TW201335711A - Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, resist film, method for manufacturing electronic device, and electronic device - Google Patents

Abstract

There is provided a pattern forming method, including: (a) forming a film by an actinic ray-sensitive or radiation-sensitive resin composition containing: (A) a resin capable of increasing polarity by an action of an acid to decrease solubility in an organic solvent-containing developer, (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, (C) a solvent, and (D) a resin, which contains substantially no fluorine atom and silicon atom and is other than the resin (A), (b) exposing the film; and (c) performing development using the organic solvent-containing developer to form a negative type pattern, wherein a receding contact angle of water on the film formed by (a) is 70 DEG or more.

Description

Pattern forming method, sensitizing ray or radiation sensitive resin composition, resist film, method of manufacturing electronic component, and electronic component

The present invention relates to a pattern forming method, a sensitized ray- or radiation-sensitive resin composition, a resist film, a method of manufacturing an electronic component, and an electronic component. More particularly, the present invention relates to a pattern forming method suitable for a manufacturing process of a semiconductor such as an IC, a manufacturing process of a liquid crystal, a thermal head or the like, and a photofabrication process. Other lithography processes; a sensitized ray- or radiation-sensitive resin composition; a resist film; a method of manufacturing an electronic component; and an electronic component. In particular, the present invention relates to a pattern forming method suitable for exposure using an ArF exposure apparatus or an ArF immersion type projection exposure apparatus and an EUV exposure apparatus, the ArF exposure apparatus or the ArF immersion type projection exposure apparatus using a wavelength of 300 nm or less than 300 nm far ultraviolet rays as a light source; a sensitized ray- or radiation-sensitive resin composition; a resist film; an electric a method of manufacturing a sub-element; and an electronic component.

Since the development of a resist for KrF excimer laser (248 nm), an image formation method called chemical amplification has been used as an image forming method for resists to compensate for light absorption. Desensitization. In exemplifying and describing a positive-type chemically amplified image forming method, the method is an image forming method in which an acid generator in an exposed portion is decomposed to generate an acid by exposure, and then by exposure In the Post Exposure Bake (PEB), the generated acid was used as a reaction catalyst, and the alkali-insoluble group was changed to an alkali-soluble group to remove the exposed portion by alkali development. A positive image forming method using a chemical amplification mechanism has become mainstream.

Further, in order to achieve a high resolution by further shortening the wavelength, a so-called impregnation method is known in which a space having a high refractive index is filled in a space between a projection lens and a test sample (hereinafter, also It is called "immersion liquid". For example, Japanese Patent Application Laid-Open No. 2008-268933 describes an example in which a resin having a specific acid-decomposable repeating unit and a fluorine-free atom and a germanium atom are contained in a positive resist composition. Specific resins to improve the follow-up property.

However, in the positive image forming method described above, the isolation line or the dot pattern can be favorably formed, but the shape of the pattern is easily deteriorated when the isolation spacer or the fine pattern is formed.

Therefore, in order to further refine the pattern, a technique has recently been known in which an organic developer is used for a chemically amplified resist group. A negative resist pattern is analyzed by a resist film obtained as a positive resist composition of the current mainstream. As the technique, for example, in a negative pattern forming method using an impregnation method using an organic type developer, a technique of adding a resin containing a ruthenium atom or a fluorine atom is known (see, for example, Japanese Patent Application Laid-Open No. 2008) -309879).

However, recently, the demand for a fine pattern having a line width of 60 nm or less is sharply increased, and in response to this, a line width is formed on the resist film by using an organic developing solution by a dipping method. When a fine negative pattern of 60 nm or less is used, it is necessary to further improve the uniformity of the film thickness and further reduce bridge defects and watermark defects.

The present invention has been made in view of the above problems, and an object thereof is to provide a pattern forming method in which a line width of 60 nm or less is formed by using an organic type developer by a dipping method. The fineness of the film is excellent in the uniformity of the film thickness and suppresses the occurrence of bridging defects and watermark defects; a sensitizing ray-sensitive or radiation-sensitive resin composition used; a resist film; a method of manufacturing an electronic component; An electronic component.

The present invention has the following configurations, and thus achieves the objects of the present invention.

(1) A pattern forming method comprising: (a) forming a film by using a photosensitive ray-sensitive or radiation-sensitive resin composition containing: capable of increasing polarity under an action of an acid to reduce an organic solvent The solubility of the resin (A) in the developer can produce an acid compound after irradiation with actinic rays or radiation, (B), solvent (C), and substantially no fluorine atom and germanium atom and are different from the resin. (A) a resin (D); (b) exposing the film; and (c) developing by using an organic solvent-containing developer to form a negative pattern in which water is formed by the film formed by (a) The upper receding contact angle is 70 degrees or greater.

(2) The method according to (1), wherein the solvent (C) is a mixed solvent containing two or more solvents, the two or more solvents having at least one boiling point of 200 ° C or more Solvent.

