TWI699391B - Method for producing resin composition and resin composition - Google Patents

Abstract

A subject of the invention is to provide a method for producing an actinic ray-sensitive or a radioactive ray-sensitive resin composition, and an actinic ray-sensitive or a radioactive ray-sensitive resin composition produced by the producing method. The method for producing the actinic ray-sensitive or the radioactive ray-sensitive resin composition of the invention includes a filtering step in which the actinic ray-sensitive or the radioactive ray-sensitive resin composition is filtered by passing through a filter. The filtering step is executed by passing the actinic ray-sensitive or the radioactive ray-sensitive resin composition through a first filter having an aperture of 10 nm or less for 5 times or more.

Description

Manufacturing method of resin composition and resin composition

The present invention relates to a microlithography process or other manufacturing processes that can be preferably used in the manufacture of large scale integrated circuits (Large Scale Integration, LSI) or high-capacity microchips (microlithography) or other processing (fabrication) processes. A method for producing an actinic ray-sensitive or radiation-sensitive resin composition that can form a high-definition pattern, and an actinic ray-sensitive or radiation-sensitive resin composition produced by the production method.

If a miniaturized resist pattern of 50 nm or less is required as in recent years, in addition to the resolution of the resist, it is necessary to improve the defects (surface defects) of the resist pattern after development. The defects are all defects that are detected when the developed resist pattern is observed from directly above using a surface defect observation device (trade name "KLA") made by KLA Tencor, for example. The defects include, for example, scum, bubbles, dust, and bridges between resist patterns after development.

Examples of the cause of such defects include particles (foreign materials or deposits of resist components) contained in the resist composition. Therefore, it is expected to reduce the number of manufacturing resist groups The particles that exist soon after the product is formed, and improve the temporal stability of the resist composition, thereby suppressing the precipitation of particles after storage. For example, Patent Document 1 and Patent Document 2 disclose a method of filtering a resin solution for a resist to suppress the increase of particles in the resist resin solution. In addition, Patent Document 3 proposes a method of manufacturing a resist composition in which the amount of fine particles in the resist composition is reduced by passing the resist composition through a filter in a circulating filtration method. However, in the case of forming an ultra-fine pattern with a line width of 50 nm or less, the storage stability is not sufficiently improved even if the method described above is used.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-282080

[Patent Document 2] Japanese Patent Laid-Open No. 2006-83214

[Patent Document 3] Japanese Patent Laid-Open No. 2002-62667

The object of the present invention is to provide a photosensitive material that can form defect-free ultra-fine patterns (for example, a line width of 50 nm or less), and has a very small amount of particles shortly after manufacture, excellent stability over time, and suppressed precipitation of stored particles. A method for producing a chemical radiation-sensitive or radiation-sensitive resin composition, and a photosensitive radiation-sensitive or radiation-sensitive resin composition produced by the manufacturing method.

One aspect of the present invention is as follows.

[1] A method for producing a sensitizing ray-sensitive or radiation-sensitive resin composition, which includes a filtering step of filtering the sensitizing ray-sensitive or radiation-sensitive resin composition through a filter, and the filtering step causes the The sensitizing radiation-sensitive or radiation-sensitive resin composition is passed through the first filter having a pore diameter of 10 nm or less five times or more.

[2] The manufacturing method according to [1], wherein the filtering step is to further introduce the photosensitive ray-sensitive or radiation-sensitive resin composition that has passed through the first filter into the same first filter , So as to block the circulating filtration steps in the system.

[3] The production method according to [1] or [2], wherein the filtering step allows the photosensitive ray-sensitive or radiation-sensitive resin composition to further pass through a second filter different from the first filter. Device.

[4] The manufacturing method according to any one of [1] to [3], wherein the actinic radiation-sensitive or radiation-sensitive resin composition is passed through the first filter 10 times or more.

[5] The production method according to any one of [1] to [4], wherein the solid content concentration of the actinic radiation-sensitive or radiation-sensitive resin composition is 7 mass% or less.

[6] The production method according to any one of [1] to [5], wherein the material of the first filter is polyolefin resin.

[7] The production method as described in any one of [3] to [6], wherein the material of the second filter is polyamide resin.

[8] The manufacturing method according to any one of [3] to [7], wherein the pore size of the second filter is greater than 10 nm.

[9] The production method according to any one of [1] to [8], wherein the pore diameter of the first filter is 5 nm or less.

[10] The manufacturing method according to any one of [1] to [9], which includes passing the resin solution through the filter 1 before the filtering step of filtering the photosensitive radiation or radiation sensitive resin composition. The filtering step of filtering is performed more than once, and the resin solution contains the resin and the solvent as the constituent components of the sensitizing ray-sensitive or radiation-sensitive resin composition, and does not substantially contain an acid generator.

[11] The production method according to [10], wherein the step of filtering the resin solution is to further introduce the resin solution that has passed the filter to the same filter to circulate in a closed system. step.

[12] The production method according to any one of [1] to [11], wherein before the filtering step of filtering the sensitizing radiation or radiation-sensitive resin composition, filtering is included as the sensitizing radiation A step of filtering the solvent of the constituent components of the sexual or radiation-sensitive resin composition.

[13] The production method according to any one of [1] to [12], wherein the actinic radiation-sensitive or radiation-sensitive resin composition contains a resin, an acid generator, and a solvent.

[14] The production method according to any one of [1] to [12], wherein the actinic radiation-sensitive or radiation-sensitive resin composition contains a resin and a solvent, and the resin has It is decomposed by radiation to produce acid in the side chain The structural part.

[15] A sensitizing radiation-sensitive or radiation-sensitive resin composition produced by the production method described in any one of [1] to [14].

According to the present invention, it is possible to produce a sensitized ray-sensitive or radiation-sensitive resin composition that has a very small amount of particles shortly after production, excellent stability over time, and suppressed precipitation of stored particles. Therefore, it is possible to provide a defect-free resin composition. Ultra-fine patterns.

1: slot

2: mercury

3: Flowmeter

4: Treatment liquid filling container

5, 6, 7, 9, 10: flow path

8: Filling port

100: String with the first filter

100': pipe string with the 1st filter

200: Pipe string with second filter

200': pipe string with 2'filter

300: The pipe string with the third filter

300': pipe string with 3'filter

Fig. 1 is a diagram schematically showing an aspect of an apparatus preferably used in the manufacturing method of the present invention.

Fig. 2 is a diagram schematically showing another aspect of an apparatus preferably used in the manufacturing method of the present invention.

Fig. 3 is a diagram schematically showing another aspect of an apparatus preferably used in the manufacturing method of the present invention.

Fig. 4 is a diagram schematically showing another aspect of an apparatus preferably used in the manufacturing method of the present invention.

Hereinafter, the mode for implementing the present invention will be described in detail.

In addition, in the expressions of groups (atomic groups) in this specification, expressions that do not describe substituted and unsubstituted include groups (atomic groups) without substituents, and also include groups (atomic groups) having substituents . For example, the so-called "alkyl" not only includes an unsubstituted alkyl group (unsubstituted alkyl), but also includes Substituted alkyl (substituted alkyl).

In the present invention, "actinic rays" or "radiation rays" refer to, for example, the bright line spectrum of mercury lamps, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV (Extreme Ultraviolet) light), X-rays, electron beams, etc. . In addition, the term "light" in the present invention refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this manual refers not only to exposure using mercury lamps, excimer lasers, such as extreme ultraviolet, X-rays, EUV light, etc., but also to drawing using particle beams such as electron beams and ion beams. Also included in the exposure.

The present invention will be described in detail below.

The method for producing the sensitizing radiation or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "manufacturing method of the present invention") uses a first filter with a pore diameter of 10 nm or less to treat the sensitizing radiation or radiation sensitive resin composition. The first feature is that the resin composition is filtered 5 times or more.

