by the following general formula (pA) is preferable.

Here, R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. The plurality of Rs may be the same or different.
A is a single group or two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group. Represents a combination. Above all, a single bond is preferable.
Rp ₁ represents any group of the above formulas (pI) to (pV).

The repeating unit represented by the general formula (pA) is preferably a repeating unit made of 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate.

A specific example of the repeating unit represented by the general formula (pA) is shown below.

Examples of the halogen atom in the above general formula (II-AB), R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, an iodine atom and the like independently.

Examples _{of the alkyl group in R 11} ′ and R ₁₂ ′ are independent linear or branched alkyl groups having 1 to 10 carbon atoms.

The alicyclic structure of Z'is formed by forming a repeating unit of an alicyclic hydrocarbon which may have a substituent on a resin, and among them, an alicyclic fat. A group of atoms for forming a bridge-type alicyclic structure that forms a repeating unit of a ring-type hydrocarbon is preferable.

As the skeleton of alicyclic hydrocarbon formed include the same skeletons as the alicyclic hydrocarbon group R ₁₂ to R ₂₅ in the general formula (pI) ~ (pV).

The skeleton of the alicyclic hydrocarbon may have a substituent. _{Examples of such a substituent include R 13} ′ to _{R 16} ′ in the above general formula (II-AB1) or (II-AB2).

The resin (A) is preferably a resin having a repeating unit having an acid-degradable group, and the acid-degradable group is, for example, a repeating unit having a partial structure represented by the above general formulas (pI) to (pV). , And / or may be included in the repeating unit represented by the general formula (II-AB). The acid-degradable group is preferably contained in a repeating unit having a partial structure represented by the general formulas (pI) to (pV).

The repeating unit having an acid-degradable group of the resin (A) may be used alone or in combination of two or more.

The resin (A) preferably has a repeating unit having a lactone structure or a sultone (cyclic sulfonic acid ester) structure.
As the lactone group or sultone group, any one having a lactone structure or a sultone structure can be used. Among them, a 5- to 7-membered lactone structure or a sultone structure is preferable, and a group in which another ring structure is condensed in a form of forming a bicyclo structure or a spiro structure in the 5 to 7-membered ring lactone structure or sultone structure is used. More preferred. Having a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17), general formula (SL1-1) and general formula (SL1-2). More preferred. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. As the lactone structure or sultone structure, the general formula (LC1-1), the general formula (LC1-4), the general formula (LC1-5), or the general formula (LC1-8) is preferable, and the general formula (LC1-4) Is more preferable. LWR (Line Width Roughness, fluctuation of pattern line width) and development defects can be improved by using a specific lactone structure or sultone structure.

The lactone-structured portion or sultone-structured portion may or may not have a _{substituent (Rb 2).} Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. A halogen atom, a hydroxyl group, a cyano group, or an acid-degradable group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group is more preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different, or the plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring. ..

The resin (A) preferably has a repeating unit having an organic group having a polar group, and more preferably has a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves substrate adhesion and developer affinity. As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamantyl group, or a norbornane group is preferable. As the polar group, a hydroxyl group or a cyano group is preferable.
As the alicyclic hydrocarbon structure substituted with a polar group, a partial structure represented by the following general formulas (VIIa) to (VIId) is preferable.

In the general formulas (VIIa) to (VIIc),
R _{2c to} R _4c independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, _{at least one of R 2c to} R _4c represents a hydroxyl group or a cyano group. Of these, _{it is preferable that one or two of R 2c to} R _4c are hydroxyl groups and the rest are hydrogen atoms.
Further, in the general formula (VIIa), _{it is more preferable that two of R 2c to} R _4c are hydroxyl groups and the rest are hydrogen atoms.

An example of a repeating unit having a group represented by the general formulas (VIIa) to (VIId) is at least one _{of R 13 ′ to R 16 ′ in the general formula (II-AB1) or (II-AB2).} One has repeating units (e.g., represents a _{group R 5} in -COOR ₅ is a represented by the general formula (VIIa) ~ (VIId)) having a group represented by the general formula (VII), and the following general formula ( Repeat units represented by AIIA) to (AIID) can be mentioned.

In the general formulas (AIIA) to (AIID),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydrochimethyl group.
R _2c to R _4c have the same meanings as _R 2c _{to R 4c} in formulas (VIIa) ~ (VIIc).

Specific examples of repeating units having structures represented by the general formulas (AIIA) to (AIID) are shown below.

The weight average molecular weight of the resin (A) is preferably 1000 to 200,000, more preferably 1000 to 20000, and even more preferably 1000 to 15000 in terms of polystyrene by the GPC method. By setting the weight average molecular weight to 1000 to 200,000, it is possible to prevent deterioration of heat resistance or dry etching resistance, and the developability is deteriorated, the viscosity is increased, and the film forming property is deteriorated. Can be prevented.
The dispersity is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side wall of the pattern, and the better the roughness.

The content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the photosensitive resin composition.
Further, the resin (A) may be used alone or in combination of two or more.

The resin (A) preferably does not have a fluorine atom and a silicon atom from the viewpoint of compatibility with the composition for forming an upper layer film.

<Compounds that generate acid when irradiated with active light or radiation>
The photosensitive resin composition typically comprises a compound that generates an acid upon irradiation with active light or radiation (also referred to as a "photoacid generator" or "compound (B)").
Compound (B) may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
When the compound (B) is in the form of a small molecule compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the compound (B) is in a form incorporated in a part of the polymer, it may be incorporated in a part of the above-mentioned acid-degradable resin, or may be incorporated in a resin different from the acid-degradable resin. ..
Compound (B) is preferably a small molecule compound.
The compound (B) may be subjected to irradiation with active light or radiation used in a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photocoloring agent, a microresist, or the like. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate can be mentioned.

Further, a compound in which a group or compound that generates an acid by irradiation with these active rays or radiation is introduced into the main chain or side chain of a polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407, JP-A. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853. Alternatively, the compound described in JP-A-63-146029 can be used.

Further, compounds that generate acid by light as described in US Pat. No. 3,779,778, European Patent No. 126712, etc. can also be used.