(3) The method according to (2), wherein the at least one solvent having a boiling point of 200 ° C or more is a solvent represented by one of the formulae (S1) to (S3):

Wherein R ₁ to R ₄ and R ₆ to R ₈ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₇ and R ₈ may be bonded to each other to form a bond. ring.

(4) The method according to (2) or (3), wherein the at least one solvent having a boiling point of 200 ° C or more is contained in an amount of 1% by mass or more based on the mixed solvent.

(5) The method according to any one of (1) to (4) wherein the resin (A) contains a repeating unit comprising a group capable of decomposing to generate a polar group under the action of an acid, and the repeating unit is composed of at least one Composition of repeating units represented by formula (I):

Wherein R ₀ represents a hydrogen atom or an alkyl group, and R ₁ to R ₃ each independently represent an alkyl group or a cycloalkyl group, and two of R ₁ to R ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group.

(6) The method according to any one of (1) to (5) wherein the resin (D) has at least one repeating unit represented by the following formula (II) or formula (III):

Wherein, in the formula (II), R ₂₁ to R ₂₃ each independently represent a hydrogen atom or an alkyl group, Ar ₂₁ represents an aromatic group, and R ₂₂ and Ar ₂₁ may form a ring, and in that case, R ₂₂ represents An alkyl group, in the formula (III), R ₃₁ to R ₃₃ each independently represent a hydrogen atom or an alkyl group, X ₃₁ represents -O- or -NR ₃₅ -, R ₃₅ represents a hydrogen atom or an alkyl group, and R ₃₄ Represents an alkyl or cycloalkyl group.

(7) The method according to (6), wherein the content of the repeating unit represented by the formula (II) or the formula (III) is from 50 mol% to 100 mol% based on all the repeating units in the resin (D).

(8) The method according to any one of (1) to (7) wherein the developer containing the organic solvent is a developer containing at least one organic solvent selected from the group consisting of: a ketone solvent, An ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

(9) The method according to any one of (1) to (8), further comprising: (d) washing by using a rinsing solution containing an organic solvent.

(10) The method according to any one of (1) to (9) wherein the exposure in (b) is immersion exposure.

(11) A photosensitive ray-sensitive or radiation-sensitive resin composition for use in the method according to (2).

(12) A photosensitive ray-sensitive or radiation-sensitive resin composition for use in the method according to (3).

(13) A photosensitive ray-sensitive or radiation-sensitive resin composition for use in the method according to (4).

(14) A sensitizing ray-sensitive or radiation-sensitive resin composition for use in the method according to (5).

(15) A photosensitive ray-sensitive or radiation-sensitive resin composition for use in the method according to (6).

(16) A photosensitive ray-sensitive or radiation-sensitive resin composition for use in the method according to (7).

(17) A resist film formed of the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of (11) to (16).

(18) A method of producing an electronic component, comprising the method according to any one of (1) to (10).

(19) An electronic component manufactured by the method according to (18).

The invention further preferably has the following components.

(20) The pattern forming method according to any one of (1) to (10), wherein the resin (D) has a ClogP value of 2.8 or more.

(21) The pattern forming method according to any one of (1) to (10), wherein the resin (D) contains a repeating unit corresponding to a monomer having a ClogP value of 2.8 or more.

(22) The pattern forming method according to any one of (1) to (10), wherein the resin (D) has a structure having 3 or more than 3 CH ₃ moieties in a side chain. Repeat unit.

(23) A pattern forming method according to any one of (1) to (10) and (20) to (22), wherein the resin (D) does not have a repeating unit containing an acid-decomposable group.

(24) A pattern forming method according to any one of (1) to (10) and (20) to (23), wherein the resin (D) does not have a repeating unit containing an acid group (alkali-soluble group).

(25) A pattern forming method according to any one of (1) to (10) and (20) to (24), wherein the resin (D) does not have a repeating unit having a lactone structure.

(26) The pattern forming method according to any one of (1) to (10), wherein the exposure in (b) is ArF exposure.

(27) A pattern forming method according to any one of (1) to (10), wherein the resin (A) contains a repeating unit having a structure capable of generating an alcoholic hydroxyl group in a side chain as A repeating unit containing an acid decomposable group.

(28) The pattern forming method according to any one of (1) to (10), wherein the compound (B) is a compound represented by the formula (ZI-4'):

Wherein, in the formula (ZI-4'), R ₁₃ ' represents a branched alkyl group, and R ₁₄ each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group in the presence of a plurality of R ₁₄ groups. , alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl or a group having a cycloalkyl group, R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and two R ₁₅ groups may be bonded A ring is formed, l represents an integer from 0 to 2, r represents an integer from 0 to 8, and Z ^- represents a non-nucleophilic anion.

(29) The pattern forming method according to any one of (1) to (10), wherein the compound (B) is a compound represented by the formula (ZI) or the formula (ZII):

Wherein R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group, and two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded to form a ring, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, The indole bond and the carbonyl group, R ₂₀₄ and R ₂₀₅ each independently represent an aryl group, an alkyl group or a cycloalkyl group, and Z ^- represents a non-nucleophilic anion.