The sensitizing ray-sensitive or radiation-sensitive resin composition produced (processed) in the manufacturing method of the present invention will be described in detail later. In one aspect of the present invention, the sensitizing ray-sensitive or radiation-sensitive resin composition is preferred The substance contains at least a resin, an acid generator, and a solvent. In other forms, it is preferable to contain at least an acid-decomposable resin and a solvent having a structural site that decomposes by irradiation with actinic rays or radiation to generate acid in the side chain.

The filtering step of the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention may be a one-time liquid pass or a circulation method. The one-time liquid pass is a sensitized ray or radiation-sensitive resin composition through the Multiple first filters The system connected in series once, the circulation method is to further introduce the photosensitive ray-sensitive or radiation-sensitive resin composition that has passed through the first filter to the same filter (first filter) to circulate in the closed system.

In the production method of the present invention, the number of times of filtration of the first filter having a pore diameter of 10 nm or less is at least 5 times, preferably 10 times or more, and more preferably 15 times or more. When the filtering operation is performed in a cyclic manner, for example, when there is one first filter in the locking system, the number of cycles of the photosensitive radiation or radiation sensitive resin composition is at least 5 times, preferably 10 times Above, more preferably 15 times or more.

In the manufacturing method of the present invention, the pore size of the first filter is 10 nm or less, preferably 5 nm or less, and more preferably 3 nm or less. The lower limit of the pore diameter is not particularly limited, and it may be, for example, 1 nm or more. Here, the so-called "hole diameter" refers to the manufacturer's nominal diameter value or a value based on it.

The material of the filter used in the manufacturing method of the present invention is not particularly limited. For example, polyolefin resin (polyethylene, polypropylene, etc.), polyamide resin (nylon 6, nylon 66, nylon 46, etc.), containing Fluorine resin (Polytetrafluoroethylene (PTFE), etc.).

In the filtering step in the manufacturing method of the present invention, the sensitizing radiation-sensitive or radiation-sensitive resin composition may be further filtered through a second filter different from the first filter. In one aspect of the present invention, it is preferable that the sensitizing radiation-sensitive or radiation-sensitive resin composition is circulated in a closed system including a first filter and a second filter connected in series. Here, the second filter different from the first filter may be, for example, a filter with a different material from the first filter. It may be a filter with a pore size different from that of the first filter.

When the second filter is a filter with a different material from the first filter, the first filter and the second filter are preferably, for example, a polyolefin resin filter and the second filter Polyamide resin filter. Filters made of polyolefin resin generally remove impurities by their pore size. In filters made of polyamide resin, the adsorption of the amide part of the resin also helps to remove impurities. By combining filters with different characteristics, impurities can be removed more efficiently.

When the second filter is a filter with a different pore size from the first filter, the pore size of the second filter is preferably greater than 10 nm, more preferably 15 nm or greater, and still more preferably 20 nm or greater. The upper limit of the pore diameter is not particularly limited, and it may be, for example, 50 nm or less.

In addition, in the filtering step in the manufacturing method of the present invention, a third filter different from the first filter and the second filter may be used to filter the sensitized radiation or radiation sensitive resin composition. Here, the third filter may be, for example, a filter having a different material from the first filter and the second filter, or a filter having a different pore size from the first filter and the second filter.

When the third filter is a filter with a different pore diameter from the first filter and the second filter, the pore diameter of the third filter is preferably smaller than the pore diameter of the first filter. For example, the pore size of the third filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The lower limit of the pore diameter is not particularly limited, and it may be, for example, 1 nm or more. The material of the third filter may be the same as the material of the first filter, for example.

In one aspect of the present invention, it is preferable that the sensitizing radiation-sensitive or radiation-sensitive resin composition is circulated in a closed system including a first filter, a second filter, and a third filter in a circulating filtering step.

In the manufacturing method of the present invention, when two or more types of filters with different pore diameters are used, it is preferable to connect two or more types of filters as if the filtration step using a filter with a large pore diameter is performed upstream of the flow path.

In other aspects, the manufacturing method of the present invention may further include pre-step 1 and/or pre-step 2 described below as the pre-step of the filtering step of the sensitized radiation or radiation-sensitive resin composition.

<Including the previous step 1>

The production method of the present invention may also include a step of filtering the solvent as a constituent of the sensitizing radiation or radiation sensitive resin composition through a filter (previous step 1). The solvent filtered here contains only the solvent which is the constituent component of the sensitizing radiation-sensitive or radiation-sensitive resin composition, and does not substantially contain the resin or acid generator as other constituent components. Here, the term "substantially not containing other compounds such as resins or acid generators" means that the content of other compounds other than the solvent is preferably 0 mol%, but it is not excluded from being contained in a small amount within a range that does not impair the effects of the present invention. situation.

The filter used in the previous step 1, for example, is preferably a filter with a pore size of 1nm~50nm, more preferably a filter with 1nm~20nm, further preferably a filter with 1nm~10nm, particularly preferably a filter with 1nm~5nm . The material of the filter is not particularly limited. For example, a filter of the same material as the first filter can be used.

The form of the filtration step in the previous step 1 may be a one-time liquid pass method or a circulation method, and the number of times of filtration may be one time or two or more times.

Add other compounds as constituent components of the sensitizing radiation or radiation-sensitive resin composition to the solvent after the treatment in the previous step 1, and stir to obtain the sensitizing radiation or radiation-sensitive resin composition, and the obtained It is used for the filtering step of the sensitized radiation or radiation sensitive resin composition.

<Including the previous step 2>

The production method of the present invention may also include the step of filtering a resin solution containing resin and solvent as constituent components of a sensitizing radiation-sensitive or radiation-sensitive resin composition through a filter once or more, and substantially The above does not contain acid generators.

Here, the term "substantially not containing an acid generator" means that the content of the acid generator in the resin solution is preferably 0 mol%, but it does not exclude the case where a small amount is contained within a range that does not impair the effects of the present invention.

In addition, the resin here may be, for example, an acid-decomposable resin described later, a hydrophobic resin, or a resin containing both.

Regarding the filter used in the previous step 2 (hereinafter referred to as the "first' filter"), when the previous step 2 does not include the filtering step using the second' filter described below, the first' filter The pore diameter of the device is preferably 20 nm or less, more preferably 10 nm or less. When the previous step 2 further includes a filtration step using a second' filter, the pore size of the first' filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The lower limit of the pore size is not particularly limited, for example only It should be 1nm or more. The material of the filter is not particularly limited, and for example, a filter having the same material as that of the first filter can be used.

In one aspect of the present invention, the first step 2 may further allow the resin solution to pass through a second' filter different from the first' filter for filtration. Here, the second' filter that is different from the first' filter may be, for example, a filter with a different material from the first' filter, or a filter with a different pore size from the first' filter.

When the second' filter is a filter with a different material from the first' filter, the first' filter and the second' filter are preferably, for example, the first' filter is a filter made of polyolefin resin, The 2nd' filter is a polyamide resin filter.

When the second' filter is a filter with a different pore size from the first' filter, the pore size of the second' filter is preferably greater than 10 nm, more preferably 15 nm or greater, and still more preferably 20 nm or greater. The upper limit of the pore diameter is not particularly limited, and it may be, for example, 50 nm or less.

In addition, in the previous step 2, a third' filter different from the first' filter and the second' filter can be used to filter the resin solution. Here, the 3'filter may be, for example, a filter with a different material from the first' filter and the second' filter, or a filter with a different pore size from the first' filter and the second' filter.

When the 3'filter is a filter with a pore size different from that of the 1'filter and the 2'filter, the pore size of the 3'filter is preferably smaller than the pore size of the 1'filter. For example, the pore size of the 3'filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The lower limit of the pore diameter is not particularly limited, and it may be, for example, 1 nm or more. The material of the 3'filter may be similar to the material of the 1'filter, for example. with.

