JP2018200432A - 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 pattern forming method, and a method for producing an electronic device.

  As a resist image forming method, an image forming method called chemical amplification is used. An example of a positive-type chemical amplification image forming method will be described. The photoacid generator in the exposed area is decomposed by exposure to generate an acid, and the acid generated in the post-exposure bake (PEB). This is an image forming method in which an alkali-insoluble group is changed to an alkali-soluble group using a reaction catalyst, and an exposed portion is removed by alkali development.

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

Japanese Patent Laid-Open No. 2016-200761

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

This invention makes it a subject to provide the manufacturing method of the composition for upper layer film formation or the photosensitive resin composition which has the outstanding applicability | paintability.
It is another object of the present invention to provide a pattern forming method and an electronic device manufacturing method.

As a result of intensive studies on the above problems, the present inventor has found that a desired effect can be obtained by performing a predetermined filtration treatment.
That is, the above problems can be solved by the following means.

(1) 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 It is a manufacturing method of the upper film | membrane formation composition including the 2nd filtration process which filters the film formation composition, Comprising: The said fluorine-containing resin is a repeating unit represented by General formula (1) mentioned later, and General formula The manufacturing method of the composition for upper layer film formation which has at least 1 sort (s) selected from the group which consists of a repeating unit represented by (2).
(2) The fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the following general formula (3) and a repeating unit represented by the general formula (4), (1) The manufacturing method of the composition for upper layer film formation as described in any one of.
(3) The manufacturing method of the composition for upper film | membrane formation as described in (1) or (2) whose pore diameter of the filter used for filtration is 0.5 micrometer or less in said 1st filtration process.
(4) Step 1 in which the first filtration step filters the solution containing the fluorine-containing resin using the first filter, and the fluorine-containing resin that has passed through the step 1 using the second filter The manufacturing method of the composition for upper layer film formation in any one of (1)-(3) including the process 2 which filters the solution to contain.
(5) For the upper film formation according to (4), the first filtration step further includes a step 3 of filtering the solution containing the fluorine-containing resin that has passed the step 2 using a third filter. A method for producing the composition.
(6) Any of (1) to (5), 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 manufacturing method of the composition for upper layer film formation as described in any one of.
(7) A step of forming an upper layer film on the resist film using the composition for forming an upper layer film obtained by the manufacturing method according to any one of (1) to (6), and exposing the resist film A pattern forming method including a step and a step of developing the exposed resist film.
(8) An electronic device manufacturing method 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 photosensitive resin composition using a solution containing a fluorine-containing resin that has undergone the first filtration step, and the photosensitive property It is a manufacturing method of the photosensitive resin composition including the 2nd filtration process which filters resin composition, Comprising: The said fluorine-containing resin is a repeating unit represented by General formula (1) mentioned later, and General formula (2) The manufacturing method of the photosensitive resin composition which has at least 1 sort (s) selected from the group which consists of a repeating unit represented by these.
(10) The fluorine-containing resin has at least one selected from the group consisting of a repeating unit represented by the following general formula (3) and a repeating unit represented by the general formula (4), (9) The manufacturing method of the photosensitive resin composition of description.
(11) The manufacturing method of the photosensitive resin composition as described in (9) or (10) whose pore diameter of the filter used for filtration is 0.5 micrometer or less in said 1st filtration process.
(12) Step 1 in which the first filtration step filters the solution containing the fluorine-containing resin using a first filter, and the fluorine-containing resin that has passed through the step 1 using a second filter The manufacturing method of the photosensitive resin composition in any one of (9)-(11) including the process 2 which filters the solution to contain.
(13) The photosensitive resin composition according to (12), wherein the first filtration step further includes a step 3 of filtering the solution containing the fluorine-containing resin that has passed the step 2 using a third filter. Manufacturing method.
(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 manufacturing method of the photosensitive resin composition of description.
(15) A step of forming a resist film using the photosensitive resin composition obtained by the production method according to any one of (9) to (14), a step of exposing the resist film, and the exposure A pattern forming method including a step of developing the resist film.
(16) A method for manufacturing an electronic device, comprising the pattern forming method according to (15).

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the composition for upper layer film formation or the photosensitive resin composition which has the outstanding applicability | paintability can be provided.
Furthermore, according to the present invention, a pattern forming method and an electronic device manufacturing method can be provided.

Schematic of the one aspect | mode of the apparatus used for the 1st filtration process mentioned later. Schematic of the one aspect | mode of the apparatus used for the 1st filtration process mentioned later. Schematic of the one aspect | mode of the apparatus used for the 1st filtration process mentioned later. Schematic of the one aspect | mode of the apparatus used for the 1st filtration process mentioned later.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of group (atomic group) in this specification, the description which is not describing substitution and non-substitution includes the group which has a substituent with the group which does not have a 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).
“Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams. . Moreover, the light in this specification means an actinic ray or radiation. In addition, “exposure” in the present specification is not limited to exposure with far ultraviolet rays, X-rays, EUV light or the like typified by mercury lamps and excimer lasers, unless otherwise specified, but also with electron beams or ion beams. Drawing with particle beams such as is also included in the exposure.
In the present specification, the “pore diameter” of a filter is a manufacturer's nominal diameter value or a value based thereon.
In this specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (Mw / Mn) are measured by GPC (solvent: THF) using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation). (Tetrahydrofuran), flow rate (sample injection amount): 10 μl, column: TSK gel Multipore HXL-M (× 4) manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index (RI) detector) in terms of polystyrene.
The bonding direction of the divalent group (for example, —COO—) represented in the present specification is not particularly limited. For example, when L in the general formula (1) described later is —COO—, assuming that the position bonded to the R ₂ side is * 1, and the position bonded to the R ₃ side is * 2, L is * 1-O-CO- * 2 may be sufficient and * 1-CO-O- * 2 may be sufficient.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an 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 following general formula (1) or (2) obtained by the production method of the present invention The applicability of the composition or the photosensitive resin composition is good.
This inventor discovered that the applicability | paintability of the composition for upper layer film formation or the photosensitive resin composition was influenced greatly by the said fluorine-containing resin. Specifically, since the fluorine-containing resin has a high cohesive force, polymer aggregates are likely to be formed, and such polymer aggregates affect the applicability of the upper layer film-forming composition or the photosensitive resin composition. The present inventor has found that Therefore, the present inventor attempted to prepare an upper layer film-forming composition or a photosensitive resin composition having a low content of the polymer aggregate.
The present inventor provided a solution containing a fluorine-containing resin to the first filtration step before the preparation of the upper layer film-forming composition or the photosensitive resin composition, and used the obtained filtrate for upper layer film formation. The manufacturing method of this invention which prepares a composition or a photosensitive resin composition was discovered. According to the said method, it is thought that a polymer aggregate can be removed more effectively than the method of filtering the composition for upper-layer film formation or photosensitive resin composition after preparation. As a result, the composition for forming an upper layer film or the photosensitive resin composition obtained by using the above method is excellent in coatability.
In other words, the production method of the present invention grasps the problems when using a predetermined fluorine-containing resin as described above, and selects the fluorine-containing resin as an object to be filtered, so that it can be applied more efficiently. It is possible to obtain a composition for forming an upper layer film or a photosensitive resin composition excellent in the above.

[First embodiment (Method for producing composition for forming upper layer film)]
1st embodiment of this invention is related with the manufacturing method of the composition for upper layer film formation.
The manufacturing method of the composition for upper layer film formation of this invention includes the following processes.
1st filtration process: The 1st filtration process which filters the solution containing fluorine-containing resin Preparation process: The process of preparing the composition for upper-layer film formation using the solution containing the fluorine-containing resin which passed through the 1st filtration process Second filtration step: Second filtration step of filtering the composition for forming an upper layer film Hereinafter, each step will be described in detail.

<First filtration step>
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 general formulas (1) and (2) described later. Details of the fluorine-containing resin and the general formulas (1) and (2) are collectively 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 considering the balance between the time required for filtration and the ability to remove polymer aggregates from the solution (hereinafter referred to as the pore size). , “Also excellent in filtration efficiency”) is preferably 0.5 μm or less, more preferably 0.001 to 0.5 μm, and still more preferably 0.001 to 0.2 μm.

  The material of the filter used in the method for producing the composition for forming an upper film of the present invention is not particularly limited, and specific examples include polyolefin resins (polyethylene, polypropylene, etc.), polyamide resins (nylon, etc.), and A fluorine-containing resin is mentioned. Among them, the filter material is preferably polyethylene or nylon.

The first filtration step in the method for producing the composition for forming an upper layer film of the present invention preferably includes step 1 and step 2, and more preferably includes step 1 to step 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 Step 1 above using a second filter Step 3: Third The process of filtering the solution containing fluorine-containing resin which passed through the above-mentioned step 2 using the above-mentioned filter Moreover, even if it carries out the process of filtering the solution containing fluorine-containing resin further using a different filter after process 3 Good.

  Step 1 is a step of filtering a solution containing a fluorine-containing resin using the first filter. As the first filter, the above-described filter can be suitably 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 hole diameter different from that of the first filter, or may be made of a material different from that of 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 and more preferably 0.001 to 0.1 μm from the viewpoint of excellent filtration efficiency.
The difference between the hole diameter of the second filter and the hole diameter of the first filter is preferably 0.001 to 0.1 μm.

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

In the 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 hole diameter of the third filter may be different from that of the first filter and the second filter, and the material of the third filter may be different from that of the first filter and the second filter.

From the viewpoint of excellent filtration efficiency, the hole diameter of the third filter is preferably smaller than the hole diameter of the first filter, and more preferably smaller than any hole diameter of the first filter and the second filter.
Specifically, the pore size of the third filter is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.1 μm.
The difference between the hole diameter of the third filter and the hole diameter of the first filter is preferably 0.001 to 0.1 μm.
The material of the third filter may be the same as the material of the first filter, for example.
As above-mentioned, you may implement the process of filtering the solution which contains a fluorine-containing resin further using a different filter after the process 3.