(30) The pattern forming method according to (29), wherein the non-nucleophilic anion of Z ^- is an anion capable of producing an organic acid represented by the formula (III) or (IV):

Wherein each Ef independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and each L 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 20, and z represents an integer of 0 to 10.

(31) The pattern forming method according to (30), wherein the cyclic organic group of Cy is a group containing a steroid backbone.

(32) The pattern forming method according to (29), wherein the non-nucleophilic anion of Z ^- is a sulfonate anion represented by the formula (B-1):

Wherein each R _b1 independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ), n represents an integer of 0 to 4, and X _b1 represents a single bond, an alkyl group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate linkage (-OSO ₂ - or -SO ₂ -) or a combination thereof, and R _b2 represents an organic group having 6 or more carbon atoms.

(33) The pattern forming method according to any one of (1) to (10), wherein the sensitizing ray-sensitive or radiation-sensitive resin composition further contains N-alkyl caprolactam .

(34) A photosensitive ray-sensitive or radiation-sensitive resin composition according to any one of (11) to (16), wherein the composition is a chemically amplified resist composition for developing an organic solvent.

(35) A sensitizing ray-sensitive or radiation-sensitive resin composition according to any one of (11) to (16), wherein the composition is for immersion exposure Composition.

According to the present invention, it is possible to provide a pattern forming method in which uniformity of film thickness is excellent when a fine pattern having a line width of 60 nm or less is formed by using an organic developer by a dipping method. And suppressing the occurrence of bridging defects and watermark defects; a photosensitive ray or radiation sensitive resin composition used therein; a resist film; a method of manufacturing an electronic component; and an electronic component.

Hereinafter, embodiments of the invention will be described in detail.

When a group (atomic group) is represented in the specification of the present invention, it is not described that the substituted and unsubstituted representation also includes a substituent and no substituent. For example, "an 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, the term "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, and an extreme ultraviolet ray. (extreme ultraviolet; EUV) rays, X-rays, electron beams (EB) and the like. Further, in the present invention, the term "light" means actinic rays or radiation.

In addition, unless otherwise specifically indicated, in the specification of the present invention, the term "exposure" includes not only mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV rays, and the like. Exposure is performed and also includes mapping by particle beams such as electron beams and ion beams.

The pattern forming method of the present invention comprises (a) forming a film by a sensitizing ray-sensitive or radiation-sensitive resin composition containing a substance capable of increasing polarity under an action of an acid to lower it in a developer containing an organic solvent The solubility resin (A) is a compound (B) capable of generating an acid after irradiation with actinic rays or radiation, a solvent (C), and a resin substantially free of fluorine atoms and germanium atoms and different from the resin (A). (D); (b) exposing the film; and (c) developing using a developer containing an organic solvent to form a negative pattern in which the receding contact angle of water on the film formed of (a) is 70 degrees Or greater than 70 degrees.

The pattern forming method of the present invention has excellent film thickness uniformity and suppresses bridging defects and watermarks by forming a negative pattern by using a developer containing an organic solvent to form a fine pattern having a line width of 60 nm or less. The reason for the occurrence of the defect is not clear, but it is assumed that in the pattern forming method of the present invention, the sensitization of the resin (D) containing substantially no fluorine atom and germanium atom is used in the film formation step (a). The film-forming water formed by the ray- or radiation-sensitive resin composition has a receding contact angle of 70 degrees or more.

In the positive type impregnation method of the related art, in order to solve the adverse effect caused by the use of the immersion liquid, a method of mixing a small amount of a low surface in the resist composition in addition to the main resin is carried out. Free energy and high hydrophobicity A resin (hereinafter simply referred to as "hydrophobic resin") is used to place the hydrophobic resin at the surface of the resist film. Here, it is required that a resin having low surface free energy and high hydrophobicity can be dissolved in an alkali developer even when developing, and therefore, the hydrophobic resin needs to be, for example, by having a group capable of generating an alkali-soluble group and the like. Further, it is alkali-soluble, and therefore, it is necessary to contain a fluorine atom and a ruthenium atom in the hydrophobic resin from the viewpoint of achieving high hydrophobicity (and low surface free energy).

However, when the resin in the resist composition contains a fluorine atom and a ruthenium atom, the contact angle characteristics of the immersion liquid are impaired and the immersion liquid remains as water droplets during the exposure scanning, and thus, there is a watermark defect after development. The problem.

In contrast, in the negative pattern forming method according to the present invention for developing using a developer containing an organic solvent, in order to solve the adverse effect caused by the use of the immersion liquid, a small amount of hydrophobic resin contained in the resist composition is contained. The above alkali solubility is not required, and thus, it is not even necessary to have a fluorine atom and a germanium atom. In addition, it does not substantially have a fluorine atom and a ruthenium atom, so that the problem caused by the ruthenium atom and the ruthenium atom is solved, and thus the back contact angle of the immersion liquid can be improved, and the contact angle characteristic of the immersion liquid can also be improved (minus The difference between the small advancing contact angle and the receding contact angle). As described above, assuming that there is no fluorine atom and helium atom and the receding contact angle is set to 70 degrees or more, the method can be applied to the dipping method, thereby reducing watermark defects.