The form of the filtration step in the previous step 2 may be a one-time liquid pass method or a circulation method. The number of times of filtration is preferably one or more filtration with at least the first' filter, more preferably five or more times, and still more preferably ten or more times.

In one aspect of the present invention, the first step 2 is preferably a cyclic filtration step in which the resin solution is circulated in a closed system including a first' filter and a second' filter. In other forms, the resin solution is preferably included in the The cyclic filtration step in the closed system of the first' filter, the second' filter and the third' filter.

In the previous step 2, when two or more types of filters with different pore diameters are used, it is preferable to connect two or more types of filters as if the filtration step using a filter with a large pore diameter is performed upstream of the flow path.

Add other compounds as constituent components of the sensitized radiation or radiation-sensitive resin composition to the resin solution after the treatment in the previous step 2, and stir to obtain the sensitized radiation or radiation-sensitive resin composition. It is used for the filtering step of the sensitized radiation or radiation sensitive resin composition.

<Including the case of the previous step 1 and the previous step 2>

When the manufacturing method of the present invention further includes both the previous step 1 and the previous step 2 as the previous step of the filtering step of the sensitized radiation or radiation-sensitive resin composition, it is preferably immediately after the previous step 1. Proceed to step 2.

<Acceptable radiation or radiation sensitive resin composition>

Hereinafter, the photosensitive ray-sensitive or radiation-sensitive resin composition processed in the manufacturing method of the present invention will be described.

As the sensitizing ray-sensitive or radiation-sensitive resin composition, a known positive photoresist suitable for g-rays and i-rays can be suitably used, specifically so-called naphthoquinone diazide (naphthoquinone diazide) Photoresist that produces carboxylic acid by light reaction. More specifically, you can use "Resist for CMC Publishing Supervision: New Development of Photoresist Material Development: Resist introduced in "Chapter 4 Existing Photoresist" by Matsumoto Ueda" and "Resist for Semiconductor Integrated Circuits" Diazonaphthoquinone (DNQ)-novolac resin-based positive photoresist described in "Chapter 4 G-ray/i-ray Resist Materials" of the Material Handbook of Realize Co., Ltd. "Etc., but not limited to these.

In addition, as an actinic ray-sensitive or radiation-sensitive resin composition, a compound containing a resin and an acid generated by irradiation with actinic rays or radiation (hereinafter also referred to as "acid generator" or "compound (B )”) sensitized radiation or radiation-sensitive resin composition, the resin is increased in polarity by the action of acid, solubility in alkaline developer is increased, and in a developer containing organic solvent Resin with reduced solubility.

The sensitizing radiation or radiation-sensitive resin composition is preferably the above-mentioned sensitizing radiation or radiation-sensitive resin composition. The sensitizing radiation or radiation sensitive resin composition is typically a chemically amplified resist composition.

Hereinafter, each component of the sensitizing radiation-sensitive or radiation-sensitive resin composition (hereinafter also simply referred to as "the composition of the present invention") will be described in detail.

[1] Resins with increased polarity due to the action of acid, increased solubility in alkaline developers, and decreased solubility in developers containing organic solvents

As a resin whose polarity increases due to the action of an acid, its solubility in an alkaline developer is increased, and its solubility in a developer containing an organic solvent is reduced, for example, it may be exemplified in the main chain or side chain of the resin, or main Resins (hereinafter also referred to as “acid-decomposable resins” or “resins” that have groups (hereinafter also referred to as “acid-decomposable groups”) that are decomposed by acid to generate polar groups in both chain and side chains (A)”).

The acid-decomposable group preferably has a structure protected by a group in which a polar group is decomposed and released by the action of an acid. Preferable polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

The group which is preferable as an acid-decomposable group is the group which substituted the hydrogen atom of these groups with the group which detach|eliminates by an acid.

Examples of groups detached by acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group (monocyclic or polycyclic), 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 and R ₀₂ each independently represent a hydrogen atom, an alkyl group (monocyclic or polycyclic), a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, and the like. More preferably, it is a tertiary alkyl ester group. In addition, when the pattern forming method of the present invention is performed by exposure using KrF light or EUV light, or electron beam irradiation, it is also preferable to use an acid-decomposable group that protects a phenolic hydroxyl group by an acid leaving group.

The resin (A) preferably contains a repeating unit having an acid-decomposable group.

Examples of the repeating unit include the following.

In general formula (aI) and general formula (aI')

Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a ring structure. In addition, the ring structure may contain heteroatoms such as oxygen atoms in the ring.

The divalent linking group of T includes an alkylene group, -COO-Rt- group, -O-Rt- group, and phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

From the viewpoint of insolubilization of the resist in the organic solvent-based developer, T in the general formula (aI) is preferably a single bond or a -COO-Rt- group, and more preferably a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ -group, -(CH ₂ ) ₂ -group, -(CH ₂ ) ₃ -group.

T in the general formula (aI') is preferably a single bond.

The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of Xa ₁ is preferably an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group.

Xa _{1 is} preferably a hydrogen atom or a methyl group.

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.

The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Polycyclic cycloalkyl.

The ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ are preferably monocyclic cycloalkane rings such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, and tetracyclic ring. Polycyclic cycloalkyl groups such as dodecane ring and adamantane ring. Particularly preferred is a monocyclic cycloalkane ring having 5 or 6 carbon atoms.

Rx ₁ , Rx ₂ and Rx _{3 are} preferably each independently an alkyl group, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Each of the groups may have a substituent. Examples of the substituent include an alkyl group (carbon number 1 to 4), cycloalkyl group (carbon number 3 to 8), halogen atom, alkoxy group (carbon number 1 to 4). ), carboxyl group, alkoxycarbonyl group (carbon number 2-6), etc., preferably carbon number 8 or less. Among them, from the viewpoint of further improving the dissolution contrast in a developer containing an organic solvent before and after acid decomposition, it is more preferred that it does not have a heteroatomic substituent such as an oxygen atom, a nitrogen atom, or a sulfur atom. Hydroxy-substituted alkyl groups, etc.) are more preferably groups containing only hydrogen atoms and carbon atoms, and particularly preferably linear or branched alkyl groups and cycloalkyl groups.

Specific examples of repeating units having acid-decomposable groups are given, but not limited For that.

In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Z represents a substituent, and when there are multiple, multiple Z may be the same or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of substituents that each group such as Rx ₁ to Rx ₃ may have.

[化3]

[化5]

下述具體例中，Xa表示氫原子、烷基、氰基或鹵素原子。 [化7]

In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

[化8]

[化9]

[化10]

[化11]

In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

[化12]

The repeating unit having an acid-decomposable group may be one type, or two or more types may be used in combination.

Relative to all the repeating units of the resin (A), the content of the acid-decomposable group-containing repeating units contained in the resin (A) (the total when there are multiple acid-decomposable groups) It is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more.

The resin (A) may also contain a repeating unit having a lactone structure or a sultone structure.

The following shows the weight of a group containing a lactone structure or a sultone structure Although the specific example of the multiple unit, this invention is not limited to this.

[化14]

[化15]

Two or more repeating units having a lactone structure or a sultone structure can also be used in combination.

When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferable relative to all the repeating units in the resin (A) It is 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and still more preferably 10 mol% to 50 mol%.

In addition, the resin (A) may contain a repeating unit having a cyclic carbonate structure. Specific examples are listed below, but the present invention is not limited to these.

In addition, R _A ¹ in the following specific examples represents a hydrogen atom or an alkyl group (preferably a methyl group).

The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group.

Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these.

[化17]

The resin (A) may contain a repeating unit having an acid group.

The resin (A) may not contain the repeating unit having an acid group. When it does, the content of the repeating unit having an acid group relative to all the repeating units in the resin (A) is preferably 25 mol% or less, more preferably 20mol% or less. When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.

