JP6175401B2 - Pattern forming method, electronic device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a pattern forming method used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications, and an electronic device including the pattern forming method. The present invention relates to a manufacturing method and an electronic device. In particular, the present invention relates to an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, a pattern forming method suitable for exposure in an ArF immersion projection exposure apparatus, a method for manufacturing an electronic device, and an electronic device About.

Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption.
For example, Patent Document 1 proposes a double development technique using a positive developer and a negative developer as a method for stably forming a high-precision fine pattern. More specifically, by utilizing the fact that the polarity of the resin in the resist composition by exposure is high in regions where light intensity is high and low in regions where light intensity is low, a specific resist is used. By dissolving the high exposure area of the film in a developer containing water and dissolving the low exposure area in a developer containing an organic solvent, the intermediate exposure area remains undissolved and removed by development. A line and space pattern having a half pitch is formed.

JP 2008-292975 A

In recent years, higher functionality of various electronic devices has been demanded, and accordingly, further improvement in characteristics of resist patterns used for fine processing has been demanded. In particular, narrowing of the pattern width and pitch is required. Thus, when the pattern width and pitch are narrowed, the difference in exposure amount (optical contrast) between the exposed area and the unexposed area decreases, and the developer in the low exposure area, intermediate exposure area, and high exposure area is reduced. The difference in dissolution rate is reduced.
When the present inventor formed a pattern with a narrower pattern pitch using the method described in Patent Document 1, the decrease in film thickness (so-called film slippage) in the intermediate exposure region to be a pattern is severe, and the target pattern is It was found that it was difficult to obtain.

Further, the present inventor has found that when a line and space pattern having a narrower pitch is formed using the method described in Patent Document 1, a disconnection in which the pattern is interrupted may occur depending on conditions. .
Furthermore, in general, the formation of a hole pattern having an ultrafine hole diameter is less likely to have an optical contrast than a line and space pattern. For this reason, the method described in Patent Document 1 does not satisfy the recent required level, and further improvement is necessary.

In view of the above circumstances, an object of the present invention is to provide a pattern forming method that can be suitably applied to the formation of a fine line and space pattern and a hole pattern and in which film slippage is suppressed.
Another object of the present invention is to provide an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the manufacturing method.

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above-mentioned problems can be solved by incorporating a predetermined additive into a developer containing an organic solvent.
That is, it has been found that the above object can be achieved by the following configuration.

[1] A step (1) of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition containing at least a resin having a group that decomposes by the action of an acid to generate a polar group;
Exposing the film (2);
And developing the exposed film to form a pattern (3),
Step (3) is a step of performing any one of Step A with a developer containing water and Step B with a developer containing an organic solvent, and then performing the other step.
The pattern formation method in which the additive which forms at least 1 interaction of an ionic bond, a hydrogen bond, a chemical bond, and a dipole interaction with a polar group is contained in the developing solution containing an organic solvent.
[2] Step (3) is a step of carrying out step A and step B in this order,
The pattern forming method according to [1], wherein a region having a large exposure amount due to exposure in the film is dissolved in step A, and a region having a small exposure amount due to exposure in the film is dissolved in step B.
[3] The pattern forming method according to [1] or [2], wherein the additive includes at least one selected from the group consisting of an onium salt compound, a nitrogen-containing compound, and a phosphorus compound.
[4] The onium salt compound is represented by the onium salt represented by the formula (1-1) described later, the onium salt represented by the formula (1-2) described later, and the formula (5-1) described later. The pattern formation method according to [3], which is at least one selected from the group consisting of polymers having repeating units.
[5] The nitrogen-containing compound is at least one selected from the group consisting of a polymer having a repeating unit represented by the following formula (2) and a compound represented by the following formula (3). The pattern forming method according to [3] or [4].
[6] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [5].
[7] An electronic device manufactured by the method for manufacturing an electronic device according to [6].
[8] The pattern according to any one of [1] to [5], wherein the step (3) performs the step A and the step B in this order, and an additive is contained in a developer containing an organic solvent. Forming method.

ADVANTAGE OF THE INVENTION According to this invention, the pattern formation method which can be applied suitably for formation of a fine line and space pattern and a hole pattern, and the film | membrane slip was suppressed can be provided.
Moreover, according to this invention, the electronic device manufactured from the manufacturing method of the electronic device containing the said pattern formation method and the said manufacturing method can also be provided.

It is process drawing which shows the one aspect | mode of the method of a prior art (patent document 1), (A) shows sectional drawing of the pattern formed after developing with a positive developing solution, (B) is negative development Sectional drawing of the pattern formed after developing with a liquid is shown. It is sectional drawing after implementing one aspect | mode of the pattern formation method of this invention, and implements the process developed using the developing solution containing water, and is developed using the developing solution containing an additive and an organic solvent after that. It is sectional drawing of the pattern formed after implementing a process. It is a top view which shows the reticle used in the Example.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing 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).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is also included in the exposure.
In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

A feature of the present invention is that the step of developing with a developer containing water and the step of developing with a developer containing an organic solvent are carried out in random order, and the developer containing an organic solvent out of the two is subjected to acid The point which contains the additive which forms the polar group in resin generate | occur | produced by an effect | action and a predetermined interaction is mentioned. A developer containing an organic solvent contains a predetermined additive, and this additive interacts with the polar group of the resin. The features of the present invention will be described in detail below with reference to the drawings.
FIG. 1 is a cross-sectional view showing each step of an embodiment of the pattern forming method described in the prior art (Patent Document 1). FIG. 1 shows an embodiment in which development is performed with a developer containing water (particularly alkaline water) and then development is performed with a developer containing an organic solvent. First, as shown in FIG. 1 (A), in a developer containing water to dissolve the region R _P exposure amount is large, a pattern 12 having a thickness T1 on the substrate 10. Next, when developing the small region R _N of exposure with a developing solution containing an organic solvent, if the pattern pitch is short, as shown in FIG. 1 (B), the thickness T2 of the pattern 12 remaining is reduced significantly .
On the other hand, in the case of the present invention, first, when developing with a developer containing water (particularly alkaline water), a pattern similar to FIG. 1A is formed. Next, when a developer containing a predetermined additive and an organic solvent is used, the additive and the polar group contained in the resin existing on the surface of the pattern 12 form an interaction, and the organic solvent Solubility in is reduced. As a result, as shown in FIG. 2, a pattern 14 having a thickness T3 with a small difference from the thickness T1 is formed even after development with an organic solvent.
In the above, an embodiment in which development is performed with a developer containing water and then developed with a developer containing an organic solvent has been described. However, development is first performed with a developer containing an organic solvent, and then water is contained. The desired effect can be obtained even in the case of developing with a developer.

The pattern forming method of the present invention includes at least the following three steps.
(1) Step of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition containing at least a resin having a group that decomposes by the action of an acid to generate a polar group (2) Exposing the film Step (3) Step of developing the exposed film to form a pattern Hereinafter, each step will be described in detail.

[Step (1): Film formation step]
Step (1) is a step of forming a film (hereinafter also referred to as “resist film”) on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
First, the material used at this process is explained in full detail, and the procedure of the subsequent process (1) is explained in full detail.

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “composition” or “resist film forming composition”) used in the present invention will be described below.
The composition includes a resin (A) having a group that decomposes by the action of an acid to generate a polar group.
First, the resin (A) and other optional components will be described in detail.

[1] Resin (A) having a group that decomposes by the action of an acid to generate a polar group (hereinafter, also simply referred to as resin (A))
As the resin (A) having a group that decomposes by the action of an acid and generates a polar group, contained in the composition used in the present invention, the main chain or side chain of the resin, or the main chain and side chain Resin (hereinafter also referred to as “acid-decomposable group” or “resin (A)”) having a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group. Can be mentioned.
The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves under the action of an acid.
The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methylan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -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 and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The resin (A) preferably has a repeating unit having an acid-decomposable group.
Moreover, it is preferable that resin (A) has a repeating unit represented by the following general formula (AI) as a repeating unit which has an acid-decomposable group. The repeating unit represented by the general formula (AI) generates a carboxyl group as a polar group by the action of an acid.

In 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 represents an alkyl group or a cycloalkyl group.
Two of Rx _{1 to} Rx ₃ may be bonded to form a ring structure.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a divalent linking group in that the effect of the present invention is more excellent. When T is a divalent linking group, the mobility of the polar group generated by the action of an acid is improved, and the effect of the present invention is further improved because it easily interacts with an additive described later.
In addition, as a bivalent coupling group, -COO-Rt- group is preferable. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

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 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
Xa ₁ is preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. A group having 1 to 4 carbon atoms such as a t-butyl group is preferable.
Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group Are preferred.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.
Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon). Number 1-4), a carboxyl group, an alkoxycarbonyl group (carbon number 2-6) etc. are mentioned, and carbon number 8 or less is preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to the developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable (for example, More preferably, it is not an alkyl group substituted with a hydroxyl group, etc.), more preferably a group consisting of only a hydrogen atom and a carbon atom, and particularly preferably a linear or branched alkyl group or a cycloalkyl group. .

Specific examples of the repeating unit represented by formula (AI) are given below, but the present invention is not limited to these specific examples.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents 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 a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

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

Moreover, resin (A) may have a repeating unit which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxyl group as represented below as a repeating unit which has an acid-decomposable group. In addition, this alcoholic hydroxyl group represents the concept of a pair with a phenolic hydroxyl group, and specifically refers to a hydroxyl group that does not exhibit acidity peculiar to a phenolic hydroxyl group in water.
In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

One type of repeating unit having an acid-decomposable group may be used, or two or more types may be used in combination. When two types are used in combination, a preferable combination is a combination whose structure is exemplified after paragraph [0121] of US2012 / 0009522A (in addition, US2012 / 0009522A is described in this specification). Incorporated).
Examples of the combination of two types include, for example, the following combinations, combinations of repeating units represented by the general formula (AI), and repeating units that decompose by the action of an acid to generate alcoholic hydroxyl groups, and the like. Conceivable.

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), 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. Among them, the resin (A) has a repeating unit represented by the general formula (AI), and the content of the repeating unit represented by the general formula (AI) with respect to all the repeating units of the resin (A) is 40. It is preferably at least mol%.
Since the content of the repeating unit having an acid-decomposable group with respect to all repeating units of the resin (A) is 40 mol% or more, the glass transition temperature (Tg) of the resin (A) can be reliably increased, The effect that the increase in process cost described above can be suppressed can be made more reliable.
The content of the repeating unit having an acid-decomposable group is preferably 80 mol% or less, preferably 70 mol% or less, and 65 mol% with respect to all the repeating units of the resin (A). The following is more preferable.

The resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable. Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a member ring lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LER (Line edge Roughness) and development defects are improved.

The lactone structure part or sultone structure part may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. 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. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

  The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination of two or more of them when there are a plurality of R ₀ .
Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond if there are multiple

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.

A preferable chain alkylene group for R ₀ is preferably a chain alkylene group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. . A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxyl group , Alkoxy groups, and acyloxy groups.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure. As specific examples, general formulas (LC1-1) to ( LC1-21) and a lactone structure or a sultone structure represented by any one of (SL1-1) to (SL1-3), and among these, a structure represented by (LC1-4) is particularly preferable. preferable. Further, n ₂ in (LC1-1) to (LC1-21) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

  Specific examples of the repeating unit having a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

  In order to enhance the effect of the present invention, it is possible to use two or more kinds of repeating units having a lactone structure or a sultone structure 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 5 to 60 mol% with respect to all the repeating units in the resin (A). Is more preferable, more preferably 5-55 mol%, still more preferably 10-50 mol%.