Further, when a small amount of the hydrophobic resin contained in the resist composition has a fluorine atom and a ruthenium atom, the solubility of the hydrophobic resin in the solvent (C) is reduced, and thus is formed by the film formation step (a). The film may also cause damage to the uniformity of the film thickness.

On the contrary, it is assumed that the resin (D) in the present invention does not substantially have a fluorine atom and a ruthenium atom, and therefore its solubility in the solvent (C) is excellent and the film formed by the film formation step (a) also has an excellent film thickness. Uniformity.

Further, in the case of exposing a resist film formed by using a photosensitive ray- or radiation-sensitive resin composition containing the compound (B) (hereinafter also referred to as an acid generator), the top portion of the resist film is exposed. The degree of exposure and the concentration of the generated acid are higher than the internal portion thereof, and thus the reaction between the acid and the resin (A) tends to proceed further. Further, when the exposed film is developed using a developer containing an organic solvent, there is a concern that the pattern shape may be deteriorated.

In contrast, in the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, it is assumed that the resin (D) which is substantially free of fluorine atoms and germanium atoms is easily unevenly distributed in the top portion of the resist film.

The resin (D) is unevenly distributed at a high concentration in the top portion of the resist film, and thus the solubility of the top portion of the resist film in the developer containing the organic solvent is improved. Thus, it is assumed that the deterioration of the pattern shape caused by the excessively generated acid can be counteracted or suppressed by the resin (D) improving its solubility in the developer containing the organic solvent, which is unevenly distributed in the exposed portion. In the top layer.

Also, it is assumed that the factor of the bridging defect may be a resin component which is slightly soluble in the developer containing the organic solvent at the surface of the resist film.

As described above, it is assumed that the resin (D) tends to be located at the surface portion of the resist film, and thus the solubility of the surface portion of the resist film in the developer containing the organic solvent is enhanced. Thus, it is assumed that components which are slightly soluble in the organic solvent-containing developer which may be a factor of bridging defects can be dissolved and removed.

Further, as described above, in the positive image forming method, there is a pattern A fine pattern in which the shape is easily deteriorated and it is substantially difficult to form a pattern. This is caused by the fact that when the pattern is formed by the positive image forming method, the region on which the pattern is formed becomes the exposed portion, but it is optically difficult to expose the fine exposed portion and it is difficult to analyze the portion.

In the pattern forming method of the present invention, the developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. And an ether solvent.

The pattern forming method of the present invention preferably further comprises (d) washing with a rinsing liquid containing an organic solvent.

The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The pattern forming method of the present invention preferably has (e) a heating step after the exposure step (b).

In the pattern forming method of the present invention, the resin (A) is a resin capable of increasing the polarity under the action of an acid to increase the solubility in the alkali developer, and the method may further have (f) development using an alkali developer.

The pattern forming method of the present invention may have a multiple exposure step (b).

The pattern forming method of the present invention may have a plurality of heating steps (e).

The resist film of the present invention is a film formed of a sensitized ray-sensitive or radiation-sensitive resin composition, and a film formed by, for example, applying a sensitizing ray-sensitive or radiation-sensitive resin composition onto a substrate.

Hereinafter, a photosensitive ray-sensitive or radiation-sensitive resin composition which can be used in the present invention will be described.

Further, the present invention also relates to a photosensitive ray-sensitive or radiation-sensitive resin composition which will be described hereinafter.

In negative development (in the case where the resist film is exposed, its solubility in the developer is reduced, and thus the exposed portion remains as a pattern to remove the development of the unexposed portion), especially on the resist film When a fine pattern having a line width of, for example, 60 nm or less is formed, the sensitized ray-sensitive or radiation-sensitive resin composition according to the present invention is used. That is, the sensitizing ray-sensitive or radiation-sensitive resin composition relating to the present invention can be used as a sensitizing ray- or radiation-sensitive resin composition for developing an organic solvent, which is used for the use of an organic solvent-containing compound. The developer is developed. Here, the term for organic solvent development refers to the use in the step of developing using a developer containing at least one organic solvent.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably usually a resist composition, and a negative resist composition can be obtained from the viewpoint of obtaining particularly excellent effects (i.e., for Organic solvent developed resist composition). Further, the composition related to the present invention is usually a chemically amplified resist composition.

In general, the negative image forming method using a developer containing an organic solvent has a lower contrast ratio of the unexposed portion to the exposed portion to the developer than the positive image forming method using the alkali developer. Therefore, in order to form a fine pattern, a negative image forming method is employed for the above reasons, but the negative image forming method changes due to the acid concentration in the film thickness direction of the exposed portion of the resist film (ie, the fact that an acid excess exists) The effect in the top portion of the exposed portion is greater than the positive image forming method in which the unexposed portion and the exposed portion are relatively large in contrast to the dissolution of the developer.

Therefore, the present invention can solve the film thickness unevenness which is easily apparent in the negative image forming method, and thus, its technical importance is large, which is due to It is excellent in film thickness uniformity while forming a fine pattern.