Although the specific example of the repeating unit which has an acid group is shown below, this invention is not limited to this.

In specific examples, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

[化19]

The resin (A) may further contain a repeating unit that has an alicyclic hydrocarbon structure and/or an aromatic ring structure that does not contain a polar group (for example, the acid group, a hydroxyl group, and a cyano group) and does not show acid decomposability.

Specific examples of repeating units having an alicyclic hydrocarbon structure not containing a polar group and showing no acid decomposability are listed below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

[化21]

When the composition of the present invention is used for ArF exposure, from the viewpoint of transparency to ArF light, it is preferable that the resin (A) used in the composition of the present invention has substantially no aromatic ring (specifically, ，Repeating units with aromatic groups in the resin The ratio of is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, it does not have an aromatic group), and it is preferable that the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The form of the resin (A) in the present invention may be any form of random, block, comb, and star. The resin (A) can be synthesized by, for example, radical polymerization, cationic polymerization, or anionic polymerization of unsaturated monomers corresponding to each structure. In addition, after polymerizing unsaturated monomers corresponding to the precursors of each structure, the target resin can be obtained by performing a polymer reaction.

When the composition of the present invention contains a hydrophobic resin (resin (D)) described later, from the viewpoint of compatibility with the resin (D), the resin (A) preferably does not contain fluorine atoms and silicon atoms .

The resin (A) used in the composition of the present invention preferably has all repeating units composed of (meth)acrylate-based repeating units. In this case, any of the following resins can be used: resins in which all repeating units are methacrylate-based repeating units, resins in which all repeating units are acrylate-based repeating units, and all repeating units are derived from methacrylate-based repeating units The resin of the unit and the acrylate-based repeating unit preferably has an acrylate-based repeating unit of 50 mol% or less of all the repeating units.

When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high-energy light (EUV, etc.) with a wavelength of 50 nm or less, the resin (A) may contain a repeating unit having an aromatic ring. The repeating unit having an aromatic ring is not particularly limited, and it has been exemplified in the description of each repeating unit. Examples include styrene units, hydroxystyrene units, phenyl (meth)acrylate units, (Meth) hydroxyphenyl acrylate unit and the like. More specifically, the resin (A) includes: a resin having a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and a resin containing the aromatic ring-containing repeating unit and (methyl) Resins etc. of repeating units in which the carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group. Furthermore, especially during EUV exposure, high sensitivity is usually required, and therefore it is preferable that the resin (A) contains a repeating unit containing a protective group that is prone to acid decomposition. Specific examples of such a repeating unit include: -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) or -C(R ₀₁ ) in the structure described as the group detached by acid ) (R ₀₂ ) (OR ₃₉ ) (usually referred to as the structure of the acetal type protecting group).

The resin (A) of the present invention can be synthesized and purified according to common methods (for example, free radical polymerization). As the synthesis method and purification method, for example, please refer to the description in paragraphs 0201 to 0202 of JP 2008-292975 A, etc.

The weight average molecular weight of the resin (A) in the present invention is 7,000 or more, preferably 7,000 to 200,000, more preferably 7,000 or more in terms of polystyrene conversion value obtained by the Gel Permeation Chromatography (GPC) method 7,000~50,000, more preferably 7,000~40,000, particularly preferably 7,000~30,000. If the weight average molecular weight is less than 7000, the solubility in the organic-based developer becomes too high, and there is a possibility that a precise pattern cannot be formed.

The degree of dispersion (molecular weight distribution, Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.

In the chemically amplified resist composition of the present invention, the blending rate of the resin (A) in the overall composition is preferably 30% to 99% by mass of the total solid content, more preferably 60% to 95% by mass quality%.

In addition, in the present invention, one kind of resin (A) may be used, or plural kinds may be used in combination.

Specific examples of the resin (A) are listed below (the composition ratio of the repeating unit is molar ratio), but the present invention is not limited to these. In addition, the following also exemplifies the aspect of the case where the structure corresponding to the acid generator (B) described later is supported on the resin (A).

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The resins exemplified below are examples of resins that can be preferably used particularly when performing EUV exposure or electron beam exposure.

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[2] Compounds that produce acid by irradiation of actinic rays or radiation

The composition of the present invention may generally contain a compound that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (B)" or "acid generator"). The acid generator is preferably a compound that generates an organic acid by irradiation with actinic rays or radiation.

As the acid generator, a photoinitiator for photocation polymerization, a photoinitiator for photoradical polymerization, a photodecolorizer for pigments, a photochromic agent, or a microresist, etc. can be appropriately selected. Known compounds that generate acids by irradiation with actinic rays or radiation, and mixtures of these are used.

For example, a diazonium salt, a phosphonium salt, a phosphonium salt, an iodonium salt, an imine sulfonate, an oxime sulfonate, diazo disulfonate, disulfonate, and o-nitrobenzyl sulfonate are mentioned.

The following are particularly good examples of acid generators.

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The acid generator can be synthesized by a known method, for example, according to Japanese Patent Laid-Open No. 2007-161707, Japanese Patent Laid-Open No. 2010-100595, <0200>~<0210>, and International Publication No. 2011/093280 <0051>~<0058>, International Publication No. 2008/153110 <0382>~<0385>, Japanese Patent Laid-Open No. 2007-161707, and the like.

The acid generator can be used alone or in combination of two or more.

Based on the total solid content of the composition of the present invention, the content of the compound that generates acid by irradiation with actinic rays or radiation is preferably 0.1% to 30% by mass, more preferably 0.5% by mass % To 25% by mass, more preferably 3% to 20% by mass, and particularly preferably 3% to 15% by mass.

Furthermore, depending on the sensitizing radiation-sensitive or radiation-sensitive resin composition, there is also an aspect (B') in which a structure corresponding to the acid generator is supported on the resin (A). That is, the acid-decomposable resin (A) may be a resin having a structural site that decomposes by irradiation with actinic rays or radiation to generate an acid in a side chain. Specific examples of this aspect include the structure described in Japanese Patent Laid-Open No. 2011-248019 (especially the structure described in paragraph 0164 to paragraph 0191, and the resin described in the embodiment of paragraph 0555 Contained structure), the repeating unit (R) described in paragraph 0023 to paragraph 0210 of JP 2013-80002 A, etc., these contents are incorporated into the specification of this application. In addition, even if the structure corresponding to the acid generator is supported on the resin (A), the photosensitive ray-sensitive or radiation-sensitive resin composition may additionally contain the resin (A) that is not supported on the resin (A). ) On the acid generator.

As the aspect (B'), the repeating unit described below can be exemplified, but it is not limited to this.

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[3] Solvent

The composition of the present invention usually contains a solvent.

Examples of solvents that can be used when preparing the composition of the present invention include: alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkylene alkoxypropionate Base ester, cyclic lactone (preferably carbon number 4-10), monoketone compound (preferably carbon number 4-10) that may contain a ring, alkylene carbonate, alkyl alkoxy acetate, Organic solvents such as alkyl pyruvate.

Specific examples of these solvents include the solvents described in <0441> to <0455> in the specification of U.S. Patent Application Publication No. 2008/0187860.

In the present invention, multiple organic solvents can also be mixed and used.

For example, it is also possible to mix a solvent containing a hydroxyl group and a solvent without a hydroxyl group in the structure. The combined solvent is used as an organic solvent. The exemplified compounds can be appropriately selected as a solvent containing a hydroxyl group or a solvent not containing a hydroxyl group. The solvent containing a hydroxyl group is preferably alkylene glycol monoalkyl ether, alkyl lactate, etc., more preferably propylene glycol monomethyl ether ( Propyleneglycol monomethylether, PGME; alias 1-methoxy-2-propanol), ethyl lactate. In addition, the solvent that does not contain a hydroxyl group is preferably alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound that may contain a ring, cyclic lactone, alkyl acetate, etc. Among them, propylene glycol monomethylether acetate (PGMEA; alias 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone are particularly preferred , Γ-butyrolactone, cyclohexanone, butyl acetate, most preferably propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone.