As the compound (B), a compound that generates an acid having a cyclic structure by irradiation with active light or radiation is preferable. As the cyclic structure, a monocyclic or polycyclic alicyclic group is preferable, and a polycyclic alicyclic group is more preferable. It is preferable that the carbon atom constituting the ring skeleton of the alicyclic group does not contain carbonyl carbon.
As the compound (B), for example, a compound (specific acid generator) that generates an acid by irradiation with an active ray or radiation represented by the following general formula (3) is preferable.

(Anion)
In general formula (3),
Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of them, R ₄ and R ₅ are the same, respectively. But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
W represents an organic group containing a cyclic structure.
o represents an integer of 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . Above all, it is preferable that both Xf are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, _{and when there are a plurality of them, R 4} and R ₅ are the same, respectively. But it can be different.
The alkyl group as R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
Examples of the divalent linking group include -COO- (-C (= O) -O-), -CONH-, -CO-, -O-, -S-, -SO-, -SO _2- , An alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these groups. And so on. Among them, -COO -, - CONH -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group -, or, -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group -, or, -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Of these, it is preferably a cyclic organic group.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, a diamantyl group, or an adamantyl group, is used in PEB. It is preferable from the viewpoint of suppressing the diffusivity in the membrane and improving the MEEF (Mask Error Enhancement Factor).

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Of these, a naphthyl group having a relatively low photoabsorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress the diffusion of acid more. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable. Further, examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin.

The cyclic organic group may have a substituent. The substituent may be, for example, an alkyl group (either linear or branched, preferably 1 to 12 carbon atoms) or a cycloalkyl group (either monocyclic or polycyclic). Often, 3 to 20 carbon atoms are preferable), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfone. Examples include acid ester groups. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

o represents an integer of 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.
In one embodiment, it is preferable that o in the general formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is 0. Xf is preferably a fluorine is atomic, preferably R ₄ and R ₅ are both hydrogen atoms, W is preferably a hydrocarbon group of polycyclic. o is more preferably 1 or 2, and even more preferably 1. p is more preferably an integer of 1-3, even more preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, even more preferably an adamantyl group or a diamantyl group.

(Cation)
In the general formula (3), X ⁺ represents a cation.
X ⁺ is not particularly limited as long as it is a cation, but preferred embodiments include cations (parts other than ^{Z −) in the general formulas (ZI), (ZII) and (ZIII) described later.}

(Preferable aspect)
Preferable embodiments of the specific acid generator include, for example, compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The _{number of carbon atoms of the organic group as R 201} , R ₂₀₂ and R ₂₀₃ is preferably 1 to 30, and more preferably 1 to 20.
Further, two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Z ⁻ represents an anion in the general formula (3), and specifically represents the following anion.

In addition, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, the general formula at least one of _R 201 _{to R 203} of a compound represented by (ZI), at least one of _R 201 _{to R 203} of another compound represented by formula (ZI), a single bond or It may be a compound having a structure bonded via a linking group.
Compound (B) may be used alone or in combination of two or more.
The content of compound (B) in the photosensitive resin composition (the total of a plurality of types if present) is preferably 0.1 to 30% by mass, preferably 0, based on the total solid content of the photosensitive resin composition. .5 to 25% by mass is more preferable, 3 to 20% by mass is further preferable, and 3 to 15% by mass is particularly preferable.

<Solvent>
The photosensitive resin composition may contain a solvent. Examples of the solvent include alkylene glycol monoalkyl ether carboxylate (PGMEA, etc.), alkylene glycol monoalkyl ether (PGME (propylene glycol monomethyl ether), etc.), lactic acid alkyl ester, alkyl alkoxypropionate, and a cyclic ring having 4 to 10 carbon atoms. Examples thereof include lactones (γ-butyrolactone and the like), monoketone compounds having 4 to 10 carbon atoms which may have a ring (cyclohexanone and the like), alkylene carbonates, alkyl alkoxyacetates, and organic solvents such as alkyl pyruvate.
Further, as described above, it is also preferable to use the same solvent as the solvent contained in the solution containing the fluorine-containing resin used in the first filtration step in the method for producing the photosensitive resin composition.

<Basic compound>
The photosensitive resin composition preferably contains a basic compound in order to reduce the change in performance with time from exposure to heating.
As the basic compound, compounds having a structure represented by the following formulas (A) to (E) are preferable.

In the general formulas (A) to (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and may be a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), or an aryl group (preferably 3 to 20 carbon atoms). It represents 6 to 20 carbon atoms), where R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.
It is more preferable that the alkyl groups in these general formulas (A) to (E) are unsubstituted.

As the basic compound, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin, or piperidine are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, and trialkylamine. A compound having a structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond is more preferable.

Specific examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Specific examples of compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo. [5,4,0] Undec-7-en can be mentioned. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specific examples thereof include triphenylsulfonium hydroxide and tris. Examples thereof include (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Be done. Specific examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Specific examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, and N, N-dihexylaniline. Specific examples of alkylamine derivatives having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Specific examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Further, as the basic compound, a basic compound which may be contained in the above-mentioned composition for forming an upper layer film can also be preferably used.

These basic compounds may be used alone or in combination of two or more.
The amount of the basic compound used is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the photosensitive resin composition.

The ratio of the photoacid generator to the basic compound in the photosensitive resin composition is preferably photoacid generator / basic compound (molar ratio) = 2.5 to 300. The molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to pattern thickening over time from exposure to heat treatment. Among them, the photoacid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

<Surfactant>
The photosensitive resin composition preferably further contains a surfactant, and contains fluorine-based and / or silicon-based surfactants (fluorine-based surfactant, silicon-based surfactant, and both fluorine atom and silicon atom. It is more preferable to contain any one of the surfactants) or two or more of them.

When the photosensitive resin composition contains the above-mentioned surfactant, it is possible to provide a pattern with good sensitivity and resolution, with few adhesions and development defects, when using an exposure light source of 250 nm or less, particularly 220 nm or less. ..
Examples of the fluorine-based and / or silicon-based surfactant include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. , Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, Japanese Patent Application Laid-Open No. 2002-277682, In U.S. Patent No. 5405720, U.S. Patent No. 5360692, U.S. Pat. Examples of the above-mentioned surfactants can be mentioned, and commercially available surfactants can be used as they are.