Moreover, the resin (A) may have a repeating unit having a cyclic carbonate structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In General Formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ² independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.
n represents an integer of 0 or more.

General formula (A-1) is demonstrated in detail.
The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.
Examples of the substituent represented by R _A ² include an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, and an alkoxycarbonylamino group. Preferably it is a C1-C5 alkyl group. The alkyl group may have a substituent such as a hydroxyl group.
n is an integer of 0 or more representing the number of substituents. For example, n is preferably 0 to 4, and more preferably 0.

Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination of two or more thereof. As an alkylene group, a C1-C10 alkylene group is preferable, A C1-C5 alkylene group is more preferable, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned.
In one embodiment of the present invention, A is preferably a single bond or an alkylene group.

As the monocycle represented by Z and including —O—C (═O) —O—, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 to 7-membered ring, and it is preferably a 5- or 6-membered ring (n _a = 2 or 3), more preferably a 5-membered ring (n _a = 2).
Examples of the polycycle including —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures. Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .

  The monomer corresponding to the repeating unit represented by the general formula (A-1) is, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002) and the like, and can be synthesized by a conventionally known method.

In the resin (A), one type of repeating units represented by the general formula (A-1) may be contained alone, or two or more types may be contained.
In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). 3 to 80 mol%, preferably 3 to 60 mol%, more preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR, low PEB temperature dependence, a profile, etc. can be improved.

Although the specific example of the repeating unit represented by general formula (A-1) below is given, this invention is not limited to these.
Incidentally, R _A ¹ in the following specific examples are the same meaning as R _A ¹ in the general formula (A-1).

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group.
In addition, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably different from the repeating unit having an acid-decomposable group (that is, the repeating unit is stable with respect to an acid). preferable).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
More preferable examples include a repeating unit represented by any one of the following general formulas (AIIa) to (AIIc).

In the formula, Rx represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.
Ab represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination of two or more thereof. As an alkylene group, a C1-C10 alkylene group is preferable, A C1-C5 alkylene group is more preferable, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned.
In one embodiment of the present invention, Ab is preferably a single bond or an alkylene group.
Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. The plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but when the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, The content of the repeating unit having a cyano group is preferably from 1 to 40 mol%, more preferably from 3 to 30 mol%, still more preferably from 5 to 25 mol%, based on all repeating units in the resin (A). . The resin (A) may contain two or more types of repeating units having a hydroxyl group or a cyano group having different structures.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  In addition, the monomers described in [0011] on and after International Publication No. 2011/122336 or the corresponding repeating units can be used as appropriate.

  The resin (A) may have one or more repeating unit structures having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, a naphthol structure, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit having a carboxyl group. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  The resin (A) may or may not contain a repeating unit having an acid group. However, when it is contained, the content of the repeating unit having an acid group is relative to all the repeating units in the resin (A). It is preferably 25 mol% or less, and more preferably 20 mol% or less. When resin (A) contains the repeating unit which has an acid group, content of the repeating unit which has an acid group in resin (A) is 1 mol% or more normally.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) in the present invention may further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the above acid group, hydroxyl group, and cyano group) and does not exhibit acid decomposability. . As a result, the elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. . Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As the monocyclic hydrocarbon group, a cyclopentyl group and a cyclohexyl group are preferable.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. 1 to 50 mol% is preferable with respect to all repeating units in the resin (A), more preferably 5 to 50 mol%, still more preferably 5 to 30 mol%. In addition, resin (A) may contain the repeating unit which has two or more types of alicyclic hydrocarbon structures which do not have a polar group, and which does not show acid-decomposability | different_conditions from which a structure differs.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) used in the composition is a general resin composition other than the above repeating structural units, and includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and actinic ray sensitive or radiation sensitive resin composition. It is possible to have various repeating structural units for the purpose of adjusting resolving power, heat resistance, sensitivity, and the like, which are necessary characteristics.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the resin used in the actinic ray-sensitive or radiation-sensitive resin composition, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as dry etching resistance can be performed.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition, the content molar ratio of each repeating structural unit is the dry etching resistance or standard developer suitability of the actinic ray-sensitive or radiation-sensitive resin composition, It is suitably set to adjust the substrate adhesion, resist profile, and further the resolving power, heat resistance, sensitivity, etc., which are general required performances of the actinic ray-sensitive or radiation-sensitive resin composition.

The form of the resin (A) may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
When the actinic ray-sensitive or radiation-sensitive resin composition is for ArF exposure, the resin (A) has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, it preferably has no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In the case where the actinic ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin (D) described later, the resin (A) is a fluorine atom and a fluorine atom from the viewpoint of compatibility with the hydrophobic resin (D). Does not contain silicon atoms (specifically, the proportion of repeating units containing fluorine atoms or silicon atoms in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%) It is preferable.

  The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  When the actinic ray-sensitive or radiation-sensitive resin composition is irradiated with KrF excimer laser light, electron beam, X-ray, high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) is further fragrant. It is preferable to have a repeating unit containing a ring structure, for example, a hydroxystyrene-based repeating unit. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the resin having a repeating unit containing an aromatic ring structure are shown below, but the present invention is not limited thereto.

  In the above specific example, tBu represents a t-butyl group.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization, living radical polymerization, anion polymerization). For example, reference can be made to the descriptions in paragraphs [0121] to [0128] of JP2012-074032A (paragraphs [0203] to [0211] of the corresponding US Patent Application Publication No. 2012/0777122). The contents are incorporated herein.

  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 as described above in terms of polystyrene by GPC method. 50,000 to 50,000, still more preferably 7,000 to 40,000,000, particularly preferably 7,000 to 30,000. If the weight average molecular weight is less than 7,000, the solubility in the developer becomes too high, and there is a concern that a precise pattern cannot be formed.

  The dispersity (molecular weight distribution) 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. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition, the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In the present invention, the resin (A) may be used alone or in combination.

[2] Compound (B) that generates an acid upon irradiation with an actinic ray or radiation
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is usually a compound (B) that generates an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “acid generator” “compound (B ) ”)). The compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. In addition, the compound (B) may be contained in the resin (A) described above. More specifically, the compound (B) may be linked to the resin (A) via a chemical bond.
The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be 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) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation 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, and is acid-decomposable. It may be incorporated in a resin different from the resin.
In the present invention, the compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably in the form of a low molecular compound.
As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.

  For example, examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

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 generally 1-30, preferably 1-20.
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. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cyclohexane having 3 to 30 carbon atoms. Alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, etc. Can be mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), ant Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of this substituent include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as those in the aromatic sulfonate anion.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The alkylene group formed by linking two alkyl groups in these alkyl groups and bis (alkylsulfonyl) imide anions may have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group. , An alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and an alkyl group substituted with a fluorine atom is preferred.
Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like. .

As the non-nucleophilic anion of Z ⁻ , an aliphatic sulfonate anion in which at least α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

The acid generator is preferably a compound that generates an acid represented by the following general formula (V) or (VI) upon irradiation with actinic rays or radiation. Since it is a compound that generates an acid represented by the following general formula (V) or (VI) and has a cyclic organic group, the resolution and roughness performance can be further improved.
As said non-nucleophilic anion, it can be set as the anion which produces the organic acid represented by the following general formula (V) or (VI).

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z 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. Xf is more preferably a fluorine atom or CF ₃ . In particular, it is preferable that both Xf are fluorine atoms.

R ₁₁ and R ₁₂ are each independently a hydrogen atom, a fluorine atom, or an alkyl group. This alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. The alkyl group having a substituent for R ₁₁ and R ₁₂ is preferably CF ₃ .

L represents a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, and an alkylene group. (Preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 10 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group in which two or more of these are combined. It is done. Among these, —COO—, —OCO—, —CONH—, —NHCO—, —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.

Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include alicyclic groups having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. From the viewpoint of suppressing diffusibility in the film in the PEB (post-exposure heating) step and improving 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 the polycyclic group 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 not having aromaticity include a tetrahydropyran ring, a lactone ring or 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 particularly preferable. Examples of the lactone ring or sultone ring include the lactone structure or sultone exemplified in the aforementioned resin (A).

  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), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic). 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 sulfonic acid An ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, and more preferably 0. z is preferably 0 to 8, particularly preferably 0 to 4.
Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom, or may be substituted with another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
Further, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent not containing a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.
Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.

The non-nucleophilic anion is preferably an anion represented by any one of the following general formulas (B-1) to (B-3).
First, the anion represented by the following general formula (B-1) will be described.

In the general formula (B-1),
R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).
n represents an integer of 1 to 4. n is preferably an integer of 1 to 3, and more preferably 1 or 2.
X _b1 represents a single bond, an ether bond, an ester bond (-OCO- or -COO-) or a sulfonic acid ester bond represents a (-OSO ₂ - - or -SO _3). X _b1 is preferably an ester bond (—OCO— or —COO—) or a sulfonate bond (—OSO ₂ — or —SO ₃ —).
R _b2 represents a substituent having 6 or more carbon atoms. The substituent having 6 or more carbon atoms for R _b2 is preferably a bulky group, and examples thereof include alkyl groups, alicyclic groups, aryl groups, and heterocyclic groups having 6 or more carbon atoms. The alkyl group having 6 or more carbon atoms for R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms. Examples thereof include a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. From the viewpoint of bulkiness, a branched alkyl group is preferable.

The alicyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclohexyl group and a cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (heating after exposure) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

The aryl group having 6 or more carbon atoms for R _b2 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 having 6 or more carbon atoms for R _b2 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 benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a benzofuran ring or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring include the lactone structure exemplified in the aforementioned resin (A).

The substituent having 6 or more carbon atoms for R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic, or spiro ring). And preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, And sulfonic acid ester groups. In addition, carbonyl carbon may be sufficient as the carbon (carbon which contributes to ring formation) which comprises the above-mentioned alicyclic group, an aryl group, or a heterocyclic group.
Specific examples of the anion represented by the general formula (B-1) are shown below, but the present invention is not limited to these.

  Next, the anion represented by the following general formula (B-2) will be described.

In the general formula (B-2),
Q _b1 represents a group having a lactone structure, a group having a sultone structure, or a group having a cyclic carbonate structure.
Examples of the lactone structure and sultone structure for Q _b1 include those similar to the lactone structure and sultone structure in the repeating unit having the lactone structure and sultone structure described above in the section of the resin (A). Specifically, the lactone structure represented by any one of the above general formulas (LC1-1) to (LC1-17) or any one of the above general formulas (SL1-1) to (SL1-3). A sultone structure is mentioned.
The lactone structure or sultone structure may be directly bonded to the oxygen atom of the ester group in the general formula (B-2), but the lactone structure or sultone structure is an alkylene group (for example, a methylene group or an ethylene group). ) May be bonded to an oxygen atom of the ester group. In that case, the group having the lactone structure or sultone structure can be referred to as an alkyl group having the lactone structure or sultone structure as a substituent.
Preferably the cyclic carbonate structure for Q _b1 represents a cyclic carbonate structure 5- to 7-membered ring, 1,3-dioxolan-2-one, 1,3-dioxan-2-one and the like.
The cyclic carbonate structure may be directly bonded to the oxygen atom of the ester group in the general formula (B-2), but the cyclic carbonate structure is bonded via an alkylene group (for example, a methylene group or an ethylene group). It may be bonded to an oxygen atom of the ester group. In that case, the group having the cyclic carbonate structure can be referred to as an alkyl group having a cyclic carbonate structure as a substituent.
Specific examples of the anion represented by the general formula (B-2) are shown below, but the present invention is not limited thereto.