In addition, of course, organic solvents that do not contain a hydroxyl group in the structure may be used in combination with each other. Examples of the combination include PGMEA and cyclohexanone, PGMEA and cyclopentanone, PGMEA and γ-butyrolactone, PGMEA and 2-heptanone, and the like.

For example, when two solvents are used, the mixing ratio (mass) is 1/99~99/1, preferably 10/90~90/10, more preferably 20/80~60/40.

The solvent preferably contains propylene glycol monomethyl ether acetate, more preferably a propylene glycol monomethyl ether acetate single solvent, or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

Furthermore, if an appropriate amount of a solvent with a relatively high boiling point, such as γ-butyrolactone, is used, the performance of the hydrophobic resin (D) described later is more biased toward the surface, and it is expected that the performance against liquid immersion exposure will be improved.

Furthermore, three or more kinds of solvents can also be used. In this way, delicate resist shape adjustment, viscosity adjustment, etc. may also be performed. As a combination can be listed: PGMEA. PGME. γ-Butyrolactone, PGMEA. PGME. Cyclohexanone, PGMEA. PGME. 2-Heptanone, PGMEA. Cyclohexanone. γ-Butyrolactone, PGMEA. γ-Butyrolactone. 2-Heptanone and so on.

[4] Hydrophobic resin (D)

Especially when the composition of the present invention is applied to liquid immersion exposure, it may also contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)"). Furthermore, the hydrophobic resin (D) is preferably different from the resin (A).

As a result, the hydrophobic resin (D) tends to exist on the film surface, and when the immersion medium is water, the static/dynamic contact angle of the resist film surface to water can be increased, thereby improving the followability of the immersion liquid.

Furthermore, even when the composition is not applied to liquid immersion exposure, a hydrophobic resin may be contained for various purposes. For example, when applying the composition to EUV exposure, it is also preferable to use a hydrophobic resin in anticipation of suppression of outgassing, shape adjustment of a pattern, and the like.

The hydrophobic resin (D) is preferably designed in such a way that it tends to exist on the interface as described above, but unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and it may not help to change the polarity/non-polarity. The situation where the substance is uniformly mixed.

From the viewpoint of being biased in the surface layer of the film, the hydrophobic resin (D) preferably has any one or more of "fluorine atom", "silicon atom" and "CH ₃ partial structure contained in the side chain part of the resin" , More preferably two or more.

The weight average molecule of hydrophobic resin (D) converted from standard polystyrene The amount is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

In addition, one type of hydrophobic resin (D) may be used, or multiple types may be used in combination.

Relative to the total solid content in the composition of the present invention, the content of the hydrophobic resin (D) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1% by mass to 7% by mass.

The hydrophobic resin (D) is the same as the resin (A). Of course, there are few impurities such as metals, and the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3 % By mass, more preferably 0.05% by mass to 1% by mass. Thereby, it is possible to obtain a chemically amplified resist composition free from foreign matter in the liquid or changes in sensitivity over time. In addition, in terms of resolution, resist shape, sidewall of resist pattern, roughness, etc., molecular weight distribution (Mw/Mn, also referred to as dispersion) is preferably in the range of 1 to 5, more preferably The range of 1 to 3 is more preferably the range of 1 to 2.

The hydrophobic resin (D) can use various commercially available products, and can also be synthesized by a common method (for example, radical polymerization). For example, a general synthesis method can include: a total polymerization method in which the monomer species and initiator are dissolved in a solvent and heated to perform polymerization; the monomer species and the initiator are added dropwise in the heated solvent for 1 to 10 hours. The dropping polymerization method of the solution of the initiator, etc., is preferably the dropping polymerization method.

The reaction solvent, polymerization initiator, reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described in the resin (A). When the hydrophobic resin (D) is synthesized, the reaction concentration is preferred It is 30% by mass to 50% by mass. For more details, please refer to paragraph 0320 of JP 2008-292975 A ~0329 records near paragraph.

Specific examples of the hydrophobic resin (D) are shown below. In addition, the following table shows the molar ratio of the repeating unit of each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

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[Table 1]

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[Table 2]

[5] Basic compounds

The composition of the present invention preferably contains a basic compound.

(1) In one aspect, the composition of the present invention preferably contains a basic compound or ammonium salt compound whose alkalinity is reduced by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (N)") As a basic compound.

The compound (N) preferably has a basic functional group or an ammonium group, and is Compound (N-1) in which an acidic functional group is generated by irradiation of chemical rays or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group that generates an acidic functional group by irradiation with actinic rays or radiation, or a basic compound having an ammonium group and a group that generates acidic functional groups by irradiation with actinic rays or radiation. Irradiation produces an ammonium salt compound of an acidic functional group.

Specific examples of the compound (N) include, for example, the following. In addition to the compounds listed below, for example, the compounds (A-1) to (A-44) described in the specification of U.S. Patent Application Publication No. 2010/0233629 can also be preferably used in the present invention. Or the compounds (A-1) to (A-23) described in the specification of U.S. Patent Application Publication No. 2012/0156617 are referred to as compound (N).

These compounds can be synthesized in accordance with the synthesis example described in JP 2006-330098 A, etc.

The molecular weight of compound (N) is preferably 500 to 1,000.

The composition of the present invention may contain compound (N) or not contain compound (N). When compound (N) is contained, the content of compound (N) is preferably 0.1 based on the solid content of the composition. Mass% to 20% by mass, more preferably 0.1% to 10% by mass.

(2) In other forms, the composition of the present invention may contain a basic compound (N') different from the compound (N) in order to reduce the change in performance caused by the elapse of time from exposure to heating. Basic compound.

The basic compound (N') is preferably a compound having a structure represented by the following formula (A') to formula (E').

In general formula (A') and general formula (E'), RA ²⁰⁰ , RA ^201, and RA ²⁰² may be the same or different, and represent a hydrogen atom, an alkyl group (preferably with 1 to 20 carbon atoms), a cycloalkyl group ( Preferably, it is a carbon number 3-20) or an aryl group (carbon number 6-20), where RA ²⁰¹ and RA ²⁰² can be bonded to each other to form a ring. RA ²⁰³ , RA ²⁰⁴ , RA ²⁰⁵ and RA ²⁰⁶ may be the same or different, and represent an alkyl group (preferably carbon number 1-20).

The alkyl group may also have a substituent. As a substituted alkyl group, the Preferably, it is 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.

The alkyl group in these general formulas (A') and (E') is more preferably unsubstituted.

Preferred specific examples of the basic compound (N') include: guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., more preferably Specific examples include: compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and an alkane having a hydroxyl group and/or an ether bond Amine derivatives, aniline derivatives having hydroxyl groups and/or ether bonds, etc.

Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Compounds with a diazabicyclic structure include: 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8- Diazabicyclo[5.4.0]undec-7-ene and the like. Examples of compounds having an onium hydroxide structure include triaryl sulfonium hydroxide, benzyl methyl sulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include: triphenyl sulfonium hydroxide, Tris(tertiary butylphenyl) sulfonium hydroxide, bis(tertiary butylphenyl) iodonium hydroxide, benzylmethylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure becomes a carboxylate, such as acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. . Examples of compounds having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives with hydroxyl and/or ether bonds Examples of organisms include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives having a hydroxyl group and/or ether bond include N,N-bis(hydroxyethyl)aniline and the like.

As a preferable basic compound, the amine compound which has a phenoxy group, the ammonium salt compound which has a phenoxy group, the amine compound which has a sulfonate group, and the ammonium salt compound which has a sulfonate group are mentioned further. As this specific example, the compound (C1-1)-the compound (C3-3) exemplified in <0066> of the specification of U.S. Patent Application Publication No. 2007/0224539 can be cited, but it is not limited to these compounds.