These surfactants may be used alone or in combination of several.

The amount of the surfactant used is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the photosensitive resin composition.

<Carboxylic acid onium salt>
The photosensitive resin composition may contain an onium carboxylic acid salt. Examples of the onium carboxylic acid salt include a sulfonium carboxylic acid salt, an iodonium carboxylic acid salt, and an ammonium carboxylic acid salt. Among them, as the onium carboxylic acid salt, an iodonium salt or a sulfonium salt is preferable. Further, it is preferable that the carboxylate residue of the onium carboxylic acid salt does not have an aromatic group or a carbon-carbon double bond. As the anion portion, a linear, branched chain, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. Of these, an anion of a carboxylic acid in which a part or all of the alkyl group is substituted with fluorine is preferable. An oxygen atom may be contained in the alkyl chain. This ensures transparency to light of 220 nm or less, improves sensitivity and resolution, and improves sparse density dependence and exposure margin.

Specific examples of fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, and perfluorocyclohexanecarboxylic acid. Acids and anions of 2,2-bistrifluoromethylpropionic acid can be mentioned.

These onium carboxylic acid salts can be synthesized by reacting a sulfonium hydroxide, an iodonium hydroxide, or an ammonium hydroxide with a carboxylic acid in a suitable solvent with silver oxide.

The content of the carboxylic acid onium salt in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and 1 to 7 with respect to the total solid content of the photosensitive resin composition. Mass% is more preferred.

<Other additives>
The photosensitive resin composition further comprises a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound (for example, a molecular weight of 1000) that promotes solubility in a developing solution, if necessary. The following phenol compounds, or alicyclic or aliphatic compounds having a carboxyl group) and the like can be included.

For such a phenol compound having a molecular weight of 1000 or less, refer to, for example, the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent No. 2192294, and the like. Therefore, it can be easily synthesized by those skilled in the art.
Specific examples of the alicyclic or aliphatic compound having a carboxyl group include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, an adamantancarboxylic acid derivative, an adamantandicarboxylic acid, and a cyclohexanecarboxylic acid. , Cyclohexanedicarboxylic acid.

<Method of preparing photosensitive resin composition>
The solid content concentration of the photosensitive resin composition is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass. By setting the solid content concentration in the above range, the photosensitive resin composition can be uniformly applied on the substrate, and a pattern excellent in LWR can be formed. The reason is not clear, but probably, by setting the solid content concentration to 10% by mass or less (preferably 5.7% by mass or less), the material in the photosensitive resin composition, particularly the photoacid generator, is used. It is considered that aggregation is suppressed, and as a result, a uniform resist film can be formed.
The solid content concentration is the mass percentage of the mass of other photosensitive resin compositions excluding the solvent with respect to the total mass of the photosensitive resin composition.

The photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention is prepared by dissolving the above-mentioned components in a predetermined solvent. As a source of the fluorine-containing resin contained in the photosensitive resin composition, it is preferable to use a solution containing the fluorine-containing resin that has undergone the first filtration step in the method for producing the photosensitive resin composition. The prepared photosensitive resin composition is subjected to the above-mentioned second filtration step, and can be applied and used on a predetermined support (substrate).

[Pattern formation method]
A pattern forming method using the upper layer film forming composition produced by the method for producing an upper layer film forming composition of the present invention, or a photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention. The pattern forming method using the above will be described.

The pattern forming method using the above-mentioned upper layer film forming composition preferably includes the following steps a1 to c1.
Step a1: A step of forming an upper layer film on the resist film using the above composition for forming an upper layer film Step b1: A step of exposing the resist film Step c1: A step of developing the exposed resist film Each step below Will be described in detail.

<Step a1>
Step a1 is a step of forming an upper layer film on the resist film by using the above-mentioned upper layer film forming composition.
As the resist film, a known resist film can be used. For example, a resin (A) which may be contained in the above-mentioned photosensitive resin composition, and a resist film formed by using a composition containing a photoacid generator or the like can be mentioned. More specifically, it is preferable to apply a composition containing the resin (A), a photoacid generator, and the like onto a predetermined substrate to form a resist film.
The method of applying the composition onto the substrate is not particularly limited, and examples thereof include a conventionally known spin coating method, spray method, roller coating method, dipping method, and the like, and the spin coating method is preferable.
After applying the above composition, the substrate may be heated (prebaked (PB)) if necessary. As a result, a resist film from which the insoluble residual solvent has been removed can be uniformly formed. The temperature of the prebake is not particularly limited, but is preferably 50 to 160 ° C, more preferably 60 to 140 ° C.
The film thickness of the resist film is preferably 20 to 200 nm, more preferably 30 to 100 nm.

The substrate on which the resist film is formed is not particularly limited, and specifically, _{an inorganic substrate such as silicon, SiN, SiO 2} and SiN; a coating-based inorganic substrate such as SOG (Spin on Glass); and an IC (Integrated Circuit). ), Etc., circuit boards such as liquid crystal and thermal heads, and substrates commonly used in lithography processes for other photo applications.

An antireflection film may be applied on the substrate in advance before forming the resist film.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type composed of a light absorber and a polymer material can be used. Specific examples of the organic antireflection coatings that can be used include DUV30 series and DUV-40 series manufactured by Brewer Science, AR-2, AR-3, and AR-5 manufactured by Chypre, and others. Examples thereof include commercially available organic antireflection films such as the ARC series such as ARC29A manufactured by Nissan Chemical Industries, Ltd.

The method for forming the upper layer film on the resist film by using the above-mentioned upper layer film forming composition is not particularly limited, but for example, the upper layer film forming composition is applied on the resist film, and then, if necessary. By heating (prebaking), an upper layer film can be formed on the resist film.
The method for applying the composition for forming an upper layer film is not particularly limited, and examples thereof include a conventionally known spin coating method, a spray method, a roller coating method, and a dipping method.
The prebake temperature (hereinafter, also referred to as “PB temperature”) is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, further preferably 110 ° C. or higher, particularly preferably 120 ° C. or higher, and most preferably over 120 ° C.
The upper limit of the PB temperature is not particularly limited, but is preferably 200 ° C. or lower, more preferably 170 ° C. or lower, further preferably 160 ° C. or lower, and particularly preferably 150 ° C. or lower.