  Next, the anion represented by the following general formula (B-3) will be described.

In the general formula (B-3),
L _b2 represents an alkylene group having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group, and an alkylene group having 1 to 4 carbon atoms is preferable.
X _b2 represents an ether bond or an ester bond (—OCO— or —COO—).
Q _b2 represents a group containing an alicyclic group or an aromatic ring.
The alicyclic group for Q _b2 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include alicyclic groups having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. preferable.
The aromatic ring in the group containing an aromatic ring for Q _b2 is preferably an aromatic ring having 6 to 20 carbon atoms, and examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. More preferably, it is a ring. The aromatic ring may be substituted with at least one fluorine atom, and examples of the aromatic ring substituted with at least one fluorine atom include a perfluorophenyl group.
The aromatic ring may be directly bonded to X _b2 , but the aromatic ring may be bonded to X _b2 via an alkylene group (for example, a methylene group or an ethylene group). In that case, the group containing the aromatic ring can be referred to as an alkyl group having the aromatic ring as a substituent.
Specific examples of the anion structure represented by the general formula (B-3) are shown below, but the present invention is not limited thereto.

In the formula (ZI), examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. ).

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.

  Further preferred examples of the (ZI) component include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) will be described.
The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.
Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .

Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 10 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C10 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group as the R _1c to R _5c.

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of the R _1c to R _5c.

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of the R _1c to R _5c.

Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of the R _1c to R _5c.
Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring, particularly preferably a 6-membered ring (for example, a phenyl ring). It is done.

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in formula (ZI-3) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups. In particular, the case where R _6c and R _7c are each a linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and the case where both are methyl groups is particularly preferred.

In addition, when R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as an ethylene group , Propylene group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

_Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group as R _x and R _y include a group having> C═O at the 2-position of the alkyl group and cycloalkyl group as R _{1c to} R _7c. .

Examples of the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms. Preferably, a C1-C5 linear alkyl group (for example, a methyl group, an ethyl group) can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted allyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). An allyl group is preferred.

The vinyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted vinyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). It is preferably a vinyl group.

The ring structure which may be formed by R _5c and R _x are bonded to each other, bonded R _5c and R _x each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a 5-membered ring or more (particularly preferably a 5-membered ring) formed together with the sulfur atom and the carbonyl carbon atom in the formula (ZI-3).

As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

R _{1c to} R _7c , R _x and R _y may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, and a nitro group. Group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group etc. can be mentioned.

In the general formula (ZI-3), R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c is a group other than a hydrogen atom, that is, an alkyl group, a cycloalkyl group, More preferably, it represents an aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group.

  Examples of the cation of the compound represented by formula (ZI-2) or (ZI-3) in the present invention include the following specific examples.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -A butyl group, a t-butyl group, etc. are preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), particularly cyclopropyl, cyclopentyl, cyclohexyl, Cycloheptyl and cyclooctyl are preferred.

The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, or the like.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, or the like.

Examples of the group having a cycloalkyl group represented by R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). Examples thereof include a cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The monocyclic or polycyclic cycloalkyloxy group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, It is preferable to have a cycloalkyl group. Monocyclic cycloalkyloxy group having 7 or more carbon atoms in total is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with an alkyl group, hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, alkoxy group, alkoxycarbonyl group, acyl group, acetoxy A monocyclic cycloalkyloxy group having a substituent such as a group, an acyloxy group such as a butyryloxy group, or a carboxy group, and having a total carbon number of 7 or more in combination with any substituents on the cycloalkyl group Represent.
Examples of the polycyclic cycloalkyloxy group having 7 or more total carbon atoms include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl group is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl group is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group which may have the above-mentioned substituent is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituent is 7 or more. Represents things. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.

  Examples of the alkoxy group having a polycyclic cycloalkyl group having a total carbon number of 7 or more include a norbornyl methoxy group, a norbornyl ethoxy group, a tricyclodecanyl methoxy group, a tricyclodecanyl ethoxy group, a tetracyclo group. A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantyl methoxy group, an adamantyl ethoxy group, etc. are mentioned, A norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group and the like are preferable.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4), particularly preferably Includes a 5-membered ring (that is, a tetrahydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxy group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. There may be a plurality of substituents for the ring structure, and they may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or these A polycyclic fused ring formed by combining two or more rings may be formed.
R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation of the compound represented by formula (ZI-4) in the present invention include the following.

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-1). Things can be mentioned.
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI-2), respectively. The same thing as an example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates a monovalent perfluoroalkanesulfonic acid, a monovalent fluorine atom or a fluorine atom. It is a compound that generates an aromatic sulfonic acid substituted with a containing group, or a compound that generates a monovalent fluorine atom or an imido acid substituted with a fluorine-containing group. More preferably, the acid generator is a sulfonium salt of a fluorinated substituted alkanesulfonic acid, a fluorine substituted benzenesulfonic acid, a fluorine substituted imide acid or a fluorine substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid, or a fluorinated substituted imido acid whose pKa of the generated acid is “−1” or less, and the sensitivity is improved. .

  Among acid generators, particularly preferred examples are given below.

  Further, among the compounds (B), particularly preferable examples are given below as those having an anion represented by any one of the above general formulas (B-1) to (B-3). It is not limited.

The acid generator can be synthesized by a known method. For example, [0200] to [0210] of JP-A No. 2007-161707, JP-A No. 2010-100595, and International Publication No. 2011/093280 [ [0051] to [0058], [0382] to [0385] of International Publication No. 2008/153110, Japanese Patent Application Laid-Open No. 2007-161707, and the like.
An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the compound that generates an acid upon irradiation with actinic rays or radiation (excluding the case represented by the above general formula (ZI-3) or (ZI-4)) in the composition is actinic ray sensitive or 0.1-30 mass% is preferable on the basis of the total solid content of the radiation-sensitive resin composition, more preferably 0.5-25 mass%, still more preferably 3-20 mass%, and particularly preferably 3-15. % By mass.
When the acid generator is represented by the general formula (ZI-3) or (ZI-4), the content is preferably 5 to 35% by mass based on the total solid content of the composition. 6-30 mass% is more preferable, 6-30 mass% is still more preferable, and 6-25 mass% is especially preferable.

[3] Solvent (C)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may contain a solvent (C).
Examples of the solvent (C) that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Organic solvents such as alkyl acid, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, etc. be able to.
Specific examples of these solvents include those described in paragraphs [0441] to [0455] of US Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent may be used as the solvent (C).
For example, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), ethyl lactate, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, containing a ring Two or more kinds of mixed solvents selected from monoketone compounds, cyclic lactones, alkyl acetates, etc., which may be used, are preferred, and among these, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane) (hereinafter, Solvent A), and selected from propylene glycol monomethyl ether, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate. Species or two solvents (hereinafter also referred to as a solvent B) mixed solvent of is preferred.
The mixing ratio (solvent A / solvent B) (mass ratio) of the mixed solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.
The solvent (C) preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[4] Hydrophobic resin (D)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is a hydrophobic resin (hereinafter referred to as “hydrophobic resin (D)” or simply “resin (D)”, particularly when applied to immersion exposure. May also be included). The hydrophobic resin (D) is preferably different from the resin (A).
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to. In addition, since uneven distribution of the hydrophobic resin (D) can be expected to suppress so-called outgassing, the hydrophobic resin (D) may be used when the pattern forming method of the present invention is performed by EUV exposure. preferable.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.

  When the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R _61, at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently substituted with a fluorine atom or at least one hydrogen atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more types.

  Hereinafter, as specific examples of the repeating unit having a fluorine atom, paragraphs [0274] to [0276] of JP 2012-073402 A (paragraph [0398] of the corresponding US Patent Application Publication No. 2012/0777122) [0399]) can be referred to, the contents of which are incorporated herein.

  The hydrophobic resin (D) may contain a silicon atom. As a partial structure having a silicon atom, described in paragraphs [0277] to [0281] of JP 2012-073402 A (paragraphs [0400] to [0405] of the corresponding US Patent Application Publication No. 2012/077122) The contents of which are incorporated herein by reference.

Further, as described above, the hydrophobic resin (D) also preferably includes a “CH ₃ partial structure” in the side chain portion.
Here, the hydrophobic resin (D) CH ₃ partial structure contained in the side chain moiety in (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ parts ethyl, and propyl groups have Includes structure.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the “CH ₃ partial structure”.

More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as it is”, the CH ₃ is not included in the “CH ₃ partial structure” of the side chain moiety.
On the other hand, when CH ₃ exists from the C—C main chain through some atom, it corresponds to “CH ₃ partial structure”. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure.

In the general formula (M),
R _{11 to} R ₁₄ each independently represents a side chain portion.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of monovalent organic groups for R _{11 to} R ₁₄ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyls. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

  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 a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group stable to an acid is more specifically an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Is preferred.

The alkyl group for X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
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 acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

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.

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, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25.
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. is there.
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.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  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, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.

The alkyl group for X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable to acids, more specifically, it is an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Preferably there is.

R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

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.

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

  Preferred specific examples of the repeating unit represented by the general formula (III) are shown below. Note that the present invention is not limited to this.

  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.

In the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all repeating units of the hydrophobic resin (D).

  The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.

Further, the hydrophobic resin (D) includes the following (x) to (z) even when (i) contains a fluorine atom and / or silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
As for content of the repeating unit which has an acid group (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5- 20 mol%.

  Specific examples of the repeating unit having an acid group (x) include paragraphs [0285] to [0287] of JP 2012-073402 (corresponding to paragraph [0414] of US 2012/077122). ), The contents of which are incorporated herein.

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).

  The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D), It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

  In the hydrophobic resin (D), examples of the repeating unit having a group (z) capable of decomposing by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the hydrophobic resin (D). More preferably, it is 10-80 mol%, More preferably, it is 20-60 mol%.

  The hydrophobic resin (D) may further have a repeating unit represented by the following general formula (III).

In general formula (III):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
L _c3 represents a single bond or a divalent linking group.

In general formula (III), the alkyl group represented by R _c32 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 aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (III) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

  It is also preferable that the hydrophobic resin (D) further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is more preferably 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 10 to 80% by mass. More preferably. Moreover, it is preferable that it is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.
When the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin (D). More preferably. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and it is more preferable that it is 20-100 mol%.

On the other hand, particularly when the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, it is also preferable that the resin (D) contains substantially no fluorine atom or silicon atom. The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, based on all repeating units in the hydrophobic resin (D). It is preferably 1 mol% or less, ideally 0 mol%, that is, it does not contain a fluorine atom and a silicon atom. Moreover, it is preferable that hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in all the repeating units of the hydrophobic resin (D). It is preferably 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass with respect to the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition. % Is more preferable, and 0.1-7 mass% is still more preferable.

  As for the hydrophobic resin (D), as in the resin (A), it is natural that the residual monomer and oligomer components are preferably 0.01 to 5% by mass, and more preferably less impurities such as metals. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (D), The reaction concentration is preferably 30 to 50% by mass.

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

[5] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may contain a basic compound in order to reduce a change in performance over time from exposure to heating. Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having a structure represented by the following formulas (A) to (E).