[1] (A) a resin capable of increasing polarity under the action of an acid to lower its solubility in a developer containing an organic solvent

As a resin for use in a photosensitive ray-sensitive or radiation-sensitive resin composition according to the present invention which is capable of increasing polarity under the action of an acid to lower its solubility in a developer containing an organic solvent, an example thereof is included in the main resin. a chain or a side chain or a resin having a group capable of decomposing under an acid to generate a polar group (hereinafter also referred to as an "acid-decomposable group") in the main chain and the side chain ( Hereinafter also referred to as "acid-decomposable resin" or "resin (A)").

The acid-decomposable group preferably has a structure protected by a group capable of decomposing under the action of an acid and leaving a polar group.

The polar group is not particularly limited as long as the group is a group which is sparingly soluble or insoluble in a developer containing an organic solvent, but examples thereof include an acidic group (at 2.38% by mass of tetramethylammonium hydroxide) a group dissociated in an aqueous solution, which is used as a developer of a resist in the related art, such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) ), sulfonic acid group, sulfonylamino group, sulfonimido group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) fluorenylene group, Bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)indolylene, tris(alkyl) A carbonyl)methylene group and a tris(alkylsulfonyl)methylene group, an alcoholic hydroxyl group or the like.

Further, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and the alcoholic hydroxyl group does not contain an α-position electron withdrawing group (such as a fluorine atom-substituted aliphatic alcohol (for example, a fluorinated alcohol group) (hexafluoroisopropanol group or the like)) as a hydroxyl group. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of from 12 to 20.

Examples of preferred polar groups include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferred acid-decomposable group is a group obtained by substituting a hydrogen atom of a group with a group capable of leaving under the action of an acid.

Examples of groups capable of leaving under the action of 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 similar groups.

In the above formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, and a second butyl group. , hexyl, octyl and the like.

The cycloalkyl group of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ may be a monocyclic or polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, an anthracenyl group, a dicyclopentyl group, and an α-fluorene group. A tricyclic fluorenyl group, a tetracyclododecyl group, an androstyl group, and the like. Additionally, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R ₃₆ to R ₃₉ and 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, an anthracenyl group and the like.

The aralkyl group of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and the like. .

The alkenyl group of R ₃₆ to R ₃₉ and R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like. Group.

The ring formed by combining R ₃₆ and R ₃₇ with each other is preferably a cycloalkyl group (monocyclic or polycyclic). As a cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group, a tetracyclododecyl group, and an adamantyl group are Good. 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.

As the acid-decomposable group, a cumene ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, and the like are preferable. The group is more preferably a tertiary alkyl ester group.

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

As the repeating unit having an acid-decomposable group contained in the resin (A), a repeating unit represented by the following formula (I) is preferable.

In the formula (I), R ₀ represents a hydrogen atom or a linear or branched alkyl group. R ₁ to R ₃ each independently represent a linear or branched alkyl group, or a monocyclic or polycyclic cycloalkyl group.

Two of R ₁ to R ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group.

The linear or branched alkyl group related to R ₀ may have a substituent and is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, isobutyl, tert-butyl and the like. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), and the like.

R _{0 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The alkyl group of R ₁ to R ₃ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or the like having 1 to 4 carbon atoms. .

The cycloalkyl group of R ₁ to R ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group or a tetracyclododecyl group. And adamantyl).

The cycloalkyl group formed by combining two of R ₁ to R ₃ is preferably a monocyclic cycloalkyl group (such as a cyclopentyl group and a cyclohexyl group) or a polycyclic cycloalkyl group (such as a norbornyl group, four). Cyclodecyl, tetracyclododecyl and adamantyl). Monocyclic cycloalkyl groups having 5 or 6 carbon atoms are especially preferred.

An example of a preferred aspect includes the following, wherein R ₁ is a methyl group or an ethyl group, and R ₂ to R ₃ are bonded to each other to form the above cycloalkyl group.

Each group may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group (having 1 to 4 carbon atoms), and a cycloalkyl group (having 3 to 8 carbon atoms). Alkoxy (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), and the like, and having 8 or less carbon atoms is a group having Preferably.

A particularly preferred aspect of the repeating unit represented by the formula (I) is that R ₁ , R ₂ and R ₃ each independently represent a linear or branched alkyl group.

In this aspect, the linear or branched alkyl group related to R ₁ , R ₂ and R _{3 is} preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a positive group. Propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

R _{1 is} preferably a methyl group, an ethyl group, a n-propyl group or a n-butyl group, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group.

R _{2 is} preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group.

R _{3 is} preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, more preferably methyl, ethyl, isopropyl and isobutyl, and Particularly preferred are methyl, ethyl and isopropyl.

Preferred specific examples of the repeating unit having an acid-decomposable group will be described below, but the invention is not limited to the examples.