(3) The composition of the present invention may contain a nitrogen-containing organic compound having a group detached by the action of an acid as one kind of basic compound in other forms. As an example of this compound, the specific example of a compound is shown below, for example.

The compound can be based on, for example, Japanese Patent Laid-Open No. 2009-199021 Synthesized by the method described in the newspaper.

In addition, as the basic compound (N'), a compound having an amine oxide structure may also be used. As specific examples of the compound, triethylamine pyridine N-oxide, tributylamine N-oxide, triethanolamine N-oxide, tris(methoxyethyl)amine N-oxide, tris(2 -(Methoxymethoxy)ethyl)amine N-oxide, propionic acid 2,2',2"-azatrane triethyl N-oxide, N-2-(2-methoxyethyl) (Oxy)methoxyethylmorpholine N-oxide, and amine oxide compounds exemplified in Japanese Patent Laid-Open No. 2008-102383 can be used.

The molecular weight of the basic compound (N') is preferably 250-2000, more preferably 400-1000. From the viewpoint of further reduction of Line Width Roughness (LWR) and uniformity of local pattern size, the molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and even more preferably More than 600.

These basic compounds (N') may be used in combination with the compound (N), or may be used alone or in combination of two or more kinds.

The chemically amplified resist composition of the present invention may contain a basic compound (N') or not contain a basic compound (N'). When it contains a basic compound (N'), a chemically amplified resist Based on the solid content of the agent composition, the usage amount of the basic compound (N′) is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass.

(4) The composition of the present invention may contain an onium salt represented by the following general formula (6A) or general formula (6B) as a basic compound in other forms. Due to the relationship with the acid strength of photoacid generators commonly used in resist compositions, the The onium salt controls the diffusion of the generated acid in the resist system.

In the general formula (6A), Ra represents an organic group. Among them, the fluorine atom is substituted with the carbon atom directly bonded to the carboxylic acid group in the formula, except for those.

X ⁺ represents an onium cation.

In the general formula (6B), Rb represents an organic group. Among them, those obtained by substituting a fluorine atom with a carbon atom directly bonded to the sulfonic acid group in the formula are excluded.

X ⁺ represents an onium cation.

The organic group represented by Ra and Rb preferably has a carbon atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula. However, in this case, in order to become a relatively weak acid compared with the acid generated from the photoacid generator, the fluorine atom is not substituted on the carbon atom directly bonded to the sulfonic acid group or the carboxylic acid group.

Examples of the organic groups represented by Ra and Rb include: alkyl groups having 1 to 20 carbons, cycloalkyl groups having 3 to 20 carbons, aryl groups having 6 to 30 carbons, and aryl groups having 7 to 30 carbons. An alkyl group or a heterocyclic group having 3 to 30 carbon atoms, etc. Part or all of the hydrogen atoms of these groups may be substituted.

Examples of substituents that the alkyl group, cycloalkyl group, aryl group, aralkyl group, and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

As the onium cation represented by X ⁺ in the general formula (6A) and the general formula (6B), a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, a diazonium cation, etc. are mentioned. Among them, a sulfonium cation is more preferred. .

As a cation, for example, an aryl cation having at least one aryl group is preferable, and a triaryl cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.

As an example of a cation and an iodo cation, the structure demonstrated in compound (B) can also be mentioned preferably.

The specific structure of the onium salt represented by general formula (6A) or general formula (6B) is shown below.

(5) The composition of the present invention may also contain other forms such as Japanese patent The compound contained in the formula (I) of Litkukai No. 2012-189977, the compound represented by the formula (I) of Japanese Patent Laid-Open No. 2013-6827, and the formula of Japanese Patent Laid-Open No. 2013-8020 The compound represented by the formula (I), the compound represented by the formula (I) in JP 2012-252124 A, etc. are generally compounds having both an onium salt structure and an acid anion structure in one molecule (hereinafter, Also known as betaine compounds) as basic compounds. Examples of the onium salt structure include a sulfonium salt structure, an iodonium salt structure, and an ammonium salt structure, and a sulfonium salt structure or an iodonium salt structure is preferable. In addition, as the acid anion structure, a sulfonate anion or a carboxylate anion is preferred. As an example of this compound, the following can be mentioned, for example.

[6] Surfactant

The composition of the present invention may further contain a surfactant. When the composition of the present invention contains a surfactant, it is more preferable to contain a fluorine-based surfactant and/or a silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, fluorine atom and silicon atom Both surfactants) either one, or two or more.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less, is used, a resist pattern with good sensitivity and resolution, good adhesion, and few development defects can be provided.

Examples of fluorine-based surfactants and/or silicon-based surfactants include those described in <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425, such as Fluorad FC430, Fluorad 431, Fluorad 4430 (manufactured by Sumitomo 3M (Stock)), Megafac series (manufactured by DIC (Stock)), Surflon )S-382, Surflon (Surflon) SC101, Surflon (Surflon) 102, Surflon (Surflon) 103, Surflon (Surflon) 104, Surflon (Surflon) 105, Surflon (Surflon) 106, Surflon KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical (Stock)), GF-300, GF-150 ( East Asia Synthetic Chemicals (manufactured by shares), Surflon S-393 (manufactured by Seimi Chemical (shares)), Eftop EF121, Eftop EF122A, Eftop (Eftop) EF122B, Eftop RF122C, Eftop EF125M, Eftop EF135M, Eftop EF351, Eftop EF352, Eftop ) EF801, Eftop EF802, Eftop EF601 (manufactured by Jemco (Stock)), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX -204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, 222D (manufactured by Neos (Stock)), etc. In addition, polysiloxane polymer KP-341 (Manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition, as the surfactant, in addition to the well-known surfactants shown above, the following surfactants can also be used. The surfactants can be obtained by a short-chain polymerization method (also called a short-chain polymer method). ) Or an oligomerization method (also called an oligomer method) derived from a fluoroaliphatic compound having a fluoroaliphatic group. The fluoroaliphatic compound can be synthesized by the method described in JP 2002-90991 A.

As the surfactant that meets the requirements, it can be listed: Megafac F178, Megafac F-470, Megafac F-473, Megafac F-475, Megafac ) F-476, Megafac F-472 (manufactured by Di Aisheng (Stock)), acrylate (or methacrylate) with C ₆ F ₁₃ group and (poly(oxyalkylene)) acrylate (Or methacrylate) copolymer, acrylate (or methacrylate) with C ₃ F ₇ group and (poly(oxyethylene)) acrylate (or methacrylate) and (poly( (Oxypropylene)) acrylate (or methacrylate) copolymers, etc.

In addition, in the present invention, other surfactants other than the fluorine-based surfactant and/or the silicon-based surfactant described in <0280> of the specification of US Patent Application Publication No. 2008/0248425 may also be used.

These surfactants can be used alone or in combination of several kinds.

When the composition of the present invention contains a surfactant, the amount of surfactant used is preferably 0.0001 relative to the total amount of the composition (except for the solvent) Mass% to 2% by mass, more preferably 0.0005% to 1% by mass.

On the other hand, by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the sensitizing radiation or radiation-sensitive resin composition (except for the solvent), the presence of surface bias of the hydrophobic resin is improved. Thereby, the surface of the resist film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.

[7] Other additives (G)

The composition of the present invention may also contain an onium carboxylate. Examples of such onium carboxylates include those described in US Patent Application Publication No. 2008/0187860 <0605> to <0606>.

When the composition of the present invention contains an onium carboxylate, its content relative to the total solid content of the composition is usually 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, and more Preferably, it is 1% by mass to 7% by mass.