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

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. be able to.

  Examples of the compound (N) having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the compound (N) having a diazabicyclo structure, 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 the compound (N) having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide. , Tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound (N) having an onium carboxylate structure, the anion portion of the compound (N) having an onium hydroxide structure is converted to a carboxylate. For example, acetate, adamantane-1-carboxylate, perfluoroalkylcarboxylate Etc. Examples of the compound (N) having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound (N) include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound (N) further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007 / 0224539A1.

  The following compounds are also preferable as the basic compound (N).

As the basic compound (N), in addition to the above-mentioned compounds, paragraphs [0180] to [0225] of JP2011-22560A, paragraphs [0218] to [0219] of JP2012-137735A, The compounds described in paragraphs [0416] to [0438] of International Publication No. 2011/158687 can also be used. The basic compound (N) may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.
These basic compounds (N) may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is actinic ray-sensitive or The amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the radiation-sensitive resin composition.
The use ratio of the acid generator and the basic compound (N) in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, 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 resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(2) Basic compound or ammonium salt compound (E) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition may contain a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (E)”) whose basicity is lowered by irradiation with actinic rays or radiation. preferable.
The compound (E) is preferably a compound (E-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (E) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with active light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (E) or (E-1) is decomposed by irradiation with actinic rays or radiation, and the compound with reduced basicity is represented by the following general formula (PA-I), (PA-II) or (PA -III) can be mentioned. Among these, from the viewpoint that the excellent effects regarding LWR, local pattern dimension uniformity, and DOF can be achieved at a high level, the compound represented by formula (PA-II) or (PA-III) is particularly preferred. preferable.
First, the compound represented by general formula (PA-I) is demonstrated.
_{Q-A 1 - (X)} n -B-R (PA-I)
In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents -SO ₃ H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.
Next, the compound represented by general formula (PA-II) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
Next, the compound represented by general formula (PA-III) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)
In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either Q ₁ or Q ₃ has a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
When B is —N (Qx) —, Q ₃ and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

  Hereinafter, although the specific example of a compound (E) is given, it is not limited to these. In addition to the exemplified compounds, preferred specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, and US Patent Application Publication No. (A-1)-(A-23) of 2012/0156617 specification, etc. are mentioned.

It is preferable that the molecular weight of a compound (E) is 500-1000.
The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the compound (E), but when it is contained, the content of the compound (E) is the actinic ray-sensitive or radiation-sensitive resin. 0.1-20 mass% is preferable on the basis of solid content of the composition, more preferably 0.1-10 mass%.
Further, as one aspect of the compound (E), a compound (E-2) that generates an acid (weak acid) having a strength that does not decompose the acid-decomposable group of the resin (A) by acid irradiation or radiation irradiation. Can also be mentioned.
Examples of the compound include an onium salt of a carboxylic acid having no fluorine atom (preferably a sulfonium salt) and an onium salt of a sulfonic acid having no fluorine atom (preferably a sulfonium salt). More specifically, for example, among onium salts represented by the following general formula (6A), those in which the carboxylic acid anion does not have a fluorine atom, among onium salts represented by the following general formula (6B) Examples include those in which the sulfonate anion does not have a fluorine atom. As a cation structure of a sulfonium salt, the sulfonium cation structure mentioned by the acid generator (B) can be mentioned preferably.
More specifically, as compound (E-2), compounds listed in paragraph [0170] of International Publication No. 2012/053527, paragraphs [0268] to [0269] of JP2012-173419A, Compound etc. are mentioned.
A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

(3) Low molecular weight compound (F) having a nitrogen atom and a group capable of leaving by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition may contain a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (F)”).
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight of the compound (N ″) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (F), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (F) 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 _b is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are 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, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by R _b .
R _b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two R _b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the structure represented by the general formula (d-1) include the structure disclosed in paragraph [0466] of US Patent Application Publication No. 2012/0135348. It is not limited.

  The compound (F) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group as R _a are groups in which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.
Preferred examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) The same group as the preferable example mentioned above about _Rb is mentioned.
Further, the heterocyclic ring formed by connecting R _a to each other preferably has 20 or less carbon atoms. 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-ene, indole, indoline, 1,2,3 -Groups derived from heterocyclic compounds such as tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds derived from linear and branched alkanes Groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Or a group substituted with one or more of the above.

  Specific examples of the preferred compound (F) include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (F) can be used singly or in combination of two or more.
The content of the compound (F) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.001 to 20% by mass, more preferably 0.001 based on the total solid content of the composition. -10 mass%, More preferably, it is 0.01-5 mass%.

(4) Onium salt Moreover, as a basic compound, you may include the onium salt represented by the following general formula (6A) or (6B). This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded. X ⁺ represents an onium cation.
In General Formula (6B), Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded. X ⁺ represents an onium cation.

In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or carboxylic acid group.
Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Or a C3-C30 heterocyclic group etc. are mentioned. In these groups, some or all of the hydrogen atoms may be substituted.
Examples of the substituent 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.

Examples of the onium cation represented by X ⁺ in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Of these, a sulfonium cation is more preferable.
As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.
Preferred examples of the sulfonium cation and the iodonium cation include the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B).

A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.
In addition, onium salt may be used individually by 1 type, and may be used in combination of 2 or more types.

(5) Betaine compound Furthermore, the composition includes a compound contained in formula (I) of JP2012-189777A, a compound represented by formula (I) of JP2013-6827A, and JP2013- Both an onium salt structure and an acid anion structure in one molecule, such as a compound represented by the formula (I) of No. 8020 and a compound represented by the formula (I) of JP 2012-252124 A A compound having the same (hereinafter also referred to as betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. Moreover, as an acid anion structure, a sulfonate anion or a carboxylate anion is preferable. Examples of this compound include the following.
In addition, a betaine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[6] Surfactant (F)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may further contain a surfactant. In the case of containing a surfactant, either fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, surfactant having both fluorine atom and silicon atom), or two kinds It is more preferable to contain the above.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, a resist pattern with good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. Can be given.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph [0276] of U.S. Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) ), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M), MegaFuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S- 382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical ( Co., Ltd.), Surflon S-393 (Seimi Chemical Co., Ltd.), F Top EF121, F122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 230G, 230G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the surfactant corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylate having C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.

  These surfactants may be used alone or in several combinations.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Preferably it is 0.0001-2 mass%, More preferably, it is 0.0005-1 mass%.
On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased. As a result, the surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7] Other additives (G)
The actinic ray-sensitive or radiation-sensitive resin composition includes an acid proliferator, 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 phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) may be contained.

Such a phenol compound having a molecular weight of 1000 or less is disclosed in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.
Specific examples of alicyclic or aliphatic compounds 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, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The actinic ray-sensitive or radiation-sensitive resin composition is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5. 3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, whereby aggregation of the material in the resist solution, particularly the acid generator, is suppressed, As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

The actinic ray-sensitive or radiation-sensitive resin composition is preferably prepared by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent.
During the preparation, a process of reducing metal impurities in the composition to the ppb level using an ion exchange membrane, a process of filtering impurities such as various particles using an appropriate filter, a deaeration process, etc. Good. Specifics of these steps are described in JP 2012-88574 A, JP 2010-189563 A, JP 2001-12529 A, JP 2001-350266 A, and JP 2002-99076 A. JP-A-5-307263, JP-A 2010-164980, WO 2006/121162, JP-A 2010-243866, JP-A 2010-020297, and the like.
In particular, with respect to a suitable filter used in the filtering step, a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon is used. preferable.
The actinic ray-sensitive or radiation-sensitive resin composition preferably has a low water content. Specifically, the water content is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.3% by mass or less in the total weight of the composition.

(Procedure of step (1))
The method for forming a film on the substrate using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be adopted. Especially, the method of apply | coating the said actinic-light sensitive or radiation sensitive resin composition on a board | substrate from the point which adjustment of the thickness of a film | membrane is easier is mentioned.
The application method is not particularly limited, and a known method can be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.
Moreover, you may implement the drying process for removing a solvent as needed after apply | coating actinic-ray-sensitive or radiation-sensitive resin composition. The method for the drying treatment is not particularly limited, and examples thereof include heat treatment and air drying treatment.

<Membrane>
The receding contact angle of a film (resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. , 75 ° or more, more preferably 75 to 85 °. When the receding contact angle of the resist film is in the above range, it is suitable for exposure through an immersion medium.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.

  The thickness of the resist film is not particularly limited, but is preferably 1 to 500 nm and more preferably 1 to 100 nm because a fine pattern with higher accuracy can be formed.

[Step (2): Exposure step]
Step (2) is a step of exposing the film formed in step (1). More specifically, it is a step of selectively exposing the film so that a desired pattern is formed. As a result, the film is exposed in a pattern, and the solubility of the resist film changes only in the exposed part.
“Exposing” intends to irradiate actinic rays or radiation.

The light used for the exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, it is far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
More specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, and the like can be mentioned. ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

The method for selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) in which the light transmittance of the light shielding portion is 0% or a halftone phase shift mask (HT-Mask) in which the light transmittance of the light shielding portion is 6% can be used.
In general, a binary mask is used in which a chromium film, a chromium oxide film, or the like is formed on a quartz glass substrate as a light shielding portion.
As the halftone phase shift mask, generally, a quartz glass substrate on which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a silicon oxynitride film, or the like is formed as a light shielding portion is used.
In the present invention, the exposure is not limited to exposure through a photomask, and selective exposure (pattern exposure) may be performed by exposure without using a photomask, for example, drawing with an electron beam or the like.
This step may include multiple exposures.

(Heat treatment)
Prior to this step, heat treatment (PB: Prebake) may be performed on the film. Heat treatment (PB) may be performed a plurality of times.
Moreover, you may perform a heat processing (PEB: Post Exposure Bake) with respect to a resist film after this process. The heat treatment (PEB) may be performed a plurality of times.
The reaction of the exposed part is promoted by the heat treatment, and the sensitivity and pattern profile are further improved.
In both PB and PEB, the temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.
For both PB and PEB, the heat treatment time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds.
For both PB and PEB, the heat treatment can be performed by means provided in a normal exposure / development machine, and may be performed using a hot plate or the like.

(Preferred embodiment: immersion exposure)
As a suitable aspect of exposure, for example, liquid immersion exposure can be mentioned. By using immersion exposure, a finer pattern can be formed. Note that immersion exposure can be combined with super-resolution techniques such as a phase shift method and a modified illumination method.

The immersion liquid used for immersion exposure is transparent to the exposure wavelength and has a refractive index temperature coefficient as much as possible so as to minimize distortion of the optical image projected onto the resist film. Small liquids are preferred. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used as the immersion liquid, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist film and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.
On the other hand, when an opaque material or impurities whose refractive index is significantly different from water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. For this reason, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The water used as the immersion liquid preferably has an electric resistance of 18.3 MΩcm or more, a TOC (organic substance concentration) of 20 ppb or less, and is preferably deaerated.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  In immersion exposure, the surface of the resist film may be washed with an aqueous chemical before exposure and / or after exposure (before heat treatment).