The first filtration step preferably includes a circulation filtration step in which the solution containing the fluorine-containing resin that has passed through the filter is further led 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. In addition, the first filtration step may include a circulation filtration step in which the solution containing the fluorine-containing resin that has undergone 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 led to the first filter, the second filter, or the third filter, and is 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 introduced into the first filter, and the solution containing the fluorine-containing resin that has undergone Step 2 is further introduced into the circulation filter step of circulating through the system. You may have the circulation filtration process which leads to a 2nd filter and circulates in the system.
The number of circulations can be appropriately adjusted from the viewpoint of the removal rate of the polymer aggregates and productivity, and is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15, and still more preferably 4 to 10.
In addition, the number of circulation in the case of carrying out the circulation filtration step was [subject to the integrated filtration amount / circulation filtration step by any one of the filters provided to the circulation filtration step of the solution containing the fluorine-containing resin. The amount of the solution containing a fluorine-containing resin].

  Below, the example of embodiment of a 1st filtration process is demonstrated with reference to drawings. 1-4 is the schematic of the apparatus used for a 1st filtration process.

The apparatus of FIG. 1 is an apparatus used for the 1st filtration process of the aspect which implements only the process 1 and does not implement the circulation filtration process.
In the apparatus of FIG. 1, a tank 1, a pump 2, and a column 100 provided with a first filter are connected by 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 filled.

The apparatus of FIG. 2 is an apparatus used for the 1st filtration process of the aspect which implements process 1-3 and does not implement a circulation filtration process.
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 have a flow path. 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 filled.

The apparatus of FIG. 3 is an apparatus used for the 1st filtration process of the aspect which implements the process 1 and implements the circulation filtration process.
In the apparatus of FIG. 3, a tank 1, a pump 2, and a column 100 in which a first filter is installed are connected by flow paths 5 to 7.
The flow path 7 is also connected to the tank 1, and by driving the pump 2, a solution containing a fluorine-containing resin accommodated in the tank 1 is circulated in the system. . Furthermore, a filling port 8 is provided in the flow path 7 so that the solution containing the fluorine-containing resin that has undergone a predetermined circulation filtration step is filled in the processing 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 1st filtration process of the aspect which implements process 1-3 and implements a circulation filtration process.
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 have a flow path. 5, 6, 7, 9 and 10.
The flow path 7 is also connected to the tank 1, and by driving the pump 2, a solution containing a fluorine-containing resin accommodated in the tank 1 is circulated in the system. . Furthermore, a filling port 8 is provided in the flow path 7 so that the solution containing the fluorine-containing resin that has undergone a predetermined circulation filtration step is filled in the processing 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 is a solvent capable of dissolving the fluorine-containing resin, but a solvent used in the composition for forming an upper layer film is preferable. Of these, diisoamyl ether is more preferable. The solvent used for the composition for forming an upper layer film will be described later.
The content of the fluorine-containing resin in the solution containing the fluorine-containing resin subjected to 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. % By mass is preferable, and 1 to 20% by mass is more preferable.

<Preparation process>
An upper film-forming composition 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 the upper layer film is not particularly limited as long as the 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 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 step>
The manufacturing method of the composition for upper layer film formation of this invention includes the 2nd filtration process which filters further the prepared composition for upper layer film formation.
Also in the second filtration step, a filter that can be used in the first filtration step and a similar filter can be suitably used.
Similarly to the first filtration step, the second filtration step may include a plurality of steps using a plurality of filters or 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, before and / or after the solution containing the fluorine-containing resin or the composition for forming an upper layer film is subjected to filtration, the solution containing the fluorine-containing resin or the composition for forming an upper layer film is deaerated. Etc. may be performed.
The composition for forming an upper layer film produced by using the method for producing a composition for forming an upper layer film of the present invention is excellent in coatability and can form an upper layer film having a uniform film thickness.

[Second Embodiment (Production Method of Photosensitive Resin Composition)]
The second embodiment of the present invention relates to a method for producing a photosensitive resin composition.
The manufacturing method of the photosensitive resin composition of this invention includes the following processes.
1st filtration process: 1st filtration process which filters the solution containing fluorine-containing resin Preparation process: The process of preparing the photosensitive resin composition using the solution containing the fluorine-containing resin which passed through the 1st filtration process 2nd Filtration step: second filtration step of filtering the photosensitive resin composition Hereinafter, each step will be described in detail.

<First filtration step>
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 general formulas (1) and (2) described later. Details of the fluorine-containing resin and the general formulas (1) and (2) are collectively shown in the latter part.

The preferred pore size of the filter used in the method for producing the photosensitive resin composition of the present invention is the same as the preferred 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 manufacturing method of the photosensitive resin composition of this invention is the same as the suitable material of the filter used in the manufacturing method of the said composition for upper layer film formation.

The first filtration step in the method for producing the photosensitive resin composition of the present invention preferably includes step 1 and step 2, and more preferably includes step 1 to step 3, from the viewpoint of excellent filtration efficiency.
Process 1: The process of filtering the solution containing the said fluorine-containing resin using a 1st filter Process 2: The process of filtering the solution containing the said fluorine-containing resin which passed the said process 1 using a 2nd filter Process 3: The process of filtering the solution containing the said fluorine-containing resin which passed the said process 2 using a 3rd filter Moreover, the process of filtering the solution containing a fluorine-containing resin further using a different filter is implemented after the process 3. May be.

Steps 1 to 3 in the first filtration step included in the method for producing the 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 the composition for forming an upper layer film described above. The preferred conditions are also the same.
Moreover, it circulates also in the 1st filtration process which the manufacturing method of the photosensitive resin composition of this invention contains similarly to the circulation filtration process in the 1st filtration process which the manufacturing method of the composition for upper layer film | membrane formation of this invention contains. 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 is a solvent capable of dissolving the fluorine-containing resin, but a solvent used for the photosensitive resin composition is preferable. Among these, PGMEA (propylene glycol monomethyl ether acetate) is more preferable. The solvent used for the photosensitive resin composition will be described later.
The content of the fluorine-containing resin in the solution containing the fluorine-containing resin subjected to 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 the 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. By doing so, a photosensitive resin composition is prepared.
Details of the photosensitive resin composition will be described later.

<Second filtration step>
The manufacturing method of the photosensitive resin composition of this invention includes the 2nd filtration process which further filters the prepared photosensitive resin composition.
Also in the second filtration step, a filter that can be used in the first filtration step and a similar filter can be suitably used.
Similarly to the first filtration step, the second filtration step may include a plurality of steps using a plurality of filters or 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, before and / or after the solution containing the fluorine-containing resin or the photosensitive resin composition is subjected to filtration, the solution containing the fluorine-containing resin or the photosensitive resin composition is subjected to a deaeration treatment or the like. You may go.
The photosensitive resin composition manufactured using the manufacturing method of the photosensitive resin composition of this invention is excellent in applicability | paintability, and can form the resist film which has a uniform film thickness.

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

<Fluorine-containing resin having a repeating unit represented by 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). When the repeating unit represented by the following general formula (1) or (2) is subjected to immersion exposure using an upper layer film formed using an upper layer film-forming composition containing a fluorine-containing resin, and fluorine-containing When immersion exposure is performed using a resist film formed using a photosensitive resin composition containing a resin, it contributes to an improvement in scanning speed and suppression of development defects.
It should be noted that the preferred conditions mentioned in the following description of the general formula (1) or (2) are determined from the viewpoint of excellent scanning speed and development defect suppression unless otherwise specified.

In 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, R ₁ is preferably a halogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a methyl group, and further preferably a methyl group, from the viewpoint of copolymerization of the monomer. .

In General Formula (1), R ₂ represents an alkylene group that 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.
The alkylene group represented by R ₂ may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure, and a polycyclic structure is preferred. A part of the ring structure is preferably substituted with an oxygen atom to have —COO—.
Among these, the alkylene group represented by R ₂ is preferably linear or branched.
The alkylene group represented by R ₂ may have an oxygen atom, and preferably has —COO— in the alkylene group.
The alkylene group represented by R ₂ 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, and more preferably 2 to 5.
Examples of R ₂ include —CH ₂ —, —C (C ₂ H ₅ ) H—, —C (C ₄ H ₉ ) HCH ₂ C (CF ₃ ) ₂ —, —C (CH ₃ ) _2. C (CF ₃ ) ₂ —, —C (CH ₂ OCOC ₂ F ₅ ) HCH ₂ — and the like can be mentioned.

In general formula (1), R ₃ represents a hydrogen atom or an alkyl group which may have a fluorine atom. Note that when _{R 3} is a hydrogen atom, _{-L-R 3} is, -OH, or represents a -COOH.
R ₃ is preferably an alkyl group.
1-10 are preferable, as for carbon number of the alkyl group represented by R < ₃ >, 1-5 are more preferable, and 1-2 are more preferable.
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 these, the alkyl group represented by R ₃ is preferably linear or branched, and more preferably linear.
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 still more preferably 1 to 3.

In general formula (1), L represents -O- or -COO-.
Especially, as L, -COO- is preferable.
When L represents -COO-, R ₃ is preferably an alkyl group. When L represents -O-, R ₃ is preferably a hydrogen atom.

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

In general formula (2), R ₄ represents a hydrogen atom or an alkyl group which may have a fluorine atom.
R ₄ is preferably an alkyl group.
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 these, the alkyl group represented by R ₄ is preferably linear.
The alkyl group represented by R ₄ preferably has a fluorine atom as a substituent.

In 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 or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among these, the alkylene group represented by R ₅ is preferably branched.
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 still more preferably 6.

In general formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a fluorine atom.
Among them, R ₆ is preferably a hydrogen atom from the viewpoint of solubility in a developer.
The number of carbon atoms in the alkyl group represented by R ₆ is 1 to 10, more preferably 1 to 5, 1 to 2 is more preferred.
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 general formula (2), L represents -O- or -COO-.
Especially, as L, -O- is preferable.

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

<Fluorine-containing resin having a repeating unit represented by 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).
It should be noted that the preferred conditions mentioned in the description of the following general formulas (3) and (4) are determined from the viewpoint of excellent scanning speed and development defect suppression unless otherwise noted.

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

In 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 General Formula (3), R ₇ represents an alkylene group having a fluorine atom, which may have an oxygen atom.
The alkylene group represented by R ₇ is preferably 1 to 15, more preferably 1 to 10, more preferably 2 to 4, 4 being particularly preferred.
The alkylene group represented by R ₇ may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among these, the alkylene group represented by R ₇ is preferably linear or branched, and more preferably branched.
The number of fluorine atoms included in the alkylene group represented by R ₇ is 1 to 10, more preferably from 2 to 3, 2 is more preferred.