In addition, the composition of the present invention may also contain a so-called acid proliferation agent as necessary. The acid multiplying agent is preferably used especially when performing the pattern forming method of the present invention by EUV exposure or electron beam irradiation. The specific example of the acid proliferation agent is not particularly limited, and for example, the following can be mentioned.

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The composition of the present invention may further contain dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and compounds that promote solubility in developer (for example, a compound having a molecular weight of A phenol compound of 1000 or less, alicyclic compound or aliphatic compound having a carboxyl group), etc.

From the viewpoint of enhancing the resolution, the composition of the present invention is preferably used with a film thickness of 30 nm to 250 nm, and more preferably used with a film thickness of 30 nm to 200 nm.

The solid content concentration of the composition of the present invention is usually 0.5% by mass to 10% by mass, preferably 1.0% by mass to 7.0% by mass, and more preferably 1.0% by mass to 5.0% by mass. quality%. By setting the solid content concentration in the above range, the resist solution can be uniformly coated on the substrate.

The solid content concentration refers to the weight percentage of the weight of other resist components other than the solvent relative to the total weight of the chemically amplified resist composition.

The composition of the present invention is filtered by a filter by the manufacturing method of the present invention, and then applied to a predetermined support (substrate) for use. In addition, before and after filter filtration of the sensitized radiation-sensitive or radiation-sensitive resin composition in the production method of the present invention, the composition may be subjected to degassing treatment or the like.

[Example]

The following examples illustrate the present invention in more detail, but the content of the present invention is not limited thereby.

<Synthesis of Resin (A)>

Synthesis Example 1: Synthesis of P-1

Under a nitrogen flow, 40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was added to a three-necked flask, and heated to 80°C (solvent 1). The monomers corresponding to the following repeating units were dissolved in a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether at a molar ratio of 30/10/60, respectively, A 22% by mass monomer solution (400 g) was prepared. Furthermore, in this monomer solution, 8 mol% of the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved with respect to the monomer. It took 6 hours to add the resulting solution dropwise to the solvent 1. After the dropwise addition, it was further reacted at 80°C for 2 hours. The reaction liquid was left to cool and then poured into hexane 3600ml/ethyl acetate 400ml, filtered and separated The deposited powder was dried to obtain 74 g of resin (P-1). The weight average molecular weight of the obtained resin (P-1) was 12,000, and the degree of dispersion (Mw/Mn) was 1.6.

The resin (P-2)~resin (P-10) were synthesized in the same manner as in Synthesis Example 1, except that the monomer corresponding to each repeating unit was used so as to become the required composition ratio (molar ratio). ) And hydrophobic resin (N-1)~hydrophobic resin (N-3).

<Preparation of resist>

The components shown in the following Table 4 were dissolved in the solvents shown in the table to prepare a sensitizing radiation-sensitive or radiation-sensitive resin composition Ar-1 with a total solid content concentration of 3.0% by mass. Radial resin composition Ar-13. The specific manufacturing method of each composition is as follows.

The abbreviations in Table 4 are as follows.

[Resin]

The composition ratio (molar ratio), weight average molecular weight Mw, and degree of dispersion Mw/Mn of the resin used in the examples are shown below. Here, the weight average molecular weight Mw (in terms of polystyrene), the number average molecular weight Mn (in terms of polystyrene), and the degree of dispersion Mw/Mn were calculated by GPC (solvent: Tetrahydrofuran (THF)) measurement. In addition, the composition ratio (molar ratio) was calculated by ¹ H-nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) measurement.

[化62]

[Acid Generator]

The structural formula of the acid generator is shown below.

[化63]

[Basic compound]

The structural formula of the basic compound is shown below.

[Hydrophobic resin]

The composition ratio (molar ratio), weight average molecular weight, and degree of dispersion of the hydrophobic resin used in the examples are shown below. Here, the weight average molecular weight Mw, the degree of dispersion Mw/Mn, and the composition ratio (molar ratio) are calculated in the same manner as the resin (A).

[Surfactant]

W-1: Megafac F176 (manufactured by DIC (Stock)) (fluorine-based)

W-2: Megafac R08 (manufactured by DIC (Stock)) (Fluorine-based and silicon-based)

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)

W-4: Polyfox PF-6320 (manufactured by OMNOVA) (fluorine-based)

[Solvent]

A1: Propylene glycol monomethyl ether acetate (PGMEA)

A2: γ-butyrolactone

A3: Cyclohexanone

B1: Propylene glycol monomethyl ether (PGME)

B2: Ethyl lactate

B3: 2-Heptanone

B4: propylene carbonate

<Manufacturing of sensitizing radiation or radiation sensitive resin composition>

[Example 1]

Assemble the following device as shown in Figure 1, that is, the flow path 5, the flow path 6, the flow path 7 are connected to the tank 1, the mercury 2 and the column 100 provided with the first filter, and then the flow path 7 is provided with a flow rate The meter 3 and the filling port 8 can fill the processing liquid filling container 4 with the resist composition after processing. By driving the mercury 2, the resist composition contained in the tank 1 circulates in the lock system.

In Example 1, a polyethylene filter with a pore size of 10 nm was installed on the pipe column 100 of the device as the first filter. The resist shown in Table 4 above The composition Ar-1 is accommodated in the tank 1, and the mercury 2 is driven to circulate the resist composition Ar-1 in the closed system of the flow of the tank 1→the mercury 2→the column 100. Set the number of cycles to 5 times. Here, the number of cycles is defined as [the cumulative amount of the resist composition flowing through the filter/the amount of the resist composition loaded in the tank].

[Example 2, Example 3, Example 9-Example 11, Example 17, Example 19, Example 21, Example 24, Example 25, Example 27, Example 29, Comparative Example 1-Comparison Example 4]

In Example 2, Example 3, Example 9-Example 11, Example 17, Example 19, Example 21, Example 24, Example 25, Example 27, Example 29, Comparative Example 1-Comparison In Example 4, the resist composition was processed in the same manner as in Example 1, except that the resist composition, the number of cycles, or the first filter was changed to the manufacturing conditions shown in Table 5 below.

[Example 4]

Assemble the following device as shown in Figure 2, that is, through the flow path 5, the flow path 6, the flow path 7, the flow path 9 connecting the tank 1, mercury 2, the column 100 provided with the first filter and the second filter provided The column 200 of the detector is further provided with a flow meter 3 and a filling port 8 on the flow path 7 so that the processed resist composition can be filled into the processing liquid filling container 4. By driving the mercury 2, the resist composition contained in the tank 1 circulates in the lock system.

In Example 4, a polyethylene filter with a pore size of 10 nm was set on the column 100 of the device as the first filter, and a nylon filter with a pore size of 20 nm was set on the column 200 as the second filter . The resist composition Ar-1 shown in Table 4 was placed in the tank 1, and the resist composition Ar-1 was placed in the tank by driving the mercury 2. 1→Mercury 2→Column 200→Circulation in the closed system of the flow of column 100. Set the number of cycles to 5 times.

[Example 5, Example 12, Example 13, Example 20, Example 26, Example 28]

In Example 5, Example 12, Example 13, Example 20, Example 26, and Example 28, except that the resist composition, the number of cycles, the first filter or the second filter were changed to the following table Except for the manufacturing conditions shown in 5, the resist composition was processed in the same manner as in Example 4.

[Example 6, Example 14]

In Example 6 and Example 14, as a pre-step of the treatment of the resist composition using the apparatus shown in FIG. 2, the solvent as the constituent component of the resist composition was subjected to the pre-step 1 shown below. . The subsequent treatment of the resist composition was the same as in Example 4 except that the resist composition, the number of cycles, the first filter or the second filter were changed to the manufacturing conditions shown in Table 5 below. The resist composition is processed in a way.

<Previous step 1>

The solvent described in Table 4 was filtered once with a polyethylene filter with a pore diameter of 3 nm.