[Step (3): Development step]
Step (3) is a step of developing the film exposed in step (2) to form a pattern. In this step, one of the step A with a developer containing water and the step B with a developer containing an organic solvent is performed, and then the other step is performed. That is, step A and step B are performed in no particular order. More specifically, the process B may be performed after the process A is performed, or the process A may be performed after the process B is performed. Among these, it is preferable to carry out step B after carrying out step A from the point that film slippage is further suppressed (hereinafter also referred to simply as “the point where the effect of the present invention is more excellent”).
In step A, the “region with a large amount of exposure” in step (2) is dissolved by the developer to form a so-called positive pattern. On the other hand, in the step B, the “region with a small amount of exposure” in the step (2) is dissolved by the developer, and a so-called negative pattern is formed. That is, the process A is a process of selectively dissolving / removing a region where the exposure amount is greater than or equal to the threshold value (a), and the process B is a process of selectively dissolving / removing a region where the exposure amount is less than the threshold value (b). It is a process of removing. Note that the threshold (a) is larger than the threshold (b) in terms of the magnitude relationship between the threshold (a) and the threshold (b).

  In step (3), a predetermined additive is contained in the developer containing the organic solvent used in step B. More specifically, for example, when step A is performed first and then step B is performed, it is added to the developer used in step B to be performed later (in a developer containing an organic solvent). Agent is included. Moreover, the process B may be implemented first and the process A may be implemented after that.

  As described above, the developer containing the organic solvent only needs to contain a predetermined additive, and the developer used in step A may contain an additive described later. In the case where an additive is contained in the developer in both processes, the replacement with the additive in the process to be performed later is usually performed. For example, when an onium salt is contained in the developer used in Step A and a nitrogen-containing compound is contained in the developer used in Step B, the interaction between the polar group and the onium salt is performed when Step A is performed. When Step B is performed thereafter, exchange between the onium salt and the nitrogen-containing compound occurs, and an interaction between the polar group and the nitrogen-containing compound is formed.

Among them, the onium salt compound described later is included in both the developer used in Step A and the developer used in Step B, and when used in the order of Step A and Step B, it is used in Step B. The carbon ratio of the molecular weight occupied by the carbon atom in the cation of the onium salt compound in the developer and the total molecular weight of the cation (molecular weight occupied by the carbon atom / total molecular weight of the cation) is the same as that in the developer used in Step A. It is preferably smaller than the carbon ratio of the molecular weight occupied by carbon atoms in the cation of the onium salt compound to the total molecular weight of the cation (molecular weight occupied by carbon atoms / total molecular weight of the cation).
The smaller the value of the carbon ratio (molecular weight occupied by carbon atoms / total molecular weight of the cation) is, the smaller the proportion of carbon atoms is, and the cation is more hydrophilic. When the developer of Step A and Step B contains an onium salt compound, first, when Step A is carried out, the cation A in the onium salt compound contained in the developer used in Step A is the resin (A). Interacts with polar groups and forms salts. Next, when the step B is performed, exchange between the cation A interacting with the polar group of the resin (A) and the cation B in the onium salt compound contained in the developer used in the step B occurs. That is, exchange of cations that interact with the polar group of the resin (A) occurs. At that time, when the value of the cation of the onium salt compound contained in the developer used in Step B, which is a later step, is smaller in the above-mentioned carbon ratio (molecular weight occupied by carbon atoms / total molecular weight of the cation), cation exchange is performed. Thus, a more hydrophilic pattern is obtained, and the solubility in a developer containing the organic solvent used in Step B is lowered. That is, the film slippage of the pattern is further suppressed in the subsequent process, which is preferable.
In the case of the said aspect, as a suitable aspect of the onium salt compound contained in the developing solution used at the process A, the ammonium salt which contains a hydroxide ion (OH < ^- >) as an anion is mentioned, for example.

In addition, although the aspect in which the onium salt compound mentioned later is contained in both the developing solution used at the process A and the developing solution used at the process B was described above, it is not limited to this aspect.
The carbon ratio between the molecular weight occupied by the carbon atoms in the cation of the onium salt compound and the total molecular weight of the cation (the molecular weight occupied by the carbon atoms / the total molecular weight of the cation) is defined as the carbon ratio X, and the molecular weight occupied by the carbon atoms of the nitrogen-containing compound The carbon ratio of the total molecular weight of the nitrogen compound (molecular weight occupied by the carbon atom / total molecular weight of the nitrogen-containing compound) is defined as the carbon ratio Y, and the carbon ratio of the molecular weight occupied by the carbon atom of the phosphorus compound and the total molecular weight of the phosphorus compound ( The carbon ratio Z is defined as the molecular weight occupied by carbon atoms / the total molecular weight of the phosphorus compound).
As another preferred embodiment of the step (3), a group consisting of an onium salt, a nitrogen-containing compound and a phosphorus compound is carried out in the order of the step A and the step B, and each developer used in the step A and the step B is used. In the case where any one additive is included, the carbon ratio of the additive in the developer used in Step B is preferably smaller than the carbon ratio of the additive in the developer used in Step A. .
As described above, when the value of the carbon ratio (molecular weight occupied by carbon atoms / total molecular weight) is small, in order to show hydrophilicity, the carbon ratio of the additive in the developer in the step B performed in the subsequent step When the value is small, the pattern becomes more hydrophilic, and the solubility in a developer containing the organic solvent used in Step B is lowered. That is, the film slippage of the pattern is further suppressed in the subsequent process, which is preferable.
When the additive is an onium salt, the carbon ratio is intended for the carbon ratio X, and when the additive is a nitrogen-containing compound, the carbon ratio is intended for the carbon ratio Y, and the additive is a phosphorus compound. In this case, the carbon ratio intends the carbon ratio Z. For example, when an onium salt is used in the developer of step A and a nitrogen-containing compound is used in the developer of step B, the relationship of carbon ratio of nitrogen-containing compound Y <carbon ratio X of onium salt should be satisfied. preferable.
The carbon ratio of the additive in the developer used in Step B is preferably 0.8 or less, and more preferably 0.6 or less, in that the effect of the present invention is more excellent.

Moreover, as another suitable aspect of a process (3), the additive mentioned later is contained in both the developing solution used at the process A, and the developing solution used at the process B, and it is in order of the process A and the process B. When implemented, it is preferred that the additive used in step B is more multifunctional (expensive number) than the additive used in step A. For example, when a nitrogen-containing compound is contained in the developer of both step A and step B, the number of nitrogen atoms in the nitrogen-containing compound used in step B is equal to the nitrogen in the nitrogen-containing compound used in step A. More than the number of atoms is preferred. Further, for example, when an onium salt compound is contained in both the developers of Step A and Step B, the onium salt compound used in Step B is more polyvalent than the onium salt compound used in Step A. It is preferable. More specifically, the onium salt compound represented by the formula (1-1), the onium salt compound represented by the formula (1-2), and a polymer having an onium salt have an onium salt. A polymer is most preferable as an additive used in Step B, and an onium salt compound represented by the above formula (1-2) is next preferable.
If it is the said aspect, in the case of the process B which is a subsequent process, since the additive in a developing solution forms stronger interaction with resin (A), and the solubility with respect to an organic solvent falls more, As a result, film slippage of the pattern is further suppressed during the post-process, which is preferable.

  Furthermore, as another preferred embodiment, an additive described later is included in both the developer used in Step A and the developer used in Step B, and when the steps A and B are performed in this order, It is preferred that the additive used in step B is more basic than the additive used in step A. When the additive in step B is more basic, a stronger interaction is formed with the polar group in the resin (A) generated by the action of the acid. Therefore, when performing the process B, the solubility with respect to the organic solvent of a pattern falls more. As a result, the film slippage of the pattern is further suppressed in the subsequent process, which is preferable.

  Below, the additive and developer used at this process are explained in full detail first, and the procedure of the subsequent process is explained in full detail.

(Additive)
From the point of use in this step, the additive contained in the developer includes the polar group generated by the action of the acid (resin (A)), ionic bond, hydrogen bond, chemical bond and dipole interaction. A compound capable of forming at least one interaction of As described above, when the resin (A) and this additive form a predetermined interaction, the solubility of the resin (A) is changed, and film slippage is less likely to occur. The ionic bond intends an electrostatic interaction between a cation and an anion, and includes salt formation and the like.

In terms of excellent effects of the present invention, examples of the additive include at least one selected from the group consisting of an onium salt compound, a nitrogen-containing compound, and a phosphorus compound.
Hereinafter, each compound will be described in detail.

(Onium salt compound)
As the onium salt compound, a compound having an onium salt structure is intended. The onium salt structure refers to a salt structure generated by a coordinate bond between an organic component and a Lewis base. The onium salt compound mainly forms an interaction with the polar group by an ionic bond. For example, when the polar group is a carboxyl group, a cation in the onium salt compound forms an electrostatic interaction (forms an ionic bond) with the carboxyl-derived carboxyl anion (COO ⁻ ).
The type of onium salt structure is not particularly limited, and examples thereof include structures such as ammonium salts, phosphonium salts, oxonium salts, sulfonium salts, selenonium salts, carbonium salts, diazonium salts, iodonium salts having a cation structure shown below. .
In addition, the cation in the onium salt structure includes those having a positive charge on the hetero atom of the heteroaromatic ring. Examples of such onium salts include pyridinium salts and imidazolium salts.
In the present specification, the above pyridinium salt and imidazolium salt are also included as one embodiment of the ammonium salt.

The onium salt compound may be a polyvalent onium salt compound having two or more onium ion atoms in one molecule from the viewpoint that the effect of the present invention is more excellent. As the polyvalent onium salt compound, a compound in which two or more cations are linked by a covalent bond is preferable.
Examples of the polyvalent onium salt compound include diazonium salts, iodonium salts, sulfonium salts, ammonium salts, and phosphonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and ammonium salts are preferable from the viewpoint of more excellent effects of the present invention, and ammonium salts are more preferable from the viewpoint of stability.

The anion (anion) contained in the onium salt compound (onium salt structure) may be any anion as long as it is an anion, and it may be a monovalent ion or a polyvalent ion.
For example, examples of the monovalent anion include a sulfonate anion, a formate anion, a carboxylate anion, a sulfinate anion, a boron anion, a halide ion, a phenol anion, an alkoxy anion, and a hydroxide ion. Examples of the divalent anion include oxalate ion, phthalate ion, maleate ion, fumarate ion, tartaric acid ion, malate ion, lactate ion, sulfate ion, diglycolate ion, and 2,5-flange. Examples thereof include carboxylate ions.
More specifically, monovalent anions include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH _3. COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , F (HF) _n ⁻ , (CN) ₂ N ⁻ , C ₄ F ₉ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , C ₃ F ₇ COO ⁻ , (CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ , C ₉ H ₁₉ COO ⁻ , (CH ₃ ) ₂ PO ₄ ⁻ , (C ₂ H ₅ ) ₂ PO ₄ ⁻ , C ₂ H ₅ OSO ₃ ⁻ , C ₆ H ₁₃ OSO ₃ ⁻ , C ₈ H ₁₇ OSO ₃ ⁻ , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ⁻ , C ₆ H ₄ (CH ₃ ) SO ₃ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , CH ₃ CH (OH) COO ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , FSO ₃ ⁻ , C ₆ H ₅ O ⁻ , (CF ₃ ) ₂ CHO ⁻ , (CF ₃ ) ₃ CHO ⁻ , C ₆ H ₃ (CH ₃ ) ₂ O ⁻ , C ₂ H ₅ OC ₆ H ₄ COO ⁻ Etc.
Among them, preferred are sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{− and the} like, more preferably containing carbon atoms. Is an organic anion.

  Below, the specific example of the cation contained in an onium salt structure is illustrated.