In specific examples, Rx represents a hydrogen atom, CH _3, CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent, and when a plurality of Z are present, each Z may be the same or different from all other Z. p represents 0 or a positive integer. Specific and preferred examples of Z are the same as specific and preferred examples of substituents and the like which may have each of R ₁ to R ₃ .

In the case where the resin (A) contains a repeating unit represented by the formula (I) as a repeating unit having an acid-decomposable group, the repeating unit having an acid group preferably has only at least one repeating unit represented by the formula (I) composition.

Further, the repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (IB), which decomposes under the action of an acid to give a carboxyl group, and thus, can provide roughness performance (such as line width roughness). A pattern forming method in which the uniformity of the partial pattern size and the exposure latitude are excellent and the film thickness reduction of the pattern portion formed by development (so-called film reduction) can be further suppressed.

In the above formula, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

Ry ₁ to Ry ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Ry ₁ to Ry ₃ may be bonded to each other to form a ring.

Z represents a linking group having a polycyclic hydrocarbon structure which may have a hetero atom as a (n+1) valence ring member.

L ₁ and L ₂ each independently represent a single bond or a divalent linking group. n represents an integer from 1 to 3.

When n is 2 or 3, each of L ₂ , Ry ₁ , Ry ₂ and Ry ₃ may be the same as or different from all other L ₂ , Ry ₁ , Ry ₂ and Ry ₃ .

The alkyl group of Xa 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 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, a trifluoromethyl group or the like, but the methyl group is Good.

Xa is preferably a hydrogen atom or a methyl group.

The alkyl group of Ry ₁ to Ry ₃ may be a linear or branched alkyl group, and is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or have A similar group of 1 to 4 carbon atoms.

The cycloalkyl group of Ry ₁ to Ry ₃ is preferably a monocyclic cycloalkyl group (such as a cyclopentyl group, a cyclohexyl group, and the like) and a polycyclic cycloalkyl group (such as a norbornyl group, a tetracyclic fluorenyl group, or a tetracyclic ring). Dodecyl and adamantyl).

The ring formed by combining the two of Ry ₁ to Ry ₃ is preferably a monocyclic hydrocarbon ring such as a cyclopentane ring, a cyclohexane ring and the like; and a polycyclic hydrocarbon ring such as a norbornane ring; (norbornane ring), tetracyclodecane ring, tetracyclododecane ring, adamantane ring and the like. A monocyclic hydrocarbon group having 5 or 6 carbon atoms is particularly preferred.

Ry ₁ to Ry ₃ are each independently an alkyl group, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the total number of carbon atoms as a linear or branched alkyl group of Ry ₁ to Ry ₃ is preferably 5 or less.

Ry ₁ to Ry ₃ may have a more substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, an alkoxy group. Preferred groups (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like, and having 8 or less carbon atoms are preferred. Among them, from the viewpoint of further improving the dissolution ratio before and after the acid decomposition in the developer containing the organic solvent, the substituent is more preferably a substituent having no hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom ( For example, the substituent is more preferably an alkyl group substituted by a hydroxyl group and the like, more preferably a group consisting only of a hydrogen atom and a carbon atom, and particularly preferably a linear or branched alkyl group and a cycloalkane. base.

The linking group having a polycyclic hydrocarbon structure of Z includes a ring assembly hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group, and examples thereof respectively include any removal by a self-loop combination hydrocarbon ring A group obtained by (n+1) hydrogen atoms and a group obtained by removing any (n+1) hydrogen atoms from the cross-linked cyclic hydrocarbon ring.

Examples of the ring-combined hydrocarbon ring group include a bicyclohexane ring group, a perhydronaphthalene ring group, and the like. Examples of the cross-linked cyclic hydrocarbon ring group include a bicyclic hydrocarbon ring group such as a decane ring group, a norbornane ring group, a norbornane ring group, a norbornane ring group, and a bicyclooctane ring group ( Bicyclo[2.2.2]octane ring group, bicyclo[3.2.1]octane ring group and the like); tricyclic hydrocarbon ring group, such as homobledane ring group, diamond An alkane group, a tricyclo[5.2.1.0 ^2,6 ]decane ring group and a tricyclo[4.3.1.1 ^2,5 ]undecane ring group; a tetracyclic hydrocarbon ring group such as a tetracyclic ring [4.4 .0.1 ^2,5 .1 ^7,10 ]dodecane ring group and perhydro-1,4-methylene-5,8-methylenenaphthalene ring group, and the like. Further, the cross-linked cyclic hydrocarbon ring group also contains a condensed cyclic hydrocarbon ring group, for example, a condensed ring group obtained by condensation of a plurality of 5- to 8-membered cycloalkane ring groups, such as perhydronaphthalene (decalin) a ring group, a perhydro anthracene ring group, a perhydrophenanthrene ring group, a perhydroacenaphthene ring group, a perhydrofluorene ring group, a perhydrohydroquinone ring ( Perhydroindene ring) group and perhydrophenalene ring group.

Preferred examples of the cross-linked cyclic hydrocarbon ring group include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, and a tricyclo[5,2,1,0 ^2,6 ]decane ring group. Group and similar groups.