In general formula (3), R ₃ represents a hydrogen atom or an alkyl group which may have a fluorine atom.
R ₃ is preferably an alkyl group.
1-10 are preferable, as for carbon number of the alkyl group represented by R < ₃ >, 1-5 are more preferable, and 1-2 are more preferable.
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 these, the alkyl group represented by R ₃ is preferably linear or branched, and more preferably linear.
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 still 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 general formula (4), R ₄ represents a hydrogen atom or an alkyl group which may have 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 General Formula (4), R ₈ represents an alkylene group which may have an oxygen atom.
The alkylene group represented by R ₈ is preferably 1-7, more preferably 1 to 5, 3 is more preferable.
The alkylene group represented by R ₈ may be linear or branched, and may have a ring structure. The ring structure may be a monocyclic structure or a polycyclic structure.
Among these, 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 represents an alkyl group which may have a fluorine atom.
R ₉ and the carbon number of the alkyl group represented by _{R 10} is 1 to 5, more preferably 1 to 3, 1 is more preferred.
The alkyl group represented by R ₉ and R ₁₀ 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 ₉ and R ₁₀ is 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 still more preferably 3.
Note that at least one of R ₉ and R ₁₀ has a fluorine atom.

In General Formula (4), R ₁₁ represents a hydrogen atom or an alkyl group which may have a fluorine atom.
Among them, R ₁₁ is preferably a hydrogen atom from the viewpoint of solubility in a developer.
The number of carbon atoms in the alkyl group represented by R ₁₁ is 1 to 10, more preferably 1 to 5, 1 to 2 is more preferred.
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 unit represented by the general formulas (1) to (4) described above, 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. 45-100 mol% is preferable with respect to all the repeating units of containing resin, 60-100 mol% is more preferable, and 80-100 mol% is further more preferable.

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

The fluorine-containing resin may have a repeating unit having a CH ₃ partial structure in the side chain portion. Specifically, the repeating unit represented by general formula (II) and the repeating unit represented by the following general formula (III) are mentioned.

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

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group, or represents a halogen atom, R ₂ has one or more CH ₃ partial structure, a stable organic radical to acid Represent. Here, the organic group that is stable to acid is more preferably an organic group that does not have a “group that decomposes by the action of an acid to generate a polar group”.

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

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
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.

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of the alkyl group include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 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 a 2,3,5,7-tetramethyl-4-heptyl group, preferably an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, or 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 Or 2,3,5,7-tetramethyl-4-heptyl group is more preferable.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo structure having 5 or more carbon atoms, a bicyclo structure, a tricyclo structure, a tetracyclo structure, and the like. 6-30 are preferable and, as for carbon number of a cycloalkyl group, 7-25 are more preferable. Cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group Group or cyclododecanyl group is preferable, adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, or tricyclodecanyl group is more preferable, norbornyl group, cyclopentyl group, or cyclohexyl group Is more preferable.
The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Of these, a phenyl group is preferred.
The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 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 include 5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-t-butylcyclohexyl group, and 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 -A tetramethyl-4-heptyl group, a 3,5-dimethylcyclohexyl group, a 3,5-ditert-butylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-t-butylcyclohexyl group, or an isobornyl group is preferred.

  Specific examples of the repeating unit represented by the general formula (II) are shown below.

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

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

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

X _b2 is preferably a hydrogen atom.
When _Xb2 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 a “group that decomposes by the action of an acid to generate a polar group”, which will be described later in the resin (A).

R ₃ includes an alkyl group 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.

The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of the alkyl group include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 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 a 2,3,5,7-tetramethyl-4-heptyl group, preferably an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, or 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 Or 2,3,5,7-tetramethyl-4-heptyl group is more preferable.

Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 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, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, and 2,3,5,7-tetramethyl-4-heptyl group. 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 preferable that the alkyl group having two or more CH ₃ partial structures has 5 to 20 carbon atoms.

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

  Below, the preferable specific example of the repeating unit represented by general formula (III) is shown.

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

Although content in particular of the repeating unit represented by general formula (II) is not restrict | limited, 1-50 mol% is preferable with respect to all the repeating units of a fluorine-containing resin, and 1-30 mol% is more preferable.
Although content in particular of the repeating unit represented by general formula (III) is not restrict | limited, 1-50 mol% is preferable with respect to all the repeating units of a fluorine-containing resin, and 1-30 mol% is more preferable.

  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 general formula (III), the alkyl group represented by 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 having 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-decomposable 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 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 . _R42 represents an alkyl group, a cycloalkyl group, or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Specific examples of the repeating unit represented by the general formula (VIII) are shown below.

The fluorine-containing resin preferably contains a repeating unit (d) derived from a monomer having an alkali-soluble group. Thereby, the solubility with respect to immersion water and the solubility with respect to a coating solvent are controllable. Examples of alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, sulfonamido 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 Group which has.
As the monomer having an alkali-soluble group, a monomer having an acid dissociation index 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 more preferable. By containing a monomer having a pKa of 4 or more, swelling during negative-type and positive-type development is suppressed, and not only good developability with respect to an organic developer but also good development even when an alkali developer is used. Sex is obtained.

  The acid dissociation constant pKa is as described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.), and the pKa value of a monomer containing an alkali-soluble group is, for example, infinite The measurement can be performed at 25 ° C. using a diluting solvent, and the following software package 1 can be used to calculate a value based on a Hammett substituent constant and a database of known literature values. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

  Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

The monomer having a pKa of 4 or more is not particularly limited, and examples thereof include monomers 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%, based on all repeating units of the fluorine-containing resin. 70 mol% is more preferable.

  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 more 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. Among them, a repeating unit having both a monocyclic or polycyclic cycloalkyl group and a CH ₃ partial structure is preferable, and a repeating unit having both a monocyclic or polycyclic cycloalkyl group and a CH ₃ partial 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 scanning calorimetry. For example, the specific volume changes when the sample is 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 of being able to develop and peel off using an alkali developer, the fluorine-containing resin is preferably soluble in an alkali developer.

  5-80 mass% is preferable with respect to the molecular weight of fluorine-containing resin, and, as for content of the fluorine atom in fluorine-containing resin, 10-80 mass% is more preferable.

  The weight average molecular weight in terms of standard polystyrene by GPC of the fluorine-containing resin is preferably 2000 to 20000, and more preferably 2000 to 12000. Moreover, 1-5 are preferable, as for the dispersion degree (Mw / Mn, molecular weight distribution) of fluorine-containing resin, 1-3 are more preferable, and 1-1.95 are more preferable.

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

  50-100 mass% is preferable with respect to the total solid, and, as for the compounding quantity of the fluorine-containing resin in a specific solution, 60-100 mass% is more preferable.

The method for synthesizing the fluorine-containing resin is not particularly limited, and a known method is employed. 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 producing by radical polymerization by supplying continuously or intermittently to the system is preferred.
Examples of the component other than the monomer in the monomer solution include a solvent, a polymerization inhibitor, oxygen, and a chain transfer agent. Examples of the component that can be contained in addition to the initiator of the initiator solution include a solvent.

The specific solution may contain components other than the fluorine-containing resin.
For example, the specific solution may contain a solvent. As a solvent, the solvent which the composition for upper layer film formation mentioned later can contain is mentioned, for example.

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

[Composition for forming upper layer film]
Next, the upper layer film-forming composition prepared using the solution containing the fluorine-containing resin that has undergone the first filtration step described above will be described.
The composition for forming an upper film produced by the production method of the present invention is a composition for forming an upper film for a photoresist containing a fluorine-containing resin.
The fluorine-containing resin is as described above.
The content of the fluorine-containing resin in the composition for forming an upper layer film is not particularly limited, but is preferably 50 to 100% by mass and more preferably 80 to 100% by mass with respect to 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 film forming composition produced by the method for producing an upper film forming composition of the present invention uses a solvent that does not dissolve the resist film. Preferably, it is more preferable to use a solvent having a component different from that of an organic solvent-containing developer (organic developer).
From the viewpoint of uniformly applying the upper layer film, the solid content concentration of the composition for forming the upper layer film is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 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 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. A solvent or the like is preferable, and a non-fluorinated alcohol solvent is more preferable. Thereby, 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, monovalent alcohol is preferable from the viewpoint of coatability, and monovalent 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. Of these, linear or branched alcohols are preferable. Specific examples of such alcohol solvents include 1-butanol, 2-butanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 4-methyl-1-pentanol, and 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, triethylene glycol monoethyl ether, and include glycol ethers such as methoxymethyl butanol. Among them, 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 preferable.
Specific examples of the ether solvent include dioxane, tetrahydrofuran, and diisoamyl ether in addition to the glycol ether solvent. Among the ether solvents, ether solvents having a branched structure are 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 butyrate, Isobutyl butyrate, butyl butanoate, 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, 2- Dorokishiiso butyric acid methyl, isobutyl isobutyrate, and, butyl propionate. Among the ester solvents, ester solvents having a branched structure are preferable.

Specific examples of the fluorine-based solvent include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pen. Tanol, 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7 -Dodecafluoro-1,8-octanediol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, Full B tributylamine, and perfluoro tetrapentyl amine. Of the fluorinated solvents, fluorinated alcohols or fluorinated hydrocarbon solvents are preferred.
Specific examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; and n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3 -Aliphatic hydrocarbon solvents such as methylheptane, 3,3-dimethylhexane, and 2,3,4-trimethylpentane.

These solvents may be used alone or in combination.
Further, as described above, it is also preferable to use the same solvent as the solvent contained in the specific solution.
When mixing a solvent other than the above, 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 in the upper film forming composition. Is 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 elution characteristics from the resist film, and the like can be appropriately adjusted.

  The composition for forming the 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 include at least one compound selected from the group consisting of a compound having a bond or a group.

<(A1) Basic compound or base generator>
The composition for forming an upper layer film preferably further contains at least one of a basic compound and a base generator (hereinafter 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. Moreover, the basic compound which the photosensitive resin composition contains can be used similarly.
In addition, for example, compounds classified into the following (1) to (7) can be used.

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

In general formula (BS-1),
Each 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.

Although carbon number of the alkyl group as R is not specifically limited, 1-20 are preferable and 1-12 are more preferable.
Although carbon number of the cycloalkyl group as R is not specifically limited, 3-20 are preferable and 5-15 are more preferable.