  Below, the specific example of the anion contained in an onium salt structure is illustrated.

  Specific examples of the onium salt structure are illustrated below.

A preferred embodiment of the onium salt compound is composed of the onium salt compound represented by the formula (1-1) and the onium salt compound represented by the formula (1-2) in that the effect of the present invention is more excellent. There may be mentioned at least one selected from the group.
In addition, the onium salt compound represented by Formula (1-1) may use only 1 type, or may use 2 or more types together. Moreover, the onium salt compound represented by Formula (1-2) may use only 1 type, or may use 2 or more types together. Moreover, you may use together the onium salt compound represented by Formula (1-1), and the onium salt compound represented by Formula (1-2).

In formula (1-1), M represents a nitrogen atom, a phosphorus atom, a sulfur atom, or an iodine atom. Especially, a nitrogen atom is preferable at the point which the effect of this invention is more excellent.
R each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a hetero atom, an aromatic hydrocarbon group that may contain a hetero atom, or a group in which two or more of these are combined. .
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The aliphatic hydrocarbon group may contain a hetero atom. That is, it may be a heteroatom-containing hydrocarbon group. The type of hetero atom contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom. For _{example, -Y 1 H, -Y 1 -} , - N (R a) -, - C (= Y 2) -, - CON (R b) -, - C (= Y 3) Y 4 -, - SO _t— , —SO ₂ N (R _c ) —, a halogen atom, or a group in which two or more of these are combined is included.
Y _{1 to} Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
R _a , R _b and R _c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
t represents an integer of 1 to 3.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aromatic hydrocarbon group may contain a hetero atom. The aspect in which a hetero atom is contained is as described above. In addition, when a hetero atom is contained in an aromatic hydrocarbon group, you may comprise an aromatic heterocyclic group.

  As a preferred embodiment of R, an alkyl group which may contain a heteroatom, an alkene group which may contain a heteroatom, or a cycloalkyl group which may contain a heteroatom from the viewpoint that the effects of the present invention are more excellent. And an aryl group which may contain a hetero atom.

A plurality of R may be bonded to each other to form a ring. Although the kind of ring formed is not specifically limited, For example, a 5-6 membered ring structure can be mentioned.
Moreover, the ring formed may have aromaticity, for example, the cation of the onium salt compound represented by Formula (1-1) is a pyridinium ring represented by Formula (10) below. There may be. Furthermore, a hetero atom may be contained in a part of the ring formed. For example, the cation of the onium salt compound represented by the formula (1-1) is represented by the following formula (11). It may be an imidazolium ring.
In addition, the definition of R in Formula (10) and Formula (11) is as having mentioned above about Formula (1-1).
In formula (10) and formula (11), Rv each independently represents a hydrogen atom or an alkyl group. A plurality of Rv may be bonded to each other to form a ring.

X ⁻ represents a monovalent anion. The definition of monovalent anion is as described above.

  In formula (1-1), n represents an integer of 2 to 4. In addition, when M is a nitrogen atom or a phosphorus atom, n represents 4, when M is a sulfur atom, n represents 3, and when M is an iodine atom, n represents 2.

The definitions of R and X ⁻ in formula (1-2) are as described above for formula (1-1). In formula (1-2), two X ⁻ are included.
L represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms such as a phenylene group.), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, L is preferably a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group in that the effect of the present invention is more excellent.

  In formula (1-2), m represents the integer of 1-3 each independently. In addition, when M is a nitrogen atom or a phosphorus atom, m represents 3, when M is a sulfur atom, m represents 2, and when M is an iodine atom, m represents 1.

Another preferred embodiment of the onium salt compound is a polymer having an onium salt in that the effect of the present invention is more excellent. The polymer having an onium salt intends a polymer having an onium salt structure in a side chain or main chain. In particular, a polymer having a repeating unit having an onium salt structure is preferable.
The definition of the onium salt structure is as described above, and the definitions of the cation and the anion are also synonymous.

  A preferred embodiment of the polymer having an onium salt includes a polymer having a repeating unit represented by the formula (5-1) in that the effect of the present invention is more excellent.

In formula (5-1), R _p represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
L _p represents a divalent linking group. Definition of the divalent linking group represented by L _p is the same definition of L represented by the aforementioned formula (1-2).
Among these, in terms of more excellent effects of the present invention, L _a is an alkylene group, an arylene group, —COO—, or a group in which two or more of these are combined (-arylene group-alkylene group—, —COO— Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

A _p represents formula (1-1) and residue obtained by removing one hydrogen atom from an onium salt represented by any one of formula (1-2). The residue means a group having a structure in which one hydrogen atom is extracted from any position in the structural formula showing an onium salt and can be bonded to L _p . Usually, one of the hydrogen atoms in R is withdrawn and becomes a group having a structure capable of bonding to the above L _p .
The definition of each group in Formula (1-1) and Formula (1-2) is as described above.

  The content of the repeating unit represented by the above formula (5-1) in the polymer is not particularly limited, but is 30 to 100 mol% with respect to all the repeating units in the polymer in that the effect of the present invention is more excellent. Is preferable, and 50 to 100 mol% is more preferable.

  Although the weight average molecular weight of the said polymer is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

  As a suitable aspect of the repeating unit represented by Formula (5-1), the repeating unit represented by Formula (5-2) is mentioned.

In formula (5-2), the definitions of R _p and L _p are as described above for formula (5-1), and the definitions of R and X ⁻ are as described above for formula (1-1).

  Furthermore, as a suitable aspect of the repeating unit represented by Formula (5-2), the repeating unit represented by Formula (5-3)-Formula (5-5) is mentioned.

In formula (5-3), the definition of R _p is as described above for formula (5-1), and the definitions of R and X ⁻ are as described above for formula (1-1).
In formula (5-4), the definition of R _p is as described above for formula (5-1), and the definitions of R and X ⁻ are as described above for formula (1-1).
A represents -O-, -NH-, or -NR-. The definition of R is the same as the definition of R in the above formula (1-1).
B represents an alkylene group.
In formula (5-5), the definition of R _p is as described above for formula (5-1), and the definitions of R and X ⁻ are as described above for formula (1-1).

(Nitrogen-containing compounds)
A nitrogen-containing compound intends a compound containing a nitrogen atom. In the present specification, the nitrogen-containing compound does not include the onium salt compound. The nitrogen-containing compound mainly forms an interaction between a nitrogen atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with a nitrogen atom in the nitrogen-containing compound to form a salt.
As said nitrogen-containing compound, the compound represented by following General formula (6) is mentioned, for example.

In the general formula (6), R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, or a carbon number of 3 It is a group formed by combining 2 or more types of -30 alicyclic hydrocarbon groups, C6-C14 aromatic hydrocarbon groups, or these groups. R ⁶ is a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, An n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms or an n-valent group formed by combining two or more of these groups. n is an integer of 1 or more. However, when n is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different. Further, any two of R ^{4 to} R ⁶ may be bonded to form a ring structure together with the nitrogen atom to which each is bonded.

Examples of the C1-C30 chain hydrocarbon group represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ⁶ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁶ include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the group formed by combining two or more of these groups represented by R ⁴ and R ⁵ include aralkyl groups having 6 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, and naphthylethyl group. Can be mentioned.

Examples of the n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁶ include groups exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁴ and R ^5. And a group obtained by removing (n-1) hydrogen atoms from the same group.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁶ include the same groups as those exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ^5. And a group obtained by removing (n-1) hydrogen atoms from the group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁶ are the same as those exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁵ . And a group obtained by removing (n-1) hydrogen atoms from the group.
Examples of the group formed by combining two or more of these groups represented by R ⁶ are the same as those exemplified as the group formed by combining two or more of these groups represented by R ⁴ and R ⁵ . And a group obtained by removing (n-1) hydrogen atoms from the group.

The groups represented by R ^{4 to} R ⁶ may be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxy group, a halogen atom, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Moreover, as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

Examples of the compound represented by the above formula (6) include (cyclo) alkylamine compounds, nitrogen-containing heterocyclic compounds, amide group-containing compounds, urea compounds and the like.
Examples of (cyclo) alkylamine compounds include compounds having one nitrogen atom, compounds having two nitrogen atoms, compounds having three or more nitrogen atoms, and the like.
Examples of (cyclo) alkylamine compounds having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, cyclohexylamine and the like. ;
Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri- tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine;
Substituted alkylamines such as triethanolamine;
Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, N, N-dibutylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2 , 4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- ( And aromatic amines such as 4-aminophenyl) -2- (4-hydroxyphenyl) propane.

  Examples of the (cyclo) alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4 ′. -Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis [ 1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis ( 2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) 2-imidazolidinone, 2-quinoxalinium linoleic, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like.

  Examples of the (cyclo) alkylamine compound having three or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds and nitrogen-containing aliphatic heterocyclic compounds.

As a nitrogen-containing aromatic heterocyclic compound,
For example, imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methyl-1H-imidazole ;
Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, Examples thereof include pyridines such as quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, and 2,2 ′: 6 ′, 2 ″ -terpyridine.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine;
Pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, proline, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine , 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxy. Carbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(- ) -1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpyrrolidine Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl- 1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di -T-butoxycarbonyl-1,10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t-butyl Nt such as toxoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, etc. A butoxycarbonyl group-containing amino compound;
Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric Examples include acid tris (2-hydroxyethyl).

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea and the like. Is mentioned.

  Of these, (cyclo) alkylamine compounds and nitrogen-containing aliphatic heterocyclic compounds are preferable, and 1-aminodecane, di-n-octylamine, tri-n-octylamine, tetramethylethylenediamine, N, N-dibutylaniline, Proline is more preferred.

As a preferred embodiment of the nitrogen-containing compound, a nitrogen-containing compound containing a plurality (two or more) of nitrogen atoms (multivalent nitrogen-containing compound) is preferable. In particular, an embodiment including three or more is preferable, and an embodiment including four or more is more preferable.
Moreover, as another suitable aspect of a nitrogen-containing compound, the compound represented by Formula (3) is mentioned at the point which the effect of this invention is more excellent.

In Formula (3), A represents a single bond or an n-valent organic group.
Specific examples of A include a single bond, a group represented by the following formula (1A), a group represented by the following formula (1B),

—NH—, —NR _W —, —O—, —S—, carbonyl group, alkylene group, alkenylene group, alkynylene group, cycloalkylene group, aromatic group, heterocyclic group, and combinations of two or more thereof A preferred example is an n-valent organic group consisting of a group. In —NR _W —, R _W represents an organic group, preferably an alkyl group, an alkylcarbonyl group, or an alkylsulfonyl group. Further, in the above combination, heteroatoms are not linked to each other.
Of these, an aliphatic hydrocarbon group (an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group), a group represented by the above formula (1B), —NH—, and —NR _W — are preferable.

Here, the alkylene group, alkenylene group, and alkynylene group preferably have 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms. The alkylene group may be linear or branched and may have a substituent. Here, the cycloalkylene group preferably has 3 to 40 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 5 to 12 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, and may have a substituent on the ring.
The aromatic group may be monocyclic or polycyclic, and includes non-benzene aromatic groups. Monocyclic aromatic groups include benzene, pyrrole, furan, thiophene, and indole residues. Polycyclic aromatic groups include naphthalene, anthracene, tetracene, and benzofuran. Examples include benzothiophene residues and the like. The aromatic group may have a substituent.