Examples of more preferred cross-linked cyclic hydrocarbon ring groups include norbornane ring groups and adamantane ring groups.

The linking group represented by Z having a polycyclic hydrocarbon structure may have a substituent. Examples of the substituent which Z may have include a substituent such as an alkyl group, a hydroxyl group, a cyano group, a keto group (=O), a decyloxy group, -COR, -COOR, -CON(R) ₂ , -SO ₂ R, -SO ₃ R and -SO ₂ N(R) ₂ . Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

As the substituent which Z may have, an alkyl group, an alkylcarbonyl group, a decyloxy group, -COR, -COOR, -CON(R) ₂ , -SO ₂ R, -SO ₃ R, and -SO ₂ N(R) ₂ It may have a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom).

In the linking group having a polycyclic hydrocarbon structure represented by Z, the carbon constituting the polycyclic ring (the carbon which contributes to ring formation) may be a carbonyl carbon. Further, as described above, the polycyclic ring may have a hetero atom such as an oxygen atom and a sulfur atom as a ring member.

Examples of the linking group represented by L ₁ and L ₂ include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ - an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms) A bonding group formed by combining a plurality of members of these members and the like, and a linking group having a total carbon number of 12 or less is preferred.

L _{1 is} preferably a single bond, an alkyl group, a -COO-, -OCO-, -CONH-, -NHCO-, -alkyl-COO-, -alkyl-OCO-, -alkyl-CONH -, -alkyl-NHCO-, -CO-, -O-, -SO ₂ - and -alkyl-O-, and more preferably a single bond, an alkyl group, an alkyl group - COO- or - stretch alkyl-O-.

L _{2 is} preferably a single bond, an alkyl group, a -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene-, -OCO-alkylene-,-CONH-alkylene group. -, -NHCO-alkylene-, -CO-, -O-, -SO ₂ -, -O-alkylene- and -O-cycloalkyl-, and more preferably a single bond, an alkyl group , -COO-alkylene-, -O-alkylene- or -O-cycloalkyl-.

In the above-described method, the bonding arm (bonding hand) on the left end of the "-" means in L ₁ intended to be connected ester bond on the main chain side and, in L, intended to _second connection Z, and bonded to the arms "on the right - "incorporated in L ₁ is intended to Z and bound to the ester bond in L ₂ is intended, the ester bond group bonded to a _{(Ry 1) (Ry 2)} (Ry 3) represents the C-.

Further, L ₁ and L ₂ may be bonded to the same atom constituting the polycyclic ring in Z.

n is preferably 1 or 2, and more preferably 1.

Hereinafter, a specific example of the repeating unit represented by the formula (IB) will be described below, but the present invention is not limited to the examples. In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

Further, the resin (A) may have a repeating unit having a structure capable of decomposing under an action of an acid to produce an alcoholic hydroxyl group (hereinafter, sometimes referred to as an "OH protection structure") as having an acid. A repeating unit of a decomposable group.

The OH protective structure is preferably a structure represented by at least one selected from the group consisting of the following formulas (II-1) to (II-4).

In the above formula, each R ₃ independently represents a hydrogen atom or a monovalent organic group. R ₃ may be combined with each other to form a ring.

Each R ₄ independently represents a monovalent organic group. R ₄ may be combined with each other to form a ring. R ₃ and R ₄ may be combined with each other to form a ring.

Each R ₅ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. At least two R ₅ may be combined with each other to form a ring, with the proviso that when one or both of the three R ₅ members are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group or an alkynyl group.

As the OH protective structure, at least one selected from the group consisting of the following formulas (II-5) to (II-9) is also a preferred embodiment.

In the above formula, R _{4 has} the same meanings as in the formula (II-1) to the formula (II-3).

Each R ₆ independently represents a hydrogen atom or a monovalent organic group. R ₆ may be combined with each other to form a ring.

The group capable of decomposing to form an alcoholic hydroxyl group under the action of an acid is more preferably represented by at least one selected from the group consisting of formula (II-1) to formula (II-3), more preferably by formula (II-1) or formula ( II-3) indicates that it is more preferably represented by the formula (II-1).

R ₃ represents a hydrogen atom or a monovalent organic group as described above. R _{3 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group of R ₃ may be a linear or branched alkyl group. The carbon number of the alkyl group of R ₃ is preferably from 1 to 10, more preferably from 1 to 3. Examples of the alkyl group of R ₃ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group of R ₃ may be a monocyclic or polycyclic group. The number of carbon atoms of the cycloalkyl group of R ₃ is preferably from 3 to 10, more preferably from 4 to 8. Examples of the cycloalkyl group of R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

R ₄ represents a monovalent organic group. R _{4 is} preferably an alkyl group or a cycloalkyl group, more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.

The alkyl group of R ₄ preferably has no substituent or has one or more aryl groups and/or one or more decyl groups as a substituent. The carbon number of the unsubstituted alkyl group is preferably from 1 to 20. The alkyl group in the alkyl group substituted by one or more aryl groups preferably has 1 to 25 carbon atoms. The alkyl group in the alkyl group substituted by one or more alkylidene groups preferably has 1 to 30 carbon atoms. Further, in the case where the cycloalkyl group of R ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.