Although carbon number of the aryl group as R is not specifically limited, 6-20 are preferable and 6-10 are more preferable. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, 7-20 are preferable and 7-11 are more preferable. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Specific examples of the 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, Isodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N -Dibutylaniline, N, N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by general formula (BS-1), the basic compound whose at least 1 R is the alkyl group substituted by the hydroxy group is mentioned. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, 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 thereof include tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent rows of column 3 of US6040112.

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

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Further, it may contain a hetero atom other than nitrogen. Specific examples include compounds having an imidazole structure (such as 2-phenylbenzimidazole and 2,4,5-triphenylimidazole), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2). , 6,6-pentamethyl-4-piperidyl) sebacate and the like], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more rings is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An 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. Phenoxy groups include, for example, alkyl groups, alkoxy groups, halogen atoms, cyano groups, nitro groups, carboxy groups, carboxylic acid ester groups, sulfonic acid ester groups, aryl groups, aralkyl groups, acyloxy groups, and aryloxy groups. It may have a substituent.

This compound preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. 3-9 are preferable and, as for the number of the oxyalkylene chains in 1 molecule, 4-6 are more preferable. 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 thereof include compounds (C1-1) to (C3-3).

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating to react with an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium. Then, extraction is performed with an organic solvent such as ethyl acetate or chloroform. In addition, an amine compound having a phenoxy group is reacted by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at a terminal to react strongly with sodium hydroxide, potassium hydroxide, or tetraalkylammonium. It can also be obtained by adding an aqueous base solution 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 used as appropriate. Specific examples of anions of ammonium salts include halides, sulfonates, borates, and phosphates. Among these, halide or sulfonate is 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 having 1 to 20 carbon atoms and aryl sulfonates.

  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 the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  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 this 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 hydroxide 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, aminomorpholine, and aminoalkylmorpholine. Can be mentioned. These may further have a substituent.
Specific examples of preferred substituents include amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, A hydroxyl group and a cyano group are mentioned.

  Specific examples of particularly preferable basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 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-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-amino Ethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, Examples include pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, and N- (2-aminoethyl) morpholine.

(5) A compound that has a proton acceptor functional group and generates a compound that is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor, or change from proton acceptor to acidic (PA)
The composition for forming an upper layer film has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or have a proton acceptor property. It may further contain a compound (hereinafter, also referred to as compound (PA)) that generates a compound that has been changed from acidic to acidic.

  The proton acceptor functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π conjugate. It means a functional group having a nitrogen atom with 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 represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is lowered or disappeared, or the 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 acid is a change in the proton acceptor property due to the addition of a proton to the proton acceptor functional group, Specifically, when a proton adduct is produced from a compound (PA) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium is reduced.

  Proton acceptor property can be confirmed by measuring pH. The acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation is preferably pKa <-1, more preferably -13 <pKa <-1, and -13 <pKa <-3. Is 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 upon irradiation with actinic rays or radiation. The compound represented by the general formula (PA-1) has an acidic group together with a proton acceptor functional group, so that the proton acceptor property is reduced or eliminated as compared with the compound (PA), or the proton acceptor property. It is a compound that changed from acidic to acidic.

In 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 each independently represent —SO ₂ — or —CO—.
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.

General formula (PA-1) is demonstrated still in detail.
As a bivalent coupling group in A, a C2-C12 bivalent coupling group is preferable, for example, an alkylene group and a phenylene group are mentioned. Among these, an alkylene group having at least one fluorine atom is preferable, and 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. The alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, more preferably a carbon atom bonded to the Q site has a fluorine atom, and even more preferably a perfluoroalkylene group, A perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group is particularly preferred.

  As monovalent organic group in Rx, C1-C30 is preferable, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group are mentioned. These groups may further have a substituent.

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

The divalent organic group for Ry is preferably an alkylene group.
The ring that may be formed by combining Rx and Ry with each other is preferably a 5- to 10-membered ring containing a nitrogen atom, and more preferably a 6-membered ring.

  Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, and a camphor residue). Group).

As a cycloalkyl group in Rx, a C3-C20 cycloalkyl group is preferable. The cycloalkyl group may have an oxygen atom in the ring.
The aryl group for Rx is preferably an aryl group having 6 to 14 carbon atoms.

The aralkyl group in Rx is preferably an aralkyl group having 7 to 20 carbon atoms.
Examples of the alkenyl group in Rx include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

  The proton acceptor functional group in R is as described above, and examples thereof include azacrown ether groups, primary to tertiary amine groups, and groups having a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole. It is done.

  An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkyl group in a alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group in R include a proton acceptor functional group or ammonium group And the same groups as 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), an aryl group (preferably Has 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 C2-C20) and an aminoacyl group (preferably C2-C20) are mentioned. As for the cyclic structure in the aryl group and cycloalkyl group, and the aminoacyl group, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms).

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

  Examples of the monocycle include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycycle include a structure composed of a combination of 2 or 3 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 Has 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 C2-C15) or an aminoacyl group (preferably C2-C20) is preferable. The cyclic structure in the aryl group or cycloalkyl group may further have an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent. The aminoacyl group may further have an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent.

The Rf in the _-X 1 _NHX 2 Rf represented by Q, preferred is an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. As the _{X 1} and _{X 2,} at least one of -SO ₂ - is preferably, both _{X 1} and _{X 2} are -SO ₂ - and more preferably.

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

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 portion.
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 have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.

The counter cation is preferably an onium cation. 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. A preferred example is an iodonium cation described as (R ₂₀₄ ) (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.

  In addition, 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 that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

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.

X ^- is the, X in formula (ZI) to be described later ^- include the same specific examples as.
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 compounding amount of the compound (PA) is preferably 0.1 to 10% by mass and more preferably 1 to 8% by mass with respect to 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 three nitrogens.
As the basicity of the guanidine compound (A), the pKa of the conjugate acid is preferably 6.0 or more, and the neutralization reactivity with the acid is high, and the roughness property is excellent. It is preferable and it is more preferable that it is 8.0-16.0.

  Such strong basicity can suppress acid diffusibility and contribute to the formation of an excellent pattern shape.

  In the present specification, log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. Generally, the distribution coefficient is obtained by calculation without experimentation. In this specification, CSChemDrawUltraVer. The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.

  Moreover, it is preferable that logP of a guanidine compound (A) is 10 or less. By being below the above value, it can be uniformly contained in the resist film.

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

  Moreover, it is preferable that a guanidine compound (A) does not have a nitrogen atom other than a guanidine structure.

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

(7) A low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition for forming an upper layer film is a low molecular compound having a nitrogen atom and having a group that can be eliminated by the action of an acid ( Hereinafter, “low molecular compound (D)” or “compound (D)”) may be included. The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.

  The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, carbonate group, carbamate group, tertiary ester group, tertiary hydroxyl group, or hemiaminal ether group, and a carbamate group or hemamiamide. A nal ether group is more preferred.

  The molecular weight of the low molecular compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.

  As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the 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 general formula (d-1),
R ′ each 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 bonded to each other to form a ring.

R ′ is preferably independently a linear or branched alkyl group, a cycloalkyl group, or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group. .
Specific examples of the structure represented by the general formula (d-1) are shown below.

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

  The compound (D) particularly preferably has a structure represented by the following general formula (A).

  The compound (D) may be a compound corresponding to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

In General Formula (A), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When n = 2, two R _{a s} may be the same or different, and two R _a are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less), Alternatively, a derivative thereof may be formed.

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

At least two R _b 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 R _a and R _b is a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group. Or a functional group such as an alkoxy group, or a halogen atom. The same applies to the alkoxyalkyl group represented by _Rb .

R _a and / or R _b alkyl group, cycloalkyl group, aryl group, or aralkyl group (these alkyl group, cycloalkyl group, aryl group, or aralkyl group are the above functional group, alkoxy group, halogen, (Optionally substituted with atoms)
For example, groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, as well as these alkanes A group substituted with one or more of a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and noradamantane, and groups derived from these cycloalkanes are, for example, methyl, ethyl, 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 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 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, indoline, quinoline, perhydroquinoline, indazole, and benzimidazole, and groups derived from these heterocyclic compounds, A linear or branched alkyl group or a group substituted with one or more groups derived from an aromatic compound,
A group derived from a linear or branched alkane and a group derived from a cycloalkane substituted with one or more groups derived from an aromatic compound such as a phenyl group, a naphthyl group, an anthracenyl group, and the like, and And a group in which the above 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.

In addition, the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) formed by bonding of _Ra to each other, or derivatives thereof include, for example, pyrrolidine, piperidine, morpholine, 1, 4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H -1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+ ) -2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-e , Indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, groups derived from heterocyclic compounds such as 1,5,9-triazacyclododecane, and heterocycles thereof A group derived from a formula compound is a group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group. , Amino groups, pyrrolidino groups, piperidino groups, morpholino groups, or groups substituted with one or more functional groups such as oxo groups.

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

The compound represented by the general formula (A) can be synthesized based on JP2007-298869A or JP2009-199021A.
Compound (D) may be used alone or in combination of two or more.

Other usable compounds include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869.
A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.
As the basic compound, a so-called photodegradable base may be used. Examples of the photodegradable base include onium salts of carboxylic acids and onium salts of sulfonic acids in which the α-position is not fluorinated. Specific examples of the photodegradable base include groups described in paragraph 0145, JP-A-2008-158339, and Japanese Patent No. 399146 of WO2014 / 133030A1.

(Basic compound content)
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. 1-5 mass% is further more preferable.

(Base generator)
Examples of the base generator (photobase generator) include, for example, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, and JP-A-6-6. Examples thereof include compounds described in Japanese Patent No. 194834, Japanese Patent Laid-Open No. 8-146608, Japanese Patent Laid-Open No. 10-83079, and European Patent No. 622682.
Moreover, the compounds described in JP 2010-243773 A are also used as appropriate.
Specific examples of the photobase generator include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, and 1,1-dimethyl-2- An example is phenylethyl-N-isopropylcarbamate.

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

<(A2) Compound having a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and 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. To 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.

  Compound (A2) preferably has 2 or more bonds or groups selected from the above group, more preferably 3 or more, and still more preferably 4 or more. In this case, the bonds or groups selected from an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond contained in a plurality of compounds (A2) may be the same or different. May be.

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

Moreover, 8 or more are preferable, as for carbon number contained in a compound (A2), 9 or more are more preferable, and 10 or more are more preferable.
In addition, 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 the compound (A2) is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 240 ° C. or higher.