  The n-valent organic group may have a substituent, and the kind thereof is not particularly limited, but an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkenyl group, an alkenyloxy group Alkenylcarbonyl group, alkenylcarbonyloxy group, alkenyloxycarbonyl group, alkynyl group, alkynyleneoxy group, alkynylenecarbonyl group, alkynylenecarbonyloxy group, alkynyleneoxycarbonyl group, aralkyl group, aralkyloxy group, aralkylcarbonyl group Aralkylcarbonyloxy group, aralkyloxycarbonyl group, hydroxyl group, amide group, carboxyl group, cyano group, fluorine atom and the like can be mentioned as examples.

B represents a single bond, an alkylene group, a cycloalkylene group or an aromatic group, and these alkylene group, cycloalkylene group and aromatic group may have a substituent. Here, the alkylene group, cycloalkylene group, and aromatic group are the same as those described above for A in the formula (3).
However, A and B are not both single bonds.

R _z each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a heteroatom, or an aromatic hydrocarbon group that may contain a heteroatom.
Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, aliphatic hydrocarbon groups and aromatic hydrocarbon groups include substituents (eg, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, halogen atoms, Atoms) may be included.
n represents an integer of 2 to 8, preferably an integer of 3 to 8.
In addition, it is preferable that the compound represented by the said Formula (3) has three or more nitrogen atoms. In this embodiment, when n is 2, A contains at least one nitrogen atom. That A contains a nitrogen atom includes, for example, at least one selected from the group consisting of the group represented by the above formula (1B), —NH—, and —NR _W —.

  Below, the compound represented by Formula (3) is illustrated.

Another preferred embodiment of the nitrogen-containing compound is preferably a polymer having an amino group in that the effect of the present invention is more excellent. In the present specification, the “amino group” is a concept including a primary amino group, a secondary amino group, and a tertiary amino group. The secondary amino group also includes cyclic secondary amino groups such as pyrrolidino group, piperidino group, piperazino group, hexahydrotriazino group and the like.
The amino group may be contained in either the main chain or the side chain of the polymer.
Specific examples of the side chain when the amino group is contained in a part of the side chain are shown below. In addition, * represents a connection part with a polymer.

  Examples of the polymer having an amino group include polyallylamine, polyethyleneimine, polyvinylpyridine, polyvinylimidazole, polypyrimidine, polytriazole, polyquinoline, polyindole, polypurine, polyvinylpyrrolidone, and polybenzimidazole.

  As a suitable aspect of the polymer which has an amino group, the polymer which has a repeating unit represented by Formula (2) is mentioned.

In formula (2), R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 4 is preferable and 1 to 2 is more preferable in that the effect of the present invention is more excellent.
R ² and R ³ are each independently a hydrogen atom, an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, or an aromatic group that may contain a hetero atom. Represents.
The number of carbon atoms contained in the alkyl group and cycloalkyl group is not particularly limited, but is preferably 1-20, and more preferably 1-10.
Examples of the aromatic group include aromatic hydrocarbons and aromatic heterocyclic groups.
The alkyl group, cycloalkyl group and aromatic group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, the alkyl group, cycloalkyl group, and aromatic group include substituents (eg, hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group functional group, alkoxy group, halogen Atoms) may be included.

L _a represents a divalent linking group. Definition of the divalent linking group represented by L _a is the same definition of L represented by the aforementioned formula (1-2).
Among these, in terms of more excellent effects of the present invention, L _a is an alkylene group, an arylene group, —COO—, or a group in which two or more of these are combined (-arylene group-alkylene group—, —COO— Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

Incidentally, the group represented by the above R ¹ to R ^3, and, in the divalent linking group represented by L _a, substituent group (e.g., hydroxyl, etc.) may be further substituted.

  Below, the repeating unit represented by Formula (2) is illustrated.

The content of the repeating unit represented by the above formula (2) in the polymer is not particularly limited, but is preferably 40 to 100 mol% with respect to all the repeating units in the polymer in that the effect of the present invention is more excellent. 70 to 100 mol% is more preferable.
In addition, other repeating units other than the repeating unit represented by Formula (2) may be contained in the polymer.

  Although the weight average molecular weight of the polymer which has an amino group is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

(Phosphorus compounds)
A phosphorus compound is a compound containing -P <(phosphorus atom). The phosphorus compound does not include an onium salt compound. The phosphorus compound mainly forms an interaction between a phosphorus atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with the phosphorus atom in the phosphorus compound to form a salt.
The phosphorus compound only needs to include at least one phosphorus atom, and may include a plurality (two or more).
The molecular weight of the phosphorus compound is not particularly limited, but is preferably 70 to 500, more preferably 70 to 300, from the viewpoint that the effect of the present invention is more excellent.

  A preferred embodiment of the phosphorus compound is selected from the group consisting of the compound represented by the following formula (4-1) and the compound represented by the formula (4-2) in that the effect of the present invention is more excellent. The phosphorus compound is preferable.

In formulas (4-1) and (4-2), R _W each independently represents an aliphatic hydrocarbon group that may contain a hetero atom, or an aromatic hydrocarbon group that may contain a hetero atom. Or represents a group selected from the group consisting of groups obtained by combining two or more of these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1). In addition, it is preferable that an oxygen atom is contained as a hetero atom, and it is preferable that it is contained in the aspect of -O-.

L _W represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, for example, an arylene group), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferable in that the effect of the present invention is more excellent.

  Below, the specific example of a phosphorus compound is illustrated.

The total mass of the above-mentioned additives in the developer is not particularly limited, but is preferably 0.1 to 5% by mass or less, and 1 to 5% by mass with respect to the total amount of the developer in terms of more excellent effects of the present invention. % Is more preferable, and 1-3 mass% is further more preferable.
In the present invention, as the above-mentioned additive, only one kind of compound may be used, or two or more kinds of compounds having different chemical structures may be used.

(Developer)
In step A, a developer containing water is used.
The developer used in step A contains water as a main component. The main component means that the water content exceeds 50% by mass with respect to the total amount of the developer.
As the developer, it is preferable to use an alkaline aqueous solution containing an alkali from the viewpoint of better pattern solubility.
The type of the alkaline aqueous solution is not particularly limited, and includes, for example, a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a cyclic amine, and the like. Alkaline aqueous solution etc. are mentioned. Among these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide is preferable.

Appropriate amounts of alcohols and surfactants can be added to the alkaline aqueous solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described later.
The alkali concentration of the aqueous alkali solution is usually 0.1 to 20% by mass.
The pH of the alkaline aqueous solution is usually 10.0 to 15.0.

In step B, a developer containing a soluble solvent (hereinafter also referred to as “organic developer” as appropriate) is used.
The developer used in Step B contains an organic solvent as a main component. The main component means that the content of the organic solvent is more than 50% by mass with respect to the total amount of the developer.
The organic solvent contained in the organic developer is not particularly limited, and examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. . Moreover, these mixed solvents may be sufficient.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Examples include 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, and propyl lactate. be able to.

  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, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

  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.

  In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents and ester solvents, and in particular, butyl acetate or ketone as the ester solvent. A developer containing methyl amyl ketone (2-heptanone) as a system solvent is preferred.

A plurality of organic solvents may be mixed, or may be used by mixing with other solvents or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved. As a result, dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The addition amount of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

(Development method)
As the developing method in the process A and the process B, for example, a method of immersing the substrate in a tank filled with the developer for a certain time (dip method), and raising the developer on the surface of the substrate by the surface tension and leaving it stationary for a certain time. The developing method (paddle method), the method of spraying the developer on the substrate surface (spray method), the developer is continuously discharged while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed. A method (dynamic dispensing method) or the like can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is As an example, it is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and still more preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. Details thereof are described in paragraphs [0022] to [0029] of JP 2010-232550 A in particular.
Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

(Rinse treatment)
After the development step, it is preferable to use a rinse solution as necessary.
The rinsing liquid is not particularly limited as long as the resist film is not dissolved, and a solution containing a general organic solvent can be used.

  The rinsing liquid is a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, it is a rinsing liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, alcohol solvents or ester solvents. More preferably, it is a rinsing liquid containing a monohydric alcohol, and most preferably a rinsing liquid containing a monohydric alcohol with 5 or more carbon atoms.

Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those of the organic developer described above.
Examples of the monohydric alcohol include linear, branched, and cyclic monohydric alcohols. More specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1 -Pentanol, 3-methyl-1-butanol and the like.
The rinse liquid may contain a plurality of solvents. Moreover, the rinse liquid may contain an organic solvent other than the above.

  The water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described above.

In the rinsing process, the wafer subjected to the organic solvent development is cleaned using the rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, a method of performing a cleaning process by a spin coating method, rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm after cleaning, and removing the rinse liquid from the substrate is preferable. Moreover, it is preferable to perform a heat treatment (Post Bake) after the rinsing treatment. The developer and the rinsing liquid remaining between the patterns and inside the patterns are removed by heat treatment. The heat treatment after the rinsing treatment is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
In general, the pattern obtained by the pattern forming method of the present invention is suitably used as an etching mask for a semiconductor device, but can also be used for other purposes. As other applications, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).

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

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

<Preparation of composition (composition for resist film formation)>
The components shown in Table 4 below were dissolved in the solvents shown in the same table to prepare a resist film forming composition. In addition, the ratio of the solvent in the following Table 4 intends mass ratio. Moreover, in the column of a resin and an additive, the location which has written together 2 types of components represents having used together by mass ratio 1: 1.

  The various components used in Table 4 are summarized below.

  In Table 5, the composition ratio indicates the molar ratio of the repeating units contained in the above-described resins P-1 to P-8, and the composition ratio of the repeating units in the chemical formula shown above is shown in order from the left.

  In Table 6, the composition ratio indicates the molar ratio of the repeating units contained in the above-described resins N-1 to N-3, and the composition ratio of the repeating units in the chemical formula shown above is shown in order from the left.

The following were used as the solvent.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: cyclohexanone SL-4: γ-butyrolactone

<Example 1>
<Example A>
On the silicon wafer, an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied and baked at 205 ° C. for 60 seconds. On top of this, the above resist film-forming composition was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.
The obtained resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As a reticle, a 6% halftone mask with line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Then, after baking (Post Exposure Bake; PEB) on the conditions of Table 7, it was cooled to room temperature. Next, it developed for 10 second using the 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution, and rinsed for 30 second with the pure water.
Subsequently, it developed for 20 second with the organic solvent developing solution containing the additive of Table 7, and rinsed for 10 second with 4-methyl-2- pentanol. Thereafter, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to obtain a line and space (L / S) resist pattern in which line patterns were arranged at equal intervals.

(Evaluation)
[Disconnection performance]
The obtained line and space pattern was observed using a length-measuring scanning electron microscope (SEM, Ltd., Hitachi, Ltd. S-9380II). There was no disconnection or the like, and the L / S pattern in which the line patterns were arranged at equal intervals The minimum half pitch formed was determined. A smaller value indicates that disconnection is less likely to occur even in a fine pattern.

[Evaluation of pattern thickness]
Regarding the resist pattern formed on the silicon wafer, the wafer was divided perpendicularly to the pattern with the smallest half pitch obtained by the disconnection performance, and the side surface of the pattern was assigned to a scanning electron microscope (Hitachi, Ltd. S-4800). The pattern film thickness was measured. A larger film thickness (nm) is preferable because it means that the amount of film reduction is small.