When the exposure in step b1 described later is an immersion exposure, the upper layer film is arranged between the resist film and the immersion liquid, and functions as a layer that does not directly contact the resist film with the immersion liquid. In this case, the preferable properties of the upper layer film are transparency to radiation (particularly wavelength; 193 nm) and poor solubility to immersion liquid (preferably water). Further, it is preferable that the composition for forming an upper layer film is not mixed with the resist film, has excellent coatability on the surface of the resist film, and can uniformly apply the composition for forming an upper layer film.
In order to uniformly apply the upper layer film forming composition to the surface of the resist film without dissolving the resist film, it is preferable that the upper layer film forming composition contains a solvent that does not dissolve the resist film. As the solvent that does not dissolve the resist film, it is more preferable to use a solvent having a component different from that of the organic developer described later.
The details of the composition for forming the upper layer film are as described above.

The film thickness of the upper layer film is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 300 nm, further preferably 20 to 200 nm, and particularly preferably 30 to 100 nm from the viewpoint of transparency to an exposure light source.
After forming the upper layer film, the substrate is heated as needed.
From the viewpoint of resolvability, the refractive index of the upper layer film is preferably close to the refractive index of the resist film.
From the viewpoint of immersion liquid followability, the receding contact angle (23 ° C.) of the immersion liquid with respect to the upper layer membrane is preferably 50 to 100 degrees, and is preferably 80 to 100 degrees. More preferred.
In immersion exposure, the immersion liquid needs to move on the substrate following the movement of the lens scanning on the substrate at high speed to form an exposure pattern. The contact angle of the immersion liquid is important, and in order to obtain better resist performance, it is preferable to have a receding contact angle in the above range.

When peeling the upper layer film, an organic developer described later may be used, or a peeling agent may be used separately. As the release agent, a solvent having a small penetration into the resist film is preferable. In that the upper layer film can be peeled off at the same time as the resist film is developed, it is preferable that the upper layer film can be peeled off with an organic developer. The organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the resist film, and is a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent, which will be described later. , Or a developing solution containing a hydrocarbon solvent can be selected, and a developing solution containing a ketone solvent, an ester solvent, an alcohol solvent, or an ether solvent is preferable, and a developing solution containing an ester solvent is more preferable. A developing solution containing butyl acetate is preferable, and a developing solution containing butyl acetate is more preferable.

From the viewpoint of peeling with an organic developer, the upper film preferably has a dissolution rate in an organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
Here, the dissolution rate of the upper layer film in an organic developer is the rate of decrease in film thickness when the upper layer film is exposed to the developer after being formed, and in the present specification, it is immersed in a butyl acetate solution at 23 ° C. Let it be the speed when it is made to.
By setting the dissolution rate of the upper layer film in an organic developer to 1 nm / sec or more (preferably 10 nm / sec or more), there is an effect of reducing the occurrence of development defects after developing the resist film. Further, by setting it to 300 nm / sec or less (preferably 100 nm / sec or less), the line edge roughness of the pattern after developing the resist film is better, probably due to the effect of reducing the exposure unevenness during immersion exposure. It has the effect of becoming.
The upper film may be removed by using another known developer, for example, an alkaline aqueous solution. Specific examples of the alkaline aqueous solution that can be used include an aqueous solution of tetramethylammonium hydroxide.

<Step b1>
Step b1 is a step of exposing the resist film.
The exposure in step b1 can be performed by a generally known method. For example, the resist film on which the upper layer film is formed is irradiated with active light rays or radiation through a predetermined mask. At this time, it is preferable to irradiate the active light beam or radiation through the immersion liquid, but the present invention is not limited to this. The exposure amount can be set as appropriate, but 1 to 100 mJ / cm ² is preferable.
Wavelength of the light source used for the exposure apparatus is not particularly limited, it is preferable to use a light of a wavelength 250 nm, and examples thereof, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), _{F 2} Excimer laser light (157 nm), EUV light (13.5 nm), electron beam and the like can be mentioned. Among these, it is preferable to use ArF excimer laser light (193 nm).

When the immersion exposure is performed, the surface of the film may be washed with an aqueous chemical solution before the exposure and / or after the exposure and before the heating described later.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index as small as possible so as to minimize the distortion of the optical image projected on the film, but the exposure light source is particularly suitable. In the case of ArF excimer laser light (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and handling in addition to the above viewpoints.
When water is used, an additive (liquid) that reduces the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably an additive that does not dissolve the resist film on the substrate and whose influence on the optical coating on the lower surface of the lens element can be ignored. Distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used. This makes it possible to suppress distortion of the optical image projected on the resist film due to the mixing of impurities.
Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

The pattern forming method may include step b1 (exposure step) a plurality of times. In that case, the same light source or different light sources may be used for the plurality of exposures, but it is preferable to use ArF excimer laser light (wavelength; 193 nm) for the first exposure.

After the exposure, it is preferable to further heat (PEB) and develop (preferably further rinse). This makes it possible to obtain a good pattern. The temperature of PEB is not particularly limited as long as a good pattern can be obtained, but is preferably 40 to 160 ° C. The PEB may be performed once or multiple times.