The compound (A2) is preferably a compound having an ether bond, preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.
Especially, it is preferable that a compound (A2) contains the repeating unit which has an oxyalkylene structure represented by following General formula (1).

Where
R ₁₁ represents an alkylene group which may have a substituent,
n represents an integer of 2 or more,
* Represents a binding site.

Although carbon number of the alkylene group represented by R < ₁₁ > in General formula (1) is not restrict | limited in particular, 1-15 are preferable, 1-5 are more preferable, 2 or 3 is further more preferable, and 2 is especially preferable. When this alkylene group has a substituent, the substituent is not particularly limited, but for example, an alkyl group (preferably having 1 to 10 carbon atoms) is preferable.
n is preferably 2 to 20, and among them, 10 or less is more preferable 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, more preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. Here, the “average value of n” means the value of n determined so that the weight average molecular weight of the compound (A2) is measured by GPC and the obtained weight average molecular weight matches the general formula. If n is not an integer, round it off.
A plurality of R ₁₁ may be the same or different.

  Moreover, it is preferable that the compound which has the partial structure represented by the said General formula (1) is a compound represented by the following general formula (1-1) from the reason for DOF becoming larger.

Where
R ₁₁ is the same as _{R 11} in general formula (1).
R ₁₂ and R ₁₃ each independently represents a hydrogen atom or an alkyl group. Although carbon number in particular of an alkyl group is not restrict | limited, 1-15 are preferable. R ₁₂ and R ₁₃ may combine 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 DOF is larger.
The average value of m is preferably 20 or less, more preferably 1 to 10, more 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 “average value of n” described above.
When m is 2 or more, a plurality of R ₁₁ 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.

  Compound (A2) may be a commercially available product, or may be synthesized by a known method.

  Specific examples of the compound (A2) are shown below.

  The content of the compound (A2) in the upper layer film-forming composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content of the upper layer film-forming composition. -20% by mass is more preferable, and 3-18% 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 an anionic surfactant, a cationic surfactant, and a surfactant can be formed as long as the composition for forming the upper layer film can be uniformly formed and can be dissolved in the solvent for the composition for forming the upper layer film. Any of the nonionic surfactants can be used.
0.001-20 mass% is preferable with respect to the composition for upper layer film formation, and, as for the addition amount of surfactant, 0.01-10 mass% is more preferable.
Surfactant may be used by 1 type and may use 2 or more types together.

Examples of the surfactant include alkyl cationic surfactants, amide type quaternary cationic surfactants, ester type quaternary cationic surfactants, amine oxide surfactants, betaine surfactants, alkoxy Rate surfactants, fatty acid ester surfactants, amide surfactants, alcohol surfactants, ethylenediamine surfactants, and fluorine and / or silicon surfactants (fluorine surfactants, Silicon-based surfactants and surfactants having both fluorine atoms and silicon atoms) are preferred.
Specific examples of surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenol ether, and , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether; 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 , Surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Agents.
Examples of commercially available surfactants that can be used include F-top EF301 and 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 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (Asahi Glass ( Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, and GF-150 (manufactured by Toagosei Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135 , EF351, 352, EF801, EF802, and EF601 (manufactured by Gemco), PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA), and FTX-204D, 208G, 218G, 230G, 204D, 208D , 212D, 218, and 222D (manufactured by Neos Co., Ltd.), and other fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

<Method for Preparing Composition for Forming Upper Layer Film>
The composition for forming an upper layer film produced by the method for producing the composition for forming an upper layer film of the present invention is preferably prepared by dissolving the above components in a solvent. As above-mentioned, as a supply source of fluorine-containing resin, the solution containing the fluorine-containing resin which passed through the 1st filtration process in the manufacturing method of the said composition for upper layer film formation is used. The prepared composition for forming an upper layer film is subjected to the second filtration step described above.
It is preferable that the composition for forming an upper layer film 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, even more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device). .

[Photosensitive resin composition]
Next, the photosensitive resin composition manufactured with the manufacturing method of the photosensitive resin composition of this invention is demonstrated.
As above-mentioned, the photosensitive resin composition is prepared using the solution containing the fluorine-containing resin which passed through the 1st filtration process in the manufacturing method of the said 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.
Although content in particular of the fluorine-containing resin in the photosensitive resin composition is not restrict | limited, 0.01-20 mass% is preferable with respect to the total solid, and 0.1-10 mass% is more preferable.
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 photosensitive resin composition or a positive 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 increases by the action of an acid and whose solubility in a developer containing an organic solvent decreases. .
Resins whose polarity increases by the action of an acid and their solubility in a developer containing an organic solvent decreases (hereinafter also referred to as “resin (A)”) are the main chain or side chain of the resin, or the main chain and side chain. Both of them are preferably resins having a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”).
Furthermore, 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-decomposable resin”). A resin having a monocyclic or polycyclic alicyclic hydrocarbon structure has high hydrophobicity, and it is considered that developability is improved when a region having a low light irradiation intensity of a resist film is developed with an organic developer.

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

The polar group in the acid-decomposable group typically includes an acid group, and specifically includes a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (Alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) ) Groups having an imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) methylene group.
Preferred polar groups include carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonic acid groups, and the like.
A preferable group as an acid-decomposable group (acid-decomposable group) is a group obtained by substituting a hydrogen atom of these polar groups with a group capable of leaving with an acid.
Examples of the group capable of leaving with an acid include -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.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
As the acid-decomposable 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 at least selected from the group consisting of repeating units having a partial structure represented by the following general formula (pI) to general formula (pV) and repeating units represented by the following general formula (II-AB). A resin having one kind is preferred.

In 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 necessary for forming a cycloalkyl group together with a carbon atom. Represents an atomic group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group. 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 represents 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 each independently represents 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. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

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

  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 ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —X—A′—R. ₁₇ ′ represents 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, a hydroxyl group, an 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 the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo structure having 5 or more carbon atoms, a bicyclo structure, a tricyclo structure, a tetracyclo structure, and the like. 6-30 are preferable and, as for carbon number of a cycloalkyl group, 7-25 are more preferable. These cycloalkyl groups may have a substituent.

  Cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group 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.

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

  The structures represented by the general formulas (pI) to (pV) in the resin can be used for protecting polar groups. Examples of the polar group include various groups known in this technical field.

  Specific examples 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). Among these, a structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a structure represented by general formulas (pI) to (pV) is preferable.

  As the repeating unit having a polar group protected by the structure represented by the general formulas (pI) to (pV), a 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 R may be the same or different.
A represents 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 single group of two or more groups selected from the group consisting of urea groups. Represents a combination. Among these, 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 of 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (pA) are shown below.

As a halogen atom in the said general formula (II-AB), R < ₁₁ '> and R < ₁₂ '>, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned each independently.

Examples of the alkyl group in R ₁₁ ′ and R ₁₂ ′ include, independently of each other, a linear or branched alkyl group having 1 to 10 carbon atoms.

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

Examples of the alicyclic hydrocarbon skeleton to be formed include the same skeleton as the alicyclic hydrocarbon groups of R _{12 to} R ₂₅ in the general formulas (pI) to (pV).

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

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

  The repeating unit having an acid-decomposable group contained in 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 sulfonate ester) structure.
Any lactone group or sultone group may be used as long as it has a lactone structure or sultone structure. Among them, a 5- to 7-membered lactone structure or sultone structure is preferable, and a group in which another ring structure is condensed in a form that forms a bicyclo structure or a spiro structure in the 5- to 7-membered lactone structure or sultone structure. More preferred. It has 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. A lactone structure or a sultone structure may be directly bonded to the main chain. As the lactone structure or sultone structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), or general formula (LC1-8) is preferable, and general formula (LC1-4) Is more preferable. By using a specific lactone structure or sultone structure, LWR (Line Width Roughness, fluctuation in pattern line width) and development defects can be improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). As the substituent (Rb ₂ ), 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, a carboxyl group, A halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is more preferable. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded 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 the substrate adhesion and developer compatibility. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.
As the alicyclic hydrocarbon structure substituted with a polar group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In general formulas (VIIa) to (VIIc),
R _{2c to} R _4c each independently represents 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. Among these, it is preferable that one or two of R _{2c to} R _4c are a hydroxyl group and the remainder is a hydrogen atom.
In general formula (VIIa), it is more preferable that two members out of R _{2c to} R _4c are a hydroxyl group and the rest are hydrogen atoms.

Examples of the repeating unit having a group represented by the general formulas (VIIa) to (VIId) include at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). One repeating unit having a group represented by the above general formula (VII) (for example, R ₅ in —COOR ₅ represents a group represented by general formulas (VIIa) to (VIId)), and the following general formula ( AIIa) to repeating units represented by (AIId) are exemplified.

In general formulas (AIIa) to (AIId),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _<2c > -R < _4c > is synonymous with R < _2c > -R < _4c > in general formula (VIIa)-(VIIc).

  Below, the specific example of the repeating unit which has a structure represented by general formula (AIIa)-(AIId) is shown.

As for the weight average molecular weight of resin (A), 1000-200000 are preferable as a polystyrene conversion value by GPC method, 1000-20000 are more preferable, and 1000-15000 are more preferable. By setting the weight average molecular weight to 1000 to 200000, deterioration of heat resistance or dry etching resistance can be prevented, and developability is deteriorated, and viscosity is increased and film formability 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 walls of the pattern, and the better the roughness.

The content of the resin (A) is preferably 50 to 99.9% by mass and more preferably 60 to 99.0% by mass with respect to the total solid content of the photosensitive resin composition.
Moreover, resin (A) may be used by 1 type and may use 2 or more types together.

  The resin (A) preferably has no fluorine atom or silicon atom from the viewpoint of compatibility with the composition for forming an upper layer film.

<Compound that generates acid upon irradiation with actinic ray or radiation>
The photosensitive resin composition typically contains a compound (also referred to as “photo acid generator” or “compound (B)”) that generates an acid upon irradiation with actinic rays or radiation.
The compound (B) may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the compound (B) is in the form of a low molecular 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 acid-decomposable resin described above or may be incorporated in a resin different from the acid-decomposable resin. .
The compound (B) is preferably a low molecular compound.
As compound (B), photocationic polymerization photoinitiator, radical photopolymerization photoinitiator, dye photodecoloring agent, photochromic agent, irradiation of actinic rays or radiation used in microresist, etc. Known compounds that generate an acid and mixtures thereof can be appropriately selected and used.

  Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a compound in which a group or a compound capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3,914,407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853 Alternatively, compounds described in JP-A-63-146029 can be used.

  Further, compounds capable of generating an acid by light as described in US Pat. No. 3,777,778 or European Patent No. 126712 can also be used.

The compound (B) is preferably a compound that generates an acid having a cyclic structure when irradiated with actinic rays or radiation. As the cyclic structure, a monocyclic or polycyclic alicyclic group is preferable, and a polycyclic alicyclic group is more preferable. The carbon atom constituting the ring skeleton of the alicyclic group preferably does not contain a carbonyl carbon.
As a compound (B), the compound (specific acid generator) which generate | occur | produces an acid by irradiation of the actinic ray or radiation represented with the following general formula (3), for example is preferable.

(Anion)
In general formula (3),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R ₅ each independently represents 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 R ₄ and R ₅ , R ₄ and R ₅ are the same 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 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. 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, more preferably a fluorine atom or CF ₃ . Especially, it is preferable that both Xf is a 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 R ₄ and R ₅ , R ₄ and R ₅ are the same 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 a hydrogen atom.
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 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 having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group in which a plurality of these groups are combined Etc. 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, a cyclic organic group is preferred.
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 of 7 or more carbon atoms such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, diamantyl group, or adamantyl group is used in PEB. It is preferable from the viewpoint of suppression of diffusibility in the film and improvement of 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. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity 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 heterocyclic ring that does not have aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin.

  The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), a cycloalkyl group (whether monocyclic or polycyclic). Well, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfone. An acid ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
In one embodiment, o in the general formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is preferably 0. Xf is preferably a fluorine atom, both R ₄ and R ₅ are preferably hydrogen atoms, and W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, and further preferably 1. p is more preferably an integer of 1 to 3, further preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, and further 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, and preferred embodiments include, for example, cations (parts other than Z ⁻ ) in formulas (ZI), (ZII), and (ZIII) described later.

(Preferred embodiment)
As a suitable aspect of a specific acid generator, the compound represented by the following general formula (ZI), (ZII), and (ZIII) is mentioned, for example.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R _{201, R 202} and _{R 203} is preferably 1 to 30, 1 to 20 is more preferable.
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 combining 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, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.
A compound (B) may be used by 1 type and may use 2 or more types together.
The content of the compound (B) in the photosensitive resin composition (the total when there are a plurality of types) is preferably 0.1 to 30% by mass with respect to 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 carboxylates (eg, PGMEA), alkylene glycol monoalkyl ethers (eg, PGME (propylene glycol monomethyl ether)), alkyl lactate esters, alkyl alkoxypropionates, and cyclic rings having 4 to 10 carbon atoms. Examples thereof include organic solvents such as lactones (γ-butyrolactone, etc.), monoketone compounds having 4 to 10 carbon atoms, which may have a ring (cyclohexanone, etc.), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.
Moreover, as above-mentioned, it is also preferable to use the same solvent as the solvent contained in the solution containing the fluorine-containing resin used for the 1st filtration process in the manufacturing method of the said photosensitive resin composition.

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

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

Regarding the alkyl group, the alkyl group having a substituent is preferably 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.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in these general formulas (A) to (E) are more preferably unsubstituted.

  As the basic compound, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine are preferable. Imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, 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 the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo. [5, 4, 0] undec-7-ene. 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, tris (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 converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. It is 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 the alkylamine derivative 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.

  Moreover, as the basic compound, a basic compound that may be contained in the above-described composition for forming an upper layer film can also be suitably used.

These basic compounds may be used alone or in combination of two or more.
0.001-10 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for the usage-amount of a basic compound, 0.01-5 mass% is more preferable.

  The use ratio of the photoacid generator and 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 reduction in resolution due to pattern thickening over time until post-exposure 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 includes a fluorine-based and / or silicon-based surfactant (a fluorine-based surfactant, a silicon-based surfactant, and both a fluorine atom and a silicon atom). It is more preferable that any one or two or more kinds of surfactants) are included.

When the photosensitive resin composition contains the above surfactant, it is possible to give a pattern with less adhesion and development defects with good sensitivity and resolution 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, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862, US Pat. No. 5,405,720, US Pat. No. 5,360,692, US Pat. No. 5,529,881, 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. Listed surfactants, and commercially available surfactants can be used as they are.

  These surfactants may be used alone or in several combinations.

  0.01-10 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for the usage-amount of surfactant, 0.1-5 mass% is more preferable.

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

  Specific examples of fluorinated carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid. And anions of acid and 2,2-bistrifluoromethylpropionic acid.

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

  The content of the carboxylic acid onium salt in the composition is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 10 mass%, more preferably from 1 to 7 based on the total solid content of the photosensitive resin composition. More preferred is mass%.

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

Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210 or European Patent 219294. Can be easily synthesized by those skilled in the art.
Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, and And cyclohexanedicarboxylic acid.

<Method for 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 further 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 further, a pattern excellent in LWR can be formed. The reason for this is not clear, but it is likely that the solid content concentration is 10% by mass or less (preferably 5.7% by mass or less), so that the material in the photosensitive resin composition, particularly the photoacid generator, Aggregation is suppressed, and as a result, a uniform resist film can be formed.
The solid content concentration is a mass percentage of the mass of the other photosensitive resin composition 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 components in a predetermined solvent. As a supply 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 second filtration step described above, and can be used by coating on a predetermined support (substrate).

[Pattern formation method]
The photosensitive resin composition manufactured by the pattern formation method using the composition for upper layer film formation manufactured with the manufacturing method of the composition for upper layer film formation of this invention, or the manufacturing method of the photosensitive resin composition of this invention A pattern forming method using the above will be described.

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

<Step a1>
Step a1 is a step of forming an upper layer film on the resist film using the upper layer film forming composition.
A known resist film can be used as the resist film. For example, the resist film formed using the resin (A) which the photosensitive resin composition mentioned above may contain and the composition containing a photo-acid generator etc. is mentioned. More specifically, a resist film is preferably formed by applying a composition containing the resin (A), a photoacid generator, and the like onto a predetermined substrate.
The method for applying the composition onto the substrate is not particularly limited, and includes conventionally known spin coating methods, spray methods, roller coating methods, dipping methods, and the like, and spin coating methods are preferred.
After applying the above composition, the substrate may be heated (pre-baked (PB)) as necessary. Thereby, the resist film from which the insoluble residual solvent is removed can be formed uniformly. Although the temperature of prebaking is not specifically limited, 50-160 degreeC is preferable and 60-140 degreeC is more preferable.
The thickness of the resist film is preferably 20 to 200 nm, and 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) ) And the like, semiconductor substrate manufacturing processes such as liquid crystal and thermal heads, and other photo application lithography processes.

Before forming the resist film, an antireflection film may be coated on the substrate in advance.
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 made of a light absorber and a polymer material can be used. Specific examples of usable organic antireflection films include DUV30 series and DUV-40 series manufactured by Brewer Science, AR-2, AR-3, and AR-5 manufactured by Shipley, and Commercially available organic antireflection films such as ARC series such as ARC29A manufactured by Nissan Chemical Co., Ltd. can be mentioned.

The method for forming the upper layer film on the resist film by using the upper layer film forming composition is not particularly limited. 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 coating method of the composition for forming the upper layer film is not particularly limited, and examples thereof include conventionally known spin coating method, spray method, roller coating method, and dipping method.
The pre-baking 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 higher than 120 ° C.
Although the upper limit of PB temperature is not specifically limited, 200 degrees C or less is preferable, 170 degrees C or less is more preferable, 160 degrees C or less is more preferable, 150 degrees C or less is especially preferable.

When exposure in step b1 described later is immersion exposure, the upper layer film is disposed 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 properties that the upper layer film preferably have are transparency to radiation (particularly wavelength; 193 nm) and poor solubility in immersion liquid (preferably water). Moreover, it is preferable that the composition for forming an upper layer film is not mixed with the resist film, is excellent in coatability on the surface of the resist film, and can be applied uniformly.
In order to uniformly apply the upper layer film-forming composition to the surface of the resist film without dissolving the resist film, the upper layer film-forming composition preferably 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 the organic developer described later.
The details of the composition for forming the upper layer film are as described above.

The thickness of the upper layer film is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 300 nm, still more preferably 20 to 200 nm, and particularly preferably 30 to 100 nm, from the viewpoint of transparency to the exposure light source.
After forming the upper layer film, the substrate is heated as necessary.
The refractive index of the upper layer film is preferably close to the refractive index of the resist film from the viewpoint of resolution.
The receding contact angle of the upper layer film is preferably 50 to 100 degrees, more preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability. More preferred.
In immersion exposure, the immersion liquid needs to move on the substrate following the movement of the lens scanning the substrate at high speed to form an exposure pattern. The contact angle of the immersion liquid becomes 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 separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable. From the viewpoint that the upper layer film can be peeled off simultaneously with the development of the resist film, the upper layer film is preferably peelable by an organic developer. The organic developer used for the stripping is not particularly limited as long as it can dissolve and remove the low-exposed portion of the resist film, and polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents described later. Or a developer containing a hydrocarbon solvent, preferably a developer containing a ketone solvent, an ester solvent, an alcohol solvent, or an ether solvent, and more preferably a developer containing an ester solvent. A developer containing butyl acetate is more preferred.

From the viewpoint of peeling with an organic developer, the upper layer film preferably has a dissolution rate in the organic developer of 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
Here, the dissolution rate of the upper layer film with respect to the organic developer is the rate of film thickness reduction when the upper layer film is formed and then exposed to the developer. In this specification, the film is immersed in a butyl acetate solution at 23 ° C. It is the speed when letting it go.
By setting the dissolution rate of the upper layer film in the 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. In addition, 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 probably better due to the effect of reducing the exposure unevenness during immersion exposure. There is an effect of becoming.
The upper layer film may be removed using another known developer, for example, an alkaline aqueous solution. Specific examples of the aqueous alkali 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 actinic rays or radiation through a predetermined mask. At this time, although it is preferable to irradiate actinic light or a radiation through an immersion liquid, it is not limited to this. Although an exposure amount can be set suitably, 1-100 mJ / cm < ² > is preferable.
The wavelength of the light source used in the exposure apparatus is not particularly limited, but it is preferable to use light having a wavelength of 250 nm or less. Examples thereof include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), and F _2. Examples include excimer laser light (157 nm), EUV light (13.5 nm), and an electron beam. Among these, it is preferable to use ArF excimer laser light (193 nm).