<Example B>
On the silicon wafer, an organic antireflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied and baked at 205 ° C. for 60 seconds. On top of this, the above resist film-forming composition was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.
The obtained resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As the reticle, one having the pattern shown in FIG. 3 was used (the black portion is a light-shielding portion. The dimensions shown in the figure are described based on the optical image at the time of projection). Moreover, ultrapure water was used as the immersion liquid.
Subsequently, after baking (Post Exposure Bake; PEB) under the conditions shown in Table 7, it was cooled to room temperature. Next, it developed for 10 second using 2.38 mass% TMAH aqueous solution, and rinsed for 30 second with the pure water.
Subsequently, it developed for 20 second with the organic solvent developing solution containing an additive of Table 7, and rinsed with 4-methyl-2-pentanol for 10 second. Thereafter, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a contact hole pattern having a pitch of 110 nm.

(Appearance evaluation)
The hole pattern with a pitch of 110 nm obtained by the pattern formation method was observed using a length measurement scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the pattern shape was in accordance with the following criteria. evaluated.
A: A pattern is formed without connecting holes.
B: Connection between holes is confirmed.

<Examples 2 to 30, Comparative Examples 1 to 8>
Except that the resist film forming composition, PEB temperature, developer, additive, etc. were changed as shown in Table 4, patterns were formed according to the same procedures as in Example 1 (Examples A and B), Evaluation was performed. The results are summarized in Table 7 below.
In Table 7, “1st PEB” intends the condition of Post Exposure Bake; PEB. For example, “85C60s” means that baking was performed at 85 ° C. for 60 seconds.
In Table 7, “2nd developer” indicates the type of organic solvent in the organic solvent developer.
In Table 7, “addition amount” indicates the content (wt%) of the additive in the organic solvent developer with respect to the total amount of the developer.
In Table 7, “MAK” intends methyl-n-amyl ketone (2-heptanone).

  The additives used in Table 7 are summarized below.

As shown in Table 7 above, when the pattern forming method of the present invention was carried out, film slippage was suppressed, and disconnection was less likely to occur even in a finer line and space pattern. Excellent results were also obtained in the formation of contact holes.
In particular, as can be seen from the comparison of Examples 1 to 4, it was confirmed that when the additive was added in a larger amount (1.0% by mass or more), a more excellent effect was obtained.
Moreover, as can be seen from the comparison of Examples 1, 6 to 9, and 16, among the nitrogen-containing compounds as additives, nitrogen-containing compounds having a plurality of nitrogen atoms are preferable in that the above effects are more excellent. More specifically, a nitrogen-containing compound having two or more nitrogen atoms is preferable (comparison with Examples 1 and 16), and a nitrogen-containing compound having three or more nitrogen atoms is more preferable (Examples 1 and 8). Comparison), a nitrogen-containing compound having 4 or more nitrogen atoms is more preferable.
Moreover, as can be seen from the comparison between Examples 1 and 6, it was confirmed that the effect of the present invention was more excellent when the carbon ratio of the nitrogen-containing compound was smaller (carbon ratio of 0.8 or less).
Further, as can be seen from a comparison between Examples 9 and 10, it was confirmed that when an amino group-containing polymer was used, an excellent effect was obtained with a small addition amount.
Further, as can be seen from a comparison between Examples 10 and 12, it was confirmed that the polymer having an onium salt exhibits a better effect than the polymer having an amino group.
Further, as can be seen from the comparison between Examples 11 and 12, it was confirmed that the polymer having an onium salt showed a better effect than the polyvalent onium salt compound.
On the other hand, in Comparative Examples 1 to 8 in which the predetermined additive was not used, film slip was greater than in Examples 1 to 30. In the line and space pattern, disconnection is likely to occur in a larger pattern, and in the contact hole pattern, connection between holes is likely to occur.

<Example 31>
<Example C>
On the silicon wafer, an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied and baked at 205 ° C. for 60 seconds. On top of this, the above resist film-forming composition was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.
The obtained resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As a reticle, a 6% halftone mask with line: space = 1: 1 was used. Moreover, ultrapure water was used as the immersion liquid.
Subsequently, after baking (Post Exposure Bake; PEB) on the conditions of Table 8, it was made to cool to room temperature. Then, it developed for 20 second with the organic solvent developing solution containing the additive of Table 8, and rinsed for 10 second with 4-methyl-2- pentanol. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds.
Next, development was carried out for 10 seconds using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution, followed by rinsing with pure water for 30 seconds to obtain a line and space (L / S) resist pattern.

(Evaluation)
[Disconnection performance]
The obtained line and space pattern was observed using a length-measuring scanning electron microscope (SEM, Ltd., Hitachi, Ltd. S-9380II). There was no disconnection or the like, and the L / S pattern in which the line patterns were arranged at equal intervals The minimum half pitch formed was determined. A smaller value indicates that disconnection is less likely to occur even in a fine pattern.

[Evaluation of pattern thickness]
Regarding the resist pattern formed on the silicon wafer, the wafer was divided perpendicularly to the pattern with the smallest half pitch obtained by the disconnection performance, and the side surface of the pattern was assigned to a scanning electron microscope (Hitachi, Ltd. S-4800). The pattern film thickness was measured. A larger film thickness (nm) is preferable because it means that the amount of film reduction is small.

<Example D>
On the silicon wafer, an organic antireflection film ARC29A (manufactured by Nissan Chemical Co., Ltd.) was applied and baked at 205 ° C. for 60 seconds. On top of this, the above resist film-forming composition was applied and baked at 90 ° C. for 60 seconds. Thereby, a resist film having a film thickness of 85 nm was formed.
The obtained resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, C-Quad, outer sigma 0.960, inner sigma 0.709, XY deflection). went. As the reticle, one having the pattern shown in FIG. 3 was used (the black portion is a light-shielding portion. The dimensions shown in the figure are described based on the optical image at the time of projection). Moreover, ultrapure water was used as the immersion liquid.
Then, after baking (Post Exposure Bake; PEB) on the conditions of Table 8, it was cooled to room temperature. Then, it developed for 20 second with the organic solvent developing solution containing the additive of Table 8, and rinsed for 10 second with 4-methyl-2- pentanol. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds.
Next, it developed for 10 seconds using 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution, and rinsed with the pure water for 30 seconds, and the contact hole pattern with a pitch of 110 nm was formed.

(Appearance evaluation)
The hole pattern with a pitch of 110 nm obtained by the pattern formation method was observed using a length measurement scanning electron microscope (SEM, Hitachi, Ltd. S-9380II), and the pattern shape was in accordance with the following criteria. evaluated.
A: A pattern is formed without connecting holes.
B: Connection between holes is confirmed.

<Examples 32-37 and Comparative Examples 9-11>
Except for changing the resist film forming composition, PEB temperature, developer, additive and the like as shown in Table 8, patterns were formed according to the same procedures as in Example 31 (Examples C and D), Evaluation was performed. The results are summarized in Table 8 below.
In Table 8, “1st PEB” intends the condition of Post Exposure Bake; PEB. For example, “85C60s” means that baking was performed at 85 ° C. for 60 seconds.
In Table 8, “1st developer” indicates the type of organic solvent in the organic solvent developer.
In Table 8, “addition amount” indicates the content (wt%) of the additive in the organic solvent developer with respect to the total amount of the developer.
In Table 8, “MAK” intends methyl-n-amyl ketone (2-heptanone).

As shown in Table 8 above, it was confirmed that the desired effect was obtained even in an embodiment in which development was performed with a developer containing an organic solvent and then development was performed with a developer containing water.
On the other hand, in Comparative Examples 9 to 11 in which the predetermined additive was not used, the film slip was larger than those in Examples 31 to 37. In the line and space pattern, disconnection is likely to occur in a larger pattern, and in the contact hole pattern, connection between holes is likely to occur.

  In addition, although the Example which performs exposure by an ArF excimer laser immersion scanner was shown above, it can be anticipated that there exists the same effect also in the aspect performed by EUV exposure besides that.

10 substrates 12, 14 patterns

Claims (7)

A step (1) of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition containing at least a resin having a group capable of decomposing by the action of an acid to generate a polar group;
Exposing the film (2);
Developing the exposed film to form a pattern (3),
The step (3) is a step of performing any one of the step A with a developer containing water and the step B with a developer containing an organic solvent, and then performing the other step.
A developer containing an organic solvent, an ionic bond, hydrogen bond, at least one interaction of the contact and dipole interactions, include additives to form said polar group,
The pattern forming method, wherein the additive comprises at least one selected from the group consisting of an onium salt compound, a phosphorus compound, a polymer having an amino group, and a nitrogen-containing compound having three or more nitrogen atoms.   The pattern forming method according to claim 1, wherein the additive comprises at least one selected from the group consisting of an onium salt compound, a phosphorus compound, and a polymer having an amino group.   The pattern formation method of Claim 1 or 2 whose polymer which has the said amino group is a polymer which has a repeating unit represented by Formula (2).

(In formula (2), R ¹ Represents a hydrogen atom or an alkyl group. R ² And R ^Three Each independently represents a hydrogen atom, an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, or an aromatic group that may contain a heteroatom. L _a Represents a divalent linking group. R ² And R ^Three May combine with each other to form a ring. ) The step (3) is a step of performing the step A and the step B in this order,
The step A rich regions exposure amount by the exposure in the film is dissolved by the process zone is small exposure amount by the exposure in the film by B is dissolved, either of claims 1-3 1 The pattern forming method according to item . The onium salt compound is an onium salt represented by formula (1-1), an onium salt represented by formula (1-2), and a polymer having a repeating unit represented by formula (5-1). The pattern forming method according to claim 1, wherein the pattern forming method is at least one selected from the group consisting of:

(In formula (1-1) and formula (1-2), M represents a nitrogen atom, a phosphorus atom, a sulfur atom, or an iodine atom. R each independently contains a hydrogen atom or a heteroatom. Represents an aliphatic hydrocarbon group that may be present, an aromatic hydrocarbon group that may contain a hetero atom, or a group in which two or more of these are combined, and X ⁻ represents a monovalent anion.
In formula (1-1), n represents an integer of 2 to 4. In addition, when M is a nitrogen atom or a phosphorus atom, n represents 4, when M is a sulfur atom, n represents 3, and when M is an iodine atom, n represents 2.
In formula (1-2), L represents a divalent linking group.
In formula (1-2), m represents the integer of 1-3 each independently. In addition, when M is a nitrogen atom or a phosphorus atom, m represents 3, when M is a sulfur atom, m represents 2, and when M is an iodine atom, m represents 1.
A plurality of R may be bonded to each other to form a ring.
In formula (5-1), R _p represents a hydrogen atom or an alkyl group. L _p represents a divalent linking group. A _p represents formula (1-1) and residue obtained by removing one hydrogen atom from an onium salt represented by any one of formula (1-2). ) The nitrogen-containing compound having a nitrogen atom three or more, a compound represented by the formula (3), the pattern forming method according to any one of claims 1 to 5.

(In Formula (3), A represents a single bond or an n-valent organic group. B represents a single bond, an alkylene group, a cycloalkylene group, or an aromatic group, and the alkylene group, the cycloalkylene group. Alternatively, the aromatic group may have a substituent, and each R _z independently represents a hydrogen atom, an alkyl group that may contain a hetero atom, or a cycloalkyl that may contain a hetero atom. Represents an aromatic group which may contain a group or a hetero atom, n represents an integer of 3 to 8. A plurality of B may be the same or different from each other, provided that both A and B are single. Never a bond.) The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-6 .