<Step c1>
Step c1 is a step of developing the exposed resist film.
The developer used in step c1 may be an alkaline developer or a developer containing an organic solvent, but a developer containing an organic solvent is preferable. A developing step using an alkaline developer and a developing step using a developing solution containing an organic solvent may be combined.
As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, for example, an inorganic alkali, a 1st to 3rd amine, an alcohol amine, a cyclic amine or the like is used. Alkaline aqueous solution of can also be used.
Specifically, the alkaline developing solution includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and inorganic alkalis such as aqueous ammonia; ethylamine and n-propylamine. Primary amines such as diethylamine and secondary amines such as di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine Alkaline aqueous solutions such as tetramethylammonium hydroxide and quaternary ammonium salts such as tetraethylammonium hydroxide; and cyclic amines such as pyrrole and piperidine can be used. Above all, it is preferable to use an aqueous solution of tetraethylammonium hydroxide.
Further, alcohols and / or a surfactant may be added in an appropriate amount to the alkaline developer. The alkali concentration of the alkaline developer is preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.
The time for developing with an alkaline developer is preferably 10 to 300 seconds.
The alkali concentration (and pH) and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.
After development with an alkaline developer, it may be washed with a rinse solution, and pure water may be used as the rinse solution, and an appropriate amount of a surfactant may be added and used.
Further, after the developing treatment or the rinsing treatment, a treatment of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid can be performed.
Further, after the rinsing treatment or the treatment with the supercritical fluid, a heat treatment can be performed to remove the water remaining in the pattern.

As the developing solution containing an organic solvent (hereinafter, also referred to as an organic developing solution), a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent are used. Examples include a developing solution containing.
Specific examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, and methylcyclohexanone. , Phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Specific examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butylate, and the like. Isobutyl butylate, butyl butylate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate. Can be mentioned.
Specific examples of alcohol-based solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, and n-heptyl alcohol. , N-octyl alcohol, and alcohols such as n-decanol; glycol-based solvents such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol; and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, Examples thereof include triethylene glycol monoethyl ether and glycol ether-based solvents such as methoxymethylbutanol.
Specific examples of the ether solvent include dioxane and tetrahydrofuran in addition to the above glycol ether solvent.
Specific examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidi. Non is mentioned.
Specific examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as pentane, hexane, octane, and decane.
A plurality of the above solvents may be mixed, or a solvent other than the above and / or water may be mixed and used. However, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.
Specifically, the amount of the organic solvent used with respect to the organic developer is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, based on the total amount of the developer.

Among these, as the organic developer, a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. A developing solution containing a ketone solvent or an ester solvent is more preferable, and a developing solution containing butyl acetate, butyl propionate, or 2-heptanone is further preferable.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C. By reducing the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the substrate surface is improved, and as a result, dimensional uniformity in the substrate surface is improved. The sex improves.
Specific examples of the solvent having a vapor pressure of 5 kPa or less (or 2 kPa or less) include the solvent described in paragraph [0165] of JP2014-71304A.

The organic developer may contain an appropriate amount of a surfactant, if necessary.
The surfactant is not particularly limited, and examples thereof include ionic or nonionic fluorine-based and / or silicon-based surfactants. Examples of these fluorine and / or silicon-based surfactants include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. , Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988, US Patent No. 5405720, US Patent The surfactants described in No. 5360692, US Pat. No. 5,259881, US Pat. No. 5,296,330, US Pat. No. 5,436,098, US Pat. No. 5,576,143, US Pat. No. 5,294,511, and US Pat. No. 5,824,451. , Non-ionic surfactants are preferred. The nonionic surfactant is not particularly limited, but it is preferable to use a fluorine-based surfactant or a silicon-based surfactant.
The amount of the surfactant used is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, still more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.
The organic developer may contain a basic compound. Specific examples and preferable examples of the basic compound that can be contained in the organic developer are the same as those of the basic compound that can be contained in the photosensitive resin composition.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic discharge). Law) etc.

Further, after the step of developing with a developing solution containing an organic solvent, there may be a step of stopping the development while substituting with another solvent.

After the step of developing with a developing solution containing an organic solvent, a step of cleaning with a rinsing solution may be included.
The rinsing solution is not particularly limited as long as the pattern is not dissolved, and a solution containing a general organic solvent can be used. The rinsing solution is selected from, for example, the above-mentioned hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent as the organic solvent contained in the organic-based developing solution. A rinse solution containing at least one organic solvent is preferable, and a rinse solution containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. Is more preferable, and a rinsing solution containing a hydrocarbon solvent, an alcohol solvent, or an ester solvent is more preferable, and a rinsing solution containing a monovalent alcohol is particularly preferable.

Here, examples of the monohydric alcohol used in the rinsing step include linear, branched and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-methyl-2-. Pentanol, 4-methyl-2-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 1-heptanol, 2-heptanol, 3- Heptanol, 4-methyl-2-heptanol, 5-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 4-methyl-2-octanol, 5-methyl-2-octanol, 6-Methyl-2-octanol, 2-nonanol, 4-methyl-2-nonanol, 5-methyl-2-nonanol, 6-methyl-2-nonanol, 7-methyl-2-nonanol, and 2-decanol Can be mentioned. Of these, 1-hexanol, 2-hexanol, 1-pentanol, 3-methyl-1-butanol, or 4-methyl-2-heptanol is preferable.

Specific examples of the hydrocarbon solvent used in the rinsing step include aromatic hydrocarbon solvents such as toluene and xylene; and pentane, hexane, octane, decane (n-decane), undecane and the like. An aliphatic hydrocarbon solvent of the above can be mentioned.
When an ester solvent is used as the rinsing liquid, a glycol ether solvent may be used in addition to the ester solvent (1 type or 2 or more types). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably PGME) as a sub component. As a result, residual defects are suppressed.

A plurality of each of the above components may be mixed, or may be mixed and used with an organic solvent other than the above.
The water content in the rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Good developability can be obtained by setting the water content to 10% by mass or less.
The vapor pressure of the rinsing liquid is preferably 0.05 to 5 kPa, more preferably 0.1 to 5 kPa, and even more preferably 0.1 to 3 kPa at 20 ° C. By setting the vapor pressure of the rinsing liquid to 0.05 to 5 kPa, the temperature uniformity in the substrate surface is improved, swelling due to the permeation of the rinsing liquid is suppressed, and the dimensional uniformity in the substrate surface is good. To become.
An appropriate amount of a surfactant may be added to the rinse solution before use.