When immersion exposure is performed, the surface of the film may be washed with an aqueous chemical solution before exposure and / or after exposure and before heating described below.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of ArF excimer laser light (wavelength: 193 nm), in addition to the above-mentioned viewpoints, it is preferable to use water from the viewpoints of availability and ease of handling.
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 can ignore the influence on the optical coating on the lower surface of the lens element. As water to be used, distilled water is preferable. Further, pure water filtered through an ion exchange filter or the like may be used. Thereby, distortion of the optical image projected on the resist film due to mixing of impurities can be suppressed.
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 the step b1 (exposure step) a plurality of times. In this case, the same light source or different light sources may be used for the multiple exposures, but ArF excimer laser light (wavelength: 193 nm) is preferably used for the first exposure.

  After exposure, it is preferable to further heat (PEB) and develop (preferably further rinse). Thereby, a good pattern can be obtained. Although the temperature of PEB is not specifically limited as long as a favorable pattern is obtained, 40-160 degreeC is preferable. 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 alkali developer or a developer containing an organic solvent, but a developer containing an organic solvent is preferred. You may combine the image development process by an alkali developing solution, and the image development process by the developing solution containing the organic solvent.
As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but other than this, for example, an inorganic alkali, a primary to tertiary amine, an alcohol amine, or a cyclic amine, etc. An alkaline aqueous solution can also be used.
Specifically, examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and alkaline aqueous solutions such as pyrrole and cyclic amines such as piperidine can be used. Among these, it is preferable to use an aqueous solution of tetraethylammonium hydroxide.
Further, an appropriate amount of alcohol and / or surfactant may be added to the alkaline developer. The alkali concentration of the alkali developer is preferably from 0.1 to 20% by mass. The pH of the alkali developer is preferably from 10.0 to 15.0.
The time for developing with an alkali developer is preferably 10 to 300 seconds.
The alkali concentration (and pH) and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.
After the development with an alkali developer, the substrate may be washed with a rinse solution. As the rinse solution, pure water is used, and an appropriate amount of a surfactant can be added.
Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
Furthermore, after the rinsing process or the process with the supercritical fluid, a heat treatment can be performed to remove moisture remaining in the pattern.

Developer solutions containing organic solvents (hereinafter also referred to as organic developer solutions) include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. The developing solution containing is mentioned.
Specific examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone. , Phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, 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 butyrate, Isobutyl butyrate, butyl butanoate, 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, 2- Dorokishiiso butyric acid methyl, isobutyl isobutyrate, and, butyl propionate.
Specific examples of the alcohol solvent 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 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, Triethylene glycol monoethyl ether and glycol ethers such as methoxymethylbutanol Solvent and the like.
Specific examples of the ether solvent include dioxane and tetrahydrofuran in addition to the glycol ether solvent.
Specific examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolide. Non.
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 may be used by mixing with other solvents and / or water. However, the water content of the whole developer is preferably less than 10% by mass, and more preferably substantially free of moisture.
Specifically, the amount of the organic solvent used relative to the organic developer is preferably 90 to 100% by mass and more preferably 95 to 100% by mass with respect to the total amount of the developer.

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

The vapor pressure of the organic developer at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, the evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the substrate surface is improved. As a result, the dimensions in the substrate surface are uniform. Sexuality improves.
Specific examples of the solvent having a vapor pressure of 5 kPa or less (or 2 kPa or less) include the solvents described in paragraph [0165] of JP-A No. 2014-71304.

The organic developer may contain an appropriate amount of a surfactant as required.
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 surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, US Pat. No. 5,360,692, US Pat. No. 5,529,881, US Pat. No. 5,296,330, US Pat. No. 5,346,098, US Pat. No. 5,576,143, US Pat. No. 5,294,511, and US Pat. No. 5,824,451. Nonionic surfactants are preferred. Although it does not specifically limit as a nonionic surfactant, It is preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and still more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the organic developer are the same as the basic compound that can be contained in the photosensitive resin composition.

  As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing). Law).

  Moreover, you may have the process of stopping image development, substituting with another solvent after the process developed using the developing solution containing an organic solvent.

After the step of developing using a developer containing an organic solvent, a step of washing with a rinse solution may be included.
The rinse liquid is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinsing liquid is, for example, selected from the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents described above as the organic solvents contained in the organic developer. A rinsing liquid containing at least one organic solvent is preferable, and a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents. Is more preferable, a rinse liquid containing a hydrocarbon solvent, an alcohol solvent, or an ester solvent is more preferable, and a rinse liquid including a monohydric alcohol is particularly preferable.

  Here, the monohydric alcohol used in the rinsing step includes 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- Chill 2-nonanol, 6-methyl-2-nonanol, 7-methyl-2-nonanol and, include 2-decanol. Among 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), and undecane. And aliphatic hydrocarbon solvents.
When an ester solvent is used as the rinsing liquid, a glycol ether solvent may be used in addition to the ester solvent (one or more). 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 subcomponent. Thereby, residue defects are suppressed.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By making the water content 10% by mass or less, good developability can be obtained.
The vapor pressure of the rinsing liquid is preferably 0.05 to 5 kPa, more preferably 0.1 to 5 kPa, further preferably 0.12 to 3 kPa at 20 ° C. By setting the vapor pressure of the rinse liquid to 0.05 to 5 kPa, the temperature uniformity in the substrate surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the substrate surface is good. Turn into.
An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the substrate that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples include a method (dip method) or a method of spraying a rinsing liquid on the substrate surface (spray method). Among these methods, cleaning is performed by a spin coating method, and the substrate is rotated at a rotational speed of 2000 rpm to 4000 rpm after cleaning. It is preferable to remove the rinse liquid from the substrate. Moreover, it is also preferable to include a heating process (PostBake) after the rinsing process. The developer and the rinsing liquid remaining between the patterns and inside the patterns are removed by heating. 40-160 degreeC is preferable and the superheating temperature of the heating process after a rinse process has more preferable 70-95 degreeC. The heating time in the heating step after the rinsing step is preferably 10 seconds to 3 minutes, and more preferably 30 to 90 seconds.

  Moreover, the pattern formation method may have the image development process using an organic type developing solution, and the image development process using an alkali developing solution. A portion with low exposure intensity is removed by development using an organic developer, and a portion with high exposure intensity is also removed by development using an alkali developer. In this way, the multiple development process in which development is performed a plurality of times enables pattern formation without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A). [Mechanism similar to [0077]).

It is preferable that the pattern formation method using the photosensitive resin composition obtained using the specific solution mentioned above includes the following steps a2 to c2.
Step a2: Step of forming a resist film using the photosensitive resin composition Step b2: Step of exposing the resist film Step c2: Step of developing the exposed resist film The procedures of Step b2 and Step c2 have been described above. Since it is the same as process b1 and process c1, description is abbreviate | 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.
A method for forming a resist film using the photosensitive resin composition is not particularly limited, but a method of forming a resist film by applying the photosensitive resin composition on a substrate is preferable.
The coating method of the photosensitive resin composition is not particularly limited, and conventionally known spin coating method, spray method, roller coating method, dipping method and the like can be mentioned, and the spin coating method is preferable.
After application of the photosensitive resin composition, the substrate may be heated (pre-baked (PB)) as necessary. Thereby, the film | membrane from which the insoluble residual solvent was removed can be formed uniformly. Although the temperature of prebaking is not specifically limited, 50-160 degreeC is preferable and 60-140 degreeC is more preferable.
The thickness of the resist film is preferably 20 to 200 nm, and more preferably 30 to 100 nm.

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

  Composition for forming upper layer film, photosensitive resin composition, and various materials used in pattern formation method (for example, solvent, developer, rinse solution, composition for forming antireflection film, and composition for forming upper layer film) Are preferably free of impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, even more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device).

[Method of manufacturing electronic device]
The present invention also relates to an electronic device manufacturing method including the pattern forming method described above, and an electronic device manufactured by the manufacturing method.
The manufactured electronic device is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, and the like).

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

<Fluorine-containing resin>
Table 1 below shows the monomer corresponding to the repeating unit of the fluorine-containing resin used in Examples or Comparative Examples and the molar ratio of each repeating unit to the fluorine-containing resin.

<First filtration of solution containing 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 solution containing the obtained fluorine-containing resin was subjected to the first filtration step. The obtained filtrate was used for preparation of the photosensitive resin composition described later (Examples 1 to 6, 8 to 10, and 13 to 18).

<First filtration of solution containing fluorine-containing resin (for upper layer film-forming composition)>
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 solution containing the obtained fluorine-containing resin was subjected to the first filtration step. The obtained filtrate was used for the preparation of the composition for forming an upper layer film described later (Examples 7, 11, and 12).

The contents of the first filtration step of the solution containing the fluorine-containing resin in each example, and the type and pore size of the filter are shown in the following Table 2. In Table 2, the description in the lower column of each filter is the material of the filter And the pore size. Unfilled indicates that the filter does not pass through.
In Table 2, the description in the column of the number of circulations described when the circulation filtration step is carried out includes [the filtration integrated amount by the third filter of the solution containing the fluorine-containing resin / the fluorine-containing resin subjected to the circulation filtration step. Solution amount].
As described above, in Examples 7, 11, and 12, the solvent of the solution containing the fluorine-containing resin is diisoamyl ether. In another embodiment, the solvent of the solution containing the fluorine-containing resin is PGMEA.
Moreover, about two types of fluorine-containing resin used in Example 6, after preparing each in the solution containing a fluorine-containing resin separately, each solution containing the said two types of fluorine-containing resin is separately subjected to the first filtration. It used for the process.

<Preparation of photosensitive resin composition>
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 component and the ratio in the solvent component shown in Table 3 below. The obtained solution was filtered with 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.
Moreover, when the photosensitive resin composition used as an Example contains fluorine-containing resin, the solution containing fluorine-containing resin which passed through said 1st filtration process was made into the supply source of fluorine-containing resin. That is, in Examples 1 to 6, 8 to 10, and 13 to 18 shown in Table 3, a photosensitive resin using a solution containing a fluorine-containing resin that has undergone the first filtration step shown in Table 2 above is used. A composition was prepared.
Moreover, when the photosensitive resin composition used as the comparative example contains a fluorine-containing resin, the fluorine-containing resin that has not undergone the first filtration step is used as the supply source of the fluorine-containing resin. That is, in Comparative Examples 1, 2, and 5, a photosensitive resin composition is manufactured using a fluorine-containing resin that has not been subjected to the first filtration step, and only the second filtration step is performed. .
In addition, with respect to the photosensitive resin composition of the comparative example 5, the said 2nd filtration process was implemented twice.
In addition, 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 performed. Only the second filtration step was performed.