[Example 7, Example 15]

In Example 7 and Example 15, as a pre-step of the treatment of the resist composition using the apparatus shown in FIG. 2, the acid decomposable resin and the hydrophobic resin as the constituent components of the resist composition The resin solution dissolved in a solvent is The previous step 2 shown below. The subsequent treatment of the resist composition was the same as in Example 4 except that the resist composition, the number of cycles, the first filter or the second filter were changed to the manufacturing conditions shown in Table 5 below. The resist composition is processed in a way.

<Previous step 2>

Assemble the following device as shown in Figure 4, that is, through the flow path 5, the flow path 6, the flow path 7, the flow path 9, the flow path 10 connecting the tank 1, the mercury 2, and the column 100' provided with the first filter , The column 200' with the second filter and the column 300 with the third filter are installed, and the flow path 7 is provided with a flow meter 3 and a filling port 8, so that the processed resin The solution is filled in the processing liquid filling container 4. By driving the mercury 2, the resin solution contained in the tank 1 circulates in the lock system.

In the previous step 2, a polyethylene filter with a pore size of 10 nm was set on the pipe column 100' of the device as the first' filter, and a nylon filter with a pore size of 20 nm was set on the pipe column 200' as the first' filter. A 2'filter, and a polyethylene filter with a pore size of 5 nm as the 3'filter is set on the column 300'. The resin solution in which the acid-decomposable resin and hydrophobic resin shown in Table 4 are dissolved in the solvent is contained in tank 1, and the resin solution is placed in tank 1 → mercury 2 → column 200' → tube by driving mercury 2 The flow of the column 100'→the tube string 300' circulates in the closed system. Set the number of cycles to 10 times.

[Example 22]

In Example 22, as a previous step, the same previous step 1 as in Example 6 and Example 14 was performed, and the resist composition obtained by adding other components described in Table 4 to the solvent after the treatment and stirring Use the device shown in Figure 3 to perform the following The described processing.

That is, as shown in FIG. 3, the following device is assembled, that is, the flow path 5, the flow path 6, the flow path 7, the flow path 9, the flow path 10, the connecting tank 1, the mercury 2, and the column 100 provided with the first filter. , The column 200 provided with the second filter and the column 300 provided with the third filter are provided with a flow meter 3 and a filling port 8 on the flow path 7, so that the treated resist composition Fill into the processing liquid filling container 4. By driving the mercury 2, the resist composition contained in the tank 1 circulates in the lock system.

In Example 22, a polyethylene filter with a pore size of 5 nm was set on the column 100 of the device as the first filter, and a nylon filter with a pore size of 20 nm was set on the column 200 as the second filter. , And a polyethylene filter with a pore diameter of 3 nm is installed on the column 300 as the third filter. The resist composition shown in Table 4 is contained in the tank 1, and the mercury 2 is driven to flow the resist composition in the tank 1 → mercury 2 → column 200 → column 100 → column 300 The inner loop of the locking system. Set the number of cycles to 10 times.

[Example 8, Example 16, Example 18, Example 23]

In Example 8, Example 16, Example 18, and Example 23, as a pre-step of the treatment of the resist composition using the apparatus shown in FIG. 3, the same pre-processing as in Example 6 and Example 14 was performed. Step 1, and then use the treated solvent to perform the same previous step 2 as in Example 7 and Example 15. The other components described in Table 4 were added to the processed resin solution and stirred to obtain a resist composition. As the subsequent treatment of the resist composition, the resist composition, the number of cycles, the first filter, the second filter, and the third filter are changed to the manufacturing conditions shown in Table 5 below. Otherwise, the resist composition was processed in the same manner as in Example 22.

<Evaluation method>

For each of the obtained resist compositions, the number of particles in the resist composition was measured twice shortly after production and after storage at 35°C for one month. The number of particles is determined by using a particle counter KS-41 manufactured by Lion Company (unit: pcs/ml). The evaluation results are shown in Table 5.

From the above results, it can be seen that the resist composition produced by the production method of the present invention has a very small amount of particles shortly after production, has excellent stability over time, and the precipitation of stored particles is suppressed.

1‧‧‧Slot

2‧‧‧ Mercury

3‧‧‧Flowmeter

4‧‧‧Processing liquid filling container

5, 6, 7‧‧‧Flow path

8‧‧‧Filling port

100‧‧‧Pipe string with the first filter

Claims (16)

A method for manufacturing a resin composition, the resin composition having sensitizing radiation or radiation sensitivity, and the manufacturing method of the resin composition includes filtering the sensitizing radiation or radiation sensitive resin composition through a filter In the filtering step, the sensitizing or radiation-sensitive resin composition passes through a first filter with a pore diameter of 10 nm or less, a second filter different from the first filter, and a pore diameter smaller than The first filter and the third filter are performed 5 times or more and 15 times or less. The method for producing a resin composition according to the first claim, wherein the filtering step is to pass the first filter, the second filter, and the third filter The sensitizing radiation-sensitive or radiation-sensitive resin composition is further introduced into the same first filter, the second filter, and the third filter to circulate in the cyclic filtering step in the closed system. The method for producing a resin composition according to the first item of the scope of patent application, wherein the photosensitive ray-sensitive or radiation-sensitive resin composition is passed through the first filter, the second filter, and the The third filter is more than 10 times and less than 15 times. The method for producing a resin composition according to the first item of the scope of patent application, wherein the solid content concentration of the sensitizing radiation-sensitive or radiation-sensitive resin composition is 7 mass% or less. The method for manufacturing a resin composition as described in any one of items 1 to 4 of the scope of patent application, wherein the material of the first filter is a polyolefin resin. The method for manufacturing a resin composition as described in any one of items 1 to 4 of the scope of the patent application, wherein the material of the second filter is polyamide resin. The method for manufacturing a resin composition as described in any one of items 1 to 4 of the scope of the patent application, wherein the material of the first filter is polyolefin resin, and the material of the second filter is polyamide Amine resin. The method for manufacturing a resin composition according to any one of items 1 to 4 of the scope of patent application, wherein the pore size of the second filter is greater than 10 nm. The method for producing a resin composition as described in any one of items 1 to 4 of the scope of patent application, wherein the pore size of the first filter is 5 nm or less. The method for producing a resin composition according to the seventh of the scope of patent application, wherein the pore size of the second filter is greater than 10 nm, and the pore size of the first filter is 5 nm or less. The method for manufacturing a resin composition as described in the first item of the scope of the patent application, wherein before the filtering step of filtering the sensitized ray-sensitive or radiation-sensitive resin composition, it includes passing the resin solution through a filter more than once. In the filtering step of filtering, the resin solution contains resin and solvent as constituent components of the sensitizing radiation-sensitive or radiation-sensitive resin composition, and does not substantially contain an acid generator. The method for manufacturing a resin composition as described in claim 11, wherein the step of filtering the resin solution is to further introduce the resin solution that has passed through the filter to the same filter, so as to be in the lock system Cyclic filtration step of the loop. The resin group described in item 1, item 11 or item 12 of the scope of patent application The manufacturing method of the finished product, wherein before the filtering step of filtering the photosensitive ray-sensitive or radiation-sensitive resin composition, it includes filtering the solvent as a constituent of the photosensitive ray-sensitive or radiation-sensitive resin composition step. The method for producing a resin composition according to the first item of the patent application, wherein the sensitizing radiation-sensitive or radiation-sensitive resin composition contains a resin, an acid generator, and a solvent. The method for producing a resin composition according to the first item of the scope of the patent application, wherein the actinic radiation-sensitive or radiation-sensitive resin composition contains a resin and a solvent, and the resin is provided with Decomposes to generate acid in the side chain. A resin composition which has sensitizing radiation properties or radiation sensitivity, and is manufactured by the method for manufacturing the resin composition as described in item 1, 11 or 12 of the scope of patent application.

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