In the rinsing step, the substrate developed using the developer containing an organic solvent is washed with the above-mentioned rinse solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotary coating method), or a method of immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples include a method (dip method) and a method of spraying a rinse liquid on the surface of the substrate (spray method). Among these methods, a cleaning treatment is performed by a rotary coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. , It is preferable to remove the rinse liquid from the substrate. It is also preferable to include a heating step (PostBake) after the rinsing step. Heating removes the developer and rinse solutions that remain between and inside the patterns. The superheating temperature of the heating step after the rinsing step is preferably 40 to 160 ° C, more preferably 70 to 95 ° C. The overheating time of the heating step after the rinsing step is preferably 10 seconds to 3 minutes, more preferably 30 to 90 seconds.

Further, the pattern forming method may include a developing step using an organic developer and a developing step using an alkaline developer. A portion having a weak exposure intensity is removed by development using an organic developer, and a portion having a strong exposure intensity is also removed by development using an alkaline developer. By the multiple development process in which the development is performed a plurality of times in this way, the pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern than usual can be formed (paragraph of JP-A-2008-292975). Mechanism similar to [0077]).

The pattern forming method using the photosensitive resin composition obtained by using the above-mentioned specific solution preferably includes the following steps a2 and c2.
Step a2: A step of forming a resist film using the photosensitive resin composition Step b2: A step of exposing the resist film Step c2: A step of developing the exposed resist film The procedures of the step b2 and the step c2 are described above. Since it is the same as step b1 and step c1, the description thereof will be omitted.
Hereinafter, step a2 will be described in detail.

<Step a2>
Step a2 is a step of forming a resist film using the photosensitive resin composition.
The method of forming a resist film using the above-mentioned photosensitive resin composition is not particularly limited, but a method of applying the photosensitive resin composition on a substrate to form a resist film is preferable.
The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a conventionally known spin coating method, a spray method, a roller coating method, and a dipping method, and the spin coating method is preferable.
After applying the photosensitive resin composition, the substrate may be heated (prebaked (PB)) if necessary. As a result, a film from which the insoluble residual solvent has been removed can be uniformly formed. The temperature of the prebake is not particularly limited, but is preferably 50 to 160 ° C, more preferably 60 to 140 ° C.
The film thickness of the resist film is preferably 20 to 200 nm, more preferably 30 to 100 nm.

The type of substrate on which the resist film is formed is as described above in step a1.

An upper layer film forming composition, a photosensitive resin composition, and various materials used in a pattern forming method (for example, a solvent, a developing solution, a rinsing solution, an antireflection film forming composition, and an upper layer film forming composition). (Things, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and particularly preferably not substantially contained (below the detection limit of the measuring device).

[Manufacturing method of electronic device]
The present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
The manufactured electronic device is suitably mounted on an electric / electronic device (home appliance, OA / media-related device, optical device, communication device, etc.).

Examples are shown below, but the present invention is not limited thereto.

<Fluorine-containing resin>
The monomer corresponding to the repeating unit of the fluorine-containing resin used in the examples or comparative examples, and the molar ratio of each repeating unit to the fluorine-containing resin are shown in Table 1 below.

<First filtration of a solution containing a fluorine-containing resin (for photosensitive resin composition)>
The fluorine-containing resin was dissolved in PGMEA (propylene glycol monomethyl ether acetate) to prepare a solution containing the fluorine-containing resin (solid content concentration: 10% by mass). The obtained solution containing the fluorine-containing resin was subjected to the first filtration step. The obtained filtrate was used for the preparation of the photosensitive resin composition described later (Examples 1 to 6, 8 to 10 and 13 to 18).

<First filtration of a solution containing a fluorine-containing resin (for a composition for forming an upper layer film)>
The fluorine-containing resin was dissolved in diisoamyl ether to prepare a solution containing the fluorine-containing resin (solid content concentration: 20% by mass). The obtained solution containing the fluorine-containing resin was subjected to the first filtration step. The obtained filtrate was used for preparing a composition for forming an upper layer film, which will be described later (Examples 7, 11 and 12).

In each example, the content of the first filtration step of the solution containing the fluorine-containing resin, and the types and pore diameters of the filters are shown in Table 2 below. In Table 2, the description in the lower column of each filter is the material of the filter. And the hole diameter. Blank indicates that filtration by each filter is not performed.
In Table 2, the description in the column of the number of circulations described when the circulation filtration step is carried out is [Integrated filtration amount of the solution containing the fluorine-containing resin by the third filter / the fluorine-containing resin used in the circulation filtration step is included. Amount of solution].
As described above, in Examples 7, 11 and 12, the solvent of the solution containing the fluorine-containing resin is diisoamyl ether. In other examples, the solvent for the solution containing the fluorine-containing resin is PGMEA.
Further, the two types of fluorine-containing resins used in Example 6 are separately prepared into solutions containing the fluorine-containing resins, and then the solutions containing the above two types of fluorine-containing resins are separately first filtered. Used in the process.

<Preparation of photosensitive resin composition>
The resin (A) and other components were mixed to prepare a solution having a solid content concentration of 4.3% by mass and satisfying the ratio in the solid content component and the ratio in the solvent component shown in Table 3 below. The obtained solution was filtered through a polyethylene filter having a pore size of 0.03 μm as a second filtration step. The obtained filtrate was used as a photosensitive resin composition.
When the photosensitive resin composition used as an example contains a fluorine-containing resin, the solution containing the fluorine-containing resin that has undergone the first filtration step is used as the source of the fluorine-containing resin. That is, in Examples 1 to 6, 8 to 10 and 13 to 18 shown in Table 3, the photosensitive resin was used by using the solution containing the fluorine-containing resin that had undergone the first filtration step shown in Table 2 above. The composition was produced.
When the photosensitive resin composition used as a comparative example contains a fluorine-containing resin, the fluorine-containing resin that has not undergone the first filtration step is used as the source of the fluorine-containing resin. That is, in Comparative Examples 1, 2, and 5, a photosensitive resin composition is produced using a fluorine-containing resin that has not been subjected to the first filtration step, and only the second filtration step is carried out. ..
The second filtration step was carried out twice for the photosensitive resin composition of Comparative Example 5.
Further, since the photosensitive resin compositions in Examples 7, 11, and 12, and Comparative Examples 3, 4, and 6, do not contain a fluorine-containing resin, the first filtration step is not carried out. Only the second filtration step was carried out.