  Table 3 below shows the composition of the photosensitive resin composition used in Examples and Comparative Examples.

  Table 4 below shows the repeating units of the resin (A) used for the preparation of the photosensitive resin composition and the molar ratios of the repeating units to the resin (A) (corresponding in order from the left).

  The photoacid generator used for preparation of the photosensitive resin composition is shown below.

  The basic compound used for preparation of the photosensitive resin composition is shown below.

The solvent used for preparation of the photosensitive resin composition and the composition for forming an upper layer film described later is 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 layer film-forming composition used in Examples 7, 11, and 12 was 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 has a ratio in the solvent component shown in Table 5 below. It was prepared as follows. The obtained solution was filtered with a polyethylene filter having a pore size of 0.03 μm as a second filtration step. The obtained filtrate was used as an upper film forming composition.
Moreover, the upper-layer film-forming composition used in Comparative Examples 3, 4, and 6 was prepared as follows.
First, a fluorine-containing resin not subjected to the first filtration step was prepared so that the solid content concentration was 4.3% by mass and the solvent component had a ratio in the solvent component shown in Table 5 below. The obtained solution was filtered with a polyethylene filter having a pore size of 0.03 μm as a second filtration step. The obtained filtrate was used as an upper film forming composition.
That is, in the manufacture of the composition for forming an upper layer film used in Comparative Examples 3, 4, and 6, only the second filtration step is performed without performing the first filtration step.
In addition, with respect to the composition for upper layer film formation of the comparative example 6, the said 2nd filtration process was implemented twice.
In Table 5, when “TC” is described in the column of the addition form of the examples or comparative examples, the upper layer film is formed using the upper layer film forming composition containing a fluorine-containing resin in the applicability evaluation described later. It shows that it formed.
In Table 5, when “addition” is described in the column of the addition form of the examples or comparative examples, it indicates that the fluorine-containing resin is contained in the photosensitive resin composition. When the addition form is “addition”, the upper layer film is not formed in the applicability evaluation described later.

The contents of the second filtration step performed on the photosensitive resin composition and the upper layer film-forming composition in each example or comparative example, and the type and pore size of the filter used in the second filtration step are as follows. Table 6 shows.
In Table 6, when “TC” is described in the column of the addition form of the examples or comparative examples, the upper layer film is formed using the upper layer film forming composition containing a fluorine-containing resin in the evaluation of coatability described later. It shows that it formed.
In Table 6, when “addition” is described in the column of the addition form of the examples or comparative examples, it indicates that the fluorine-containing resin is contained in the photosensitive resin composition. When the addition form is “addition”, the upper layer film is not formed in the applicability evaluation 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 frequency | count of filtration shows the frequency | count of implementing the 2nd filtration process with respect to each photosensitive resin composition and the composition for upper layer film formation.
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 was not subjected to the first filtration step. Only the second filtration step was performed.
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 implementation.
In the upper layer film-forming composition of Comparative Examples 3, 4, and 6, the upper layer film-forming composition was manufactured using a fluorine-containing resin that was not subjected to the first filtration step, and the second filtration step. Only carried out.

<Evaluation of coatability>
A 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, respectively.
Furthermore, in the examples and comparative examples for forming the upper layer film, the upper layer film forming composition 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 upper layer films each having an average film thickness of 97.0 to 103.0 nm.
In addition, the said average film thickness of a resist film and an upper film is the time of measuring the film thickness in each silicon wafer plane 13 points | pieces using the film thickness measuring apparatus (VM-3110, Dainippon Screen Mfg. Co., Ltd. product). Is the average value.
Furthermore, using the film thickness measurement apparatus, each film thickness at the outer peripheral portion of the silicon wafer was measured at 96 points, and a standard deviation (3σ) was calculated.
Here, in Examples and Comparative Examples in which the upper layer film was not formed, the thickness of the resist film was measured to calculate 3σ. In Examples and Comparative Examples in which the upper layer film was formed, the thickness of the upper layer film was measured to calculate 3σ.
In addition, the outer peripheral portion of the silicon wafer is intended to be an annular region of 5 mm from the edge of the silicon wafer toward the center in the surface of the disk-shaped silicon wafer having a radius of 200 mm.
Table 7 shows the evaluation results. The smaller the value of 3σ of the film thickness in the table, the more uniform the film thickness and the better the coating property of the composition for forming an upper film or the photosensitive resin composition on which the film is formed. When the value was 1.0 nm or less, it was judged that the coating property 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 between Example 11 and Comparative Example 3. Comparison between Example 12 and Comparative Example 4. Comparison between Example 8 and Comparative Example 1. Comparison between Example 10 and Comparative Example 2. ).
Moreover, the composition which implemented the 2nd filtration process once after passing through the 1st filtration process is more than the composition which implemented only the 2nd filtration process twice without passing through the 1st filtration process, 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, in addition to the filtration by the first filter, the solution containing the fluorine-containing resin is further filtered by the second and third filters. It was confirmed that it was obtained (Comparison of Examples 8, 13, and 15. Comparison of Examples 10, 14, and 16).
In the first filtration step, it was confirmed that a composition having further excellent coatability can be obtained by performing circulation filtration (comparison of Examples 15 and 17; comparison of Examples 16 and 18).

DESCRIPTION OF SYMBOLS 1 Tank 2 Pump 3 Flowmeter 4 Processing liquid filling container 5, 6, 7, 9, 10 Flow path 8 Filling port 100 Column in which the first filter is installed 200 Column in which the second filter is installed 300 Third Column with filter

Claims (16)

A first filtration step for filtering the solution containing the 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 method for producing an upper layer film-forming composition comprising a second filtration step of filtering the upper layer film-forming composition,
Manufacture of the composition for upper layer film formation in which the said fluorine-containing resin has at least 1 sort (s) selected from the group which consists of the repeating unit represented by General formula (1), and the repeating unit represented by General formula (2). Method.
In 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 that may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₃ represents a hydrogen atom or an alkyl group which may have a fluorine atom. However, at least one of R ₂ and R ₃ has a fluorine atom. L represents -O- or -COO-.
In general formula (2), R ₄ represents a hydrogen atom or an alkyl group which may have 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 a hydrogen atom or an alkyl group which may have 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 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 forming composition.
In 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 a hydrogen atom or an alkyl group which may have a fluorine atom. R ₇ represents an alkylene group having a fluorine atom which may have an oxygen atom.
In general formula (4), R ₄ represents a hydrogen atom or an alkyl group which may have a fluorine atom. R ₈ represents an alkylene group which may have an oxygen atom. R ₉ and R ₁₀ each independently represents 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 a hydrogen atom or an alkyl group which may have a fluorine atom.   The manufacturing method of the composition for upper-layer film formation of Claim 1 or 2 whose pore diameter of the filter used for filtration is 0.5 micrometer or less in said 1st filtration process. Step 1 in which the first filtration step filters the solution containing the fluorine-containing resin using a first filter, and
The manufacturing method of the composition for upper-layer film formation of any one of Claims 1-3 including the process 2 which filters the solution containing the said fluorine-containing resin which passed through the said process 1 using a 2nd filter.   5. The upper layer film-forming composition according to claim 4, 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. Production method.   6. The method according to claim 1, 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. A method for producing a composition for forming an upper layer film. A step of forming an upper layer film on the resist film using the composition for forming an upper layer film obtained by the manufacturing method according to any one of claims 1 to 6,
Exposing the resist film; and
A pattern forming method including a step of developing the exposed resist film.   The manufacturing method of an electronic device containing the pattern formation method of Claim 7. A first filtration step for filtering the solution containing the 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 method for producing a photosensitive resin composition comprising a second filtration step of filtering the photosensitive resin composition,
The manufacturing method of the photosensitive resin composition in which the said fluorine-containing resin has at least 1 sort (s) selected from the group which consists of the repeating unit represented by General formula (1), and the repeating unit represented by General formula (2). .
In 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 that may have one or more selected from the group consisting of a fluorine atom and an oxygen atom. R ₃ represents a hydrogen atom or an alkyl group which may have a fluorine atom. However, at least one of R ₂ and R ₃ has a fluorine atom. L represents -O- or -COO-.
In general formula (2), R ₄ represents a hydrogen atom or an alkyl group which may have 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 a hydrogen atom or an alkyl group which may have a fluorine atom. However, at least one of R _{4 to} R ₆ has a fluorine atom. L represents -O- or -COO-. The photosensitivity 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 resin composition.
In 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 a hydrogen atom or an alkyl group which may have a fluorine atom. R ₇ represents an alkylene group having a fluorine atom which may have an oxygen atom.
In general formula (4), R ₄ represents a hydrogen atom or an alkyl group which may have a fluorine atom. R ₈ represents an alkylene group which may have an oxygen atom. R ₉ and R ₁₀ each independently represents 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 a hydrogen atom or an alkyl group which may have a fluorine atom.   The manufacturing method of the photosensitive resin composition of Claim 9 or 10 whose pore diameter of the filter used for filtration is 0.5 micrometer or less in said 1st filtration process. Step 1 in which the first filtration step filters the solution containing the fluorine-containing resin using a first filter, and
The manufacturing method of the photosensitive resin composition of any one of Claims 9-11 including the process 2 which filters the solution containing the said fluorine-containing resin which passed through the said process 1 using a 2nd filter.   The said 1st filtration process contains the process 3 which further filters the solution containing the said fluorine-containing resin which passed through the said process 2 using a 3rd filter, The manufacture of the photosensitive resin composition of Claim 12 Method.   14. The method according to claim 9, 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. A method for producing a photosensitive resin composition. The process of forming a resist film using the photosensitive resin composition obtained by the manufacturing method of any one of Claims 9-14,
Exposing the resist film; and
A pattern forming method including a step of developing the exposed resist film.   The manufacturing method of an electronic device containing the pattern formation method of Claim 15.