The formulations of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 3 below.

The repeating unit of the resin (A) used for preparing the photosensitive resin composition and the molar ratio of each repeating unit to the resin (A) (corresponding in order from the left) are shown in Table 4 below.

The photoacid generator used to prepare the photosensitive resin composition is shown below.

The basic compounds used in the preparation of the photosensitive resin composition are shown below.

The solvents used to prepare the photosensitive resin composition and the composition for forming an upper layer film, which will be described later, are shown below.
SL-1: PGMEA (Propylene Glycol Monomethyl Ether Acetate)
SL-2: Cyclohexanone SL-3: PGME (propylene glycol monomethyl ether)
SL-4: γ-Butyrolactone SL-5: 4-Methyl-2-pentanol SL-6: 2-Methyl-1-butanol SL-7: Diisoamyl ether

<Preparation of composition for forming upper layer film>
The upper film forming compositions used in Examples 7, 11 and 12 were prepared as follows.
First, the solution containing the fluorine-containing resin that has undergone the first filtration step shown in Table 2 above has a solid content concentration of 4.3% by mass, and the solvent component is the ratio within the solvent component shown in Table 5 below. It was prepared to be. The obtained solution was filtered through a polyethylene filter having a pore size of 0.03 μm as a second filtration step. The obtained filtrate was used as a composition for forming an upper layer film.
Moreover, the composition for forming an upper layer film used in Comparative Examples 3, 4, and 6 was prepared as follows.
First, the fluorine-containing resin that did not undergo the first filtration step was prepared so that the solid content concentration was 4.3% by mass and the solvent component had a ratio within the solvent component shown in Table 5 below. The obtained solution was filtered through a polyethylene filter having a pore size of 0.03 μm as a second filtration step. The obtained filtrate was used as a composition for forming an upper layer film.
That is, in the production of the upper layer film forming composition used in Comparative Examples 3, 4, and 6, only the second filtration step is carried out without carrying out the first filtration step.
The second filtration step was carried out twice for the composition for forming an upper layer film of Comparative Example 6.
When "TC" is described in the column of the addition form of Examples or Comparative Examples in Table 5, the upper layer film is formed by using the upper layer film forming composition containing a fluorine-containing resin in the evaluation of coatability described later. Indicates that it has been formed.
In Table 5, when "addition" is described in the column of the addition form of Examples or Comparative Examples, it indicates that the photosensitive resin composition contains a fluorine-containing resin. When the addition form is "addition", the upper layer film is not formed in the evaluation of coatability described later.

The contents of the second filtration step performed on the photosensitive resin composition and the composition for forming the upper layer film in each Example or Comparative Example, and the type and pore size of the filter used in the second filtration step are as follows. It is shown in Table 6 of.
In Table 6, when "TC" is described in the column of the addition form of Examples or Comparative Examples, the upper layer film is formed by using the upper layer film forming composition containing a fluorine-containing resin in the evaluation of coatability described later. Indicates that it has been formed.
In Table 6, when "addition" is described in the column of the addition form of Examples or Comparative Examples, it indicates that the photosensitive resin composition contains a fluorine-containing resin. When the addition form is "addition", the upper layer film is not formed in the evaluation of coatability described later.
In Table 6, the description in the lower column of the filter indicates the material and pore diameter of the filter.
In Table 6, the number of times of filtration indicates the number of times that the second filtration step was performed on each of the photosensitive resin composition and the composition for forming the upper layer film.
As described above, in the photosensitive resin compositions of Comparative Examples 1, 2, and 5, a photosensitive resin composition was produced using a fluorine-containing resin that had not been subjected to the first filtration step. Only the second filtration step was carried out.
In the photosensitive resin compositions of Examples 7, 11, and 12, and Comparative Examples 3, 4, and 6, since the photosensitive resin composition does not contain a fluorine-containing resin, the first filtration step is performed. Only the second filtration step was carried out without carrying out.
In the upper layer film forming compositions of Comparative Examples 3, 4, and 6, an upper layer film forming composition is produced using a fluorine-containing resin that has not been subjected to the first filtration step, and a second filtration step is performed. Only carried out.

<Evaluation of coatability>
The photosensitive resin composition was spin-coated on a disk-shaped silicon wafer. The applied photosensitive resin composition was heated at 100 ° C. for 60 seconds using a hot plate to form resist films having an average film thickness of 97.0 to 103.0 nm.
Further, in the examples and comparative examples of forming the upper layer film, the composition for forming the upper layer film was spin-coated on the formed resist film. The applied composition for forming an upper layer film was heated at 120 ° C. for 60 seconds using a hot plate to form an upper layer film having an average film thickness of 97.0 to 103.0 nm.
The average film thickness of the resist film and the upper layer film is obtained when the film thickness in each silicon wafer surface is measured at 13 points using a film thickness measuring device (VM-3110, manufactured by Dainippon Screen Mfg. Co., Ltd.). Is the average value of.
Further, using the above-mentioned film thickness measuring device, each film thickness on the outer peripheral portion of the silicon wafer was measured at 96 points, and the standard deviation (3σ) was calculated.
Here, in the examples and comparative examples in which the upper layer film was not formed, the film thickness of the resist film was measured and 3σ was calculated. In the examples and comparative examples in which the upper layer film was formed, the film thickness of the upper layer film was measured and 3σ was calculated.
Further, the outer peripheral portion of the silicon wafer is intended to be an annular region of 5 mm from the edge portion of the silicon wafer toward the center on the surface of the disk-shaped silicon wafer having a radius of 200 mm.
The evaluation results are shown in Table 7. The smaller the value of 3σ of the film thickness in the table, the more uniform the film thickness, and it is shown that the coating property for forming the upper layer film or the photosensitive resin composition on which the film is formed is excellent. When the value was 1.0 nm or less, it was judged that the coatability was good.

As shown in Table 7, the upper layer film forming composition and the photosensitive resin composition that have undergone the first filtration step are more than the upper layer film forming composition and the photosensitive resin composition that have not undergone the first filtration step. It was confirmed that the coating property was excellent (comparison of Example 11 and Comparative Example 3. Comparison of Example 12 and Comparative Example 4. Comparison of Example 8 and Comparative Example 1. Comparison of Example 10 and Comparative Example 2. ).
Further, the composition obtained by performing the second filtration step once after passing through the first filtration step is more than the composition obtained by performing only the second filtration step twice without passing through the first filtration step. It was confirmed that the coating property was excellent (comparison of Example 8 and Comparative Example 5. Comparison of Example 11 and Comparative Example 6).
Further, in the first filtration step, when the solution containing the fluorine-containing resin is further filtered by the second and third filters in addition to the filtration by the first filter, a composition having more excellent coatability can be obtained. It was confirmed that it was obtained (comparison of Examples 8, 13, and 15; comparison of Examples 10, 14, and 16).
It was confirmed that a composition having further excellent coatability can be obtained by performing circulation filtration in the first filtration step (comparison of Examples 15 and 17; comparison of Examples 16 and 18).

1 Tank 2 Pump 3 Flowmeter 4 Treatment liquid filling container 5, 6, 7, 9, 10 Flow path 8 Filling port 100 Column with the first filter 200 Column with the second filter 300 Third Column with filter

Claims (16)

The first filtration step, which filters a solution containing a fluorine-containing resin,
A step of preparing a photosensitive resin composition using a solution containing a fluorine-containing resin that has undergone the first filtration step, and a step of preparing a photosensitive resin composition.
A method for producing a photosensitive resin composition, which comprises a second filtration step of filtering the photosensitive resin composition.
A method for producing a photosensitive resin composition, wherein the fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). ..

In the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom. R ₂ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom. However, _{at least one of R 2} and R ₃ has a fluorine atom. L represents -O- or -COO-.
In the general formula (2), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₅ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₆ represents an alkyl group which may have a hydrogen atom or a fluorine atom. However, _{at least one of R 4 to} R ₆ has a fluorine atom. L represents -O- or -COO-. The photosensitive resin according to claim 1, wherein the fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4). A method for producing a resin composition.

In the general formula (3), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom. R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₇ represents an alkylene group having a fluorine atom, which may have an oxygen atom.
In the general formula (4), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₈ represents an alkylene group which may have an oxygen atom. R ₉ and R ₁₀ each independently represent an alkyl group which may have a fluorine atom. However, _{at least one of R 9} and R ₁₀ has a fluorine atom. R ₁₁ represents an alkyl group which may have a hydrogen atom or a fluorine atom. The method for producing a photosensitive resin composition according to claim 1 or 2, wherein in the first filtration step, the pore size of the filter used for filtration is 0.5 μm or less. The first filtration step is the step 1 of filtering the solution containing the fluorine-containing resin using the first filter, and
The method for producing a photosensitive resin composition according to any one of claims 1 to 3, which comprises a step 2 of filtering a solution containing the fluorine-containing resin that has undergone the step 1 using a second filter. The production of the photosensitive resin composition according to claim 4, wherein the first filtration step further comprises a step 3 of filtering the solution containing the fluorine-containing resin that has undergone the step 2 using a third filter. Method. The first filtration step according to any one of claims 1 to 5, further comprising a circulation filtration step of guiding a solution containing a fluorine-containing resin that has passed through the filter to the same filter and circulating it in the system. A method for producing a photosensitive resin composition. A step of forming a resist film using the photosensitive resin composition obtained by the production method according to any one of claims 1 to 6.
The step of exposing the resist film and
A pattern forming method including a step of developing the exposed resist film. A method for manufacturing an electronic device, including the pattern forming method according to claim 7. The first filtration step, which filters a solution containing a fluorine-containing resin,
A step of preparing a composition for forming an upper layer film using a solution containing a fluorine-containing resin that has undergone the first filtration step, and a step of preparing a composition for forming an upper layer film.
A method for producing an upper layer film forming composition, which comprises a second filtration step of filtering the upper layer film forming composition.
Production of a composition for forming an upper layer film, wherein the fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). Method.

In the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom. R ₂ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom. However, _{at least one of R 2} and R ₃ has a fluorine atom. L represents -O- or -COO-.
In the general formula (2), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₅ represents an alkylene group which may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₆ represents an alkyl group which may have a hydrogen atom or a fluorine atom. However, _{at least one of R 4 to} R ₆ has a fluorine atom. L represents -O- or -COO-. The upper layer film according to claim 9, wherein the fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4). A method for producing a composition for forming.

In the general formula (3), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a halogen atom. R ₃ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₇ represents an alkylene group having a fluorine atom, which may have an oxygen atom.
In the general formula (4), R ₄ represents an alkyl group which may have a hydrogen atom or a fluorine atom. R ₈ represents an alkylene group which may have an oxygen atom. R ₉ and R ₁₀ each independently represent an alkyl group which may have a fluorine atom. However, _{at least one of R 9} and R ₁₀ has a fluorine atom. R ₁₁ represents an alkyl group which may have a hydrogen atom or a fluorine atom. The method for producing an upper layer film forming composition according to claim 9 or 10, wherein in the first filtration step, the pore size of the filter used for filtration is 0.5 μm or less. The first filtration step is the step 1 of filtering the solution containing the fluorine-containing resin using the first filter, and
The method for producing an upper layer film forming composition according to any one of claims 9 to 11, further comprising a step 2 of filtering the solution containing the fluorine-containing resin that has undergone the step 1 using a second filter. The composition for forming an upper layer film according to claim 12, wherein the first filtration step further comprises a step 3 of filtering the solution containing the fluorine-containing resin that has undergone the step 2 using a third filter. Production method. The first filtration step according to any one of claims 9 to 13, further comprising a circulation filtration step of guiding a solution containing a fluorine-containing resin that has passed through the filter to the same filter and circulating the solution in the system. A method for producing a composition for forming an upper layer film. A step of forming an upper layer film on a resist film using the upper layer film forming composition obtained by the production method according to any one of claims 9 to 14.
The step of exposing the resist film and
A pattern forming method including a step of developing the exposed resist film. A method for manufacturing an electronic device, including the pattern forming method according to claim 15.

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