R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. However, when one or both of the three R ₅ members are a hydrogen atom, at least one of the remaining R ₅ represents an aryl group, an alkenyl group or an alkynyl group. R _{5 is} preferably a hydrogen atom or an alkyl group. The alkyl group may or may not have a substituent. In the case where the alkyl group does not have a substituent, the carbon number thereof is preferably from 1 to 6, more preferably from 1 to 3.

R ₆ represents a hydrogen atom or a monovalent organic group as described above. R _{6 is} preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having no substituent. R _{6 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and no substituent.

Examples of the alkyl group of R ₄ , R ₅ and R ₆ and the cycloalkyl group are the same as the examples described above for R ₃ .

Specific examples of repeating units having an OH protecting structure in a side chain include the following specific examples and are derived from US Patent Application Publication No. 2012/0064456A The repeating unit of the monomer exemplified in the paragraph [0025], but the invention is not limited to the examples.

(In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CH ₂ OH of CF ₃ )

The repeating unit having the acid-decomposable group of the resin (A) may be used singly or in combination of two or more thereof.

In the present invention, it is preferred that the dissociated substance produced by decomposing a group capable of decomposing a polar group under the action of an acid (acid-decomposable group) has a molecular weight of 140 or less (when a plurality of dissociated substances are produced). When the molecular weight is a weighted molecular weight (hereinafter also referred to as a molar average), the resin (A) has 50 moles of all repeating groups in the resin. % or more than 50% by mole of repeating units having an acid decomposable group. Therefore, when a negative image is formed, the exposed portion remains as a pattern, and thus the film thickness of the pattern portion can be prevented from being reduced due to a decrease in the molecular weight of the dissociated substance.

In the present invention, the term "the dissociated substance produced by decomposing the acid-decomposable group" means obtained by decomposing and remaining under the action of an acid. A substance corresponding to a group capable of decomposing under the action of an acid and remaining. For example, in the case of the repeating unit (α) described below (the repeating unit at the upper left portion in the examples described below), the term refers to the result of decomposing the third butyl moiety. Olefin (H ₂ C=C(CH ₃ ) ₂ ).

In the present invention, the molecular weight of the dissociated substance produced by decomposing the acid-decomposable group (the molar average value when a plurality of dissociated substances are produced) is better from the viewpoint of preventing the film thickness of the pattern portion from being reduced. It is 100 or less than 100.

Further, the lower limit of the molecular weight of the dissociated substance (the average value when a plurality of dissociated substances are produced) by decomposing the acid-decomposable group is not particularly limited, but the viewpoint of exhibiting its function from the acid-decomposable group Preferably, it is 45 and more preferably 55.

In the present invention, from the viewpoint of maintaining the film thickness of the pattern portion of the exposed portion more specifically, when the molecular weight of the dissociated substance generated by decomposing the acid decomposable group is 140 or less, The repeating unit having an acid-decomposable group (the total amount thereof in the case of containing various kinds thereof) is more preferably 60% by mole or more than 60% by mole, more preferably 65 moles, based on all the repeating units in the resin. % or greater than 65 mole %, and more preferably 70 mole % or greater than 70 mole %. Further, the upper limit is not particularly limited, but is preferably 90 mol% and more preferably 85 mol%.

The content ratio of the total amount of the repeating unit having an acid-decomposable group in terms of all the repeating units in the resin (A) is preferably 20 mol% or more, more preferably 20 mol%, more preferably 30 mol% or More than 30% by mole, more preferably 45% by mole or more than 45% by mole and particularly preferably 50% by mole or more than 50% by mole.

Further, the content ratio of the total amount of the repeating unit having an acid-decomposable group in terms of all the repeating units in the resin (A) is preferably 90 mol% or less than 90 mol% and more preferably 85 mol%. % or less than 85% by mole.

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

As the lactone structure or the sultone structure, any structure may be used as long as the structure has a lactone structure or a sultone structure, but a 5- to 7-membered ring lactone structure is preferable, and another ring is used. It is preferred that the structure is condensed to form a 5- to 7-membered cyclic lactone structure of a bicyclic or spiro ring structure. More preferably, the structure has a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-17) or from the following formula (SL1-1) to (SL1-3) Any of the repeating units of the sultone structure. Further, the lactone structure or the 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), and (LC1-17), and especially A preferred lactone structure is (LC1-4). LWR and development defects are improved by using the specific lactone structure.

The lactone structure or the sultone moiety may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and An alkoxycarbonyl group of 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid decomposable group, and the like. An alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid decomposable group are more preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, each substituent (Rb ₂ ) may be the same as or different from all other substituents (Rb ₂ ). In addition, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

The repeating unit having a lactone group or a sultone structure usually has an optical isomer, but any optical isomer can be used. In addition, an optical difference can be used alone. The construct may be mixed with a plurality of optical isomers and a mixture may be used. When an optical isomer is mainly used, its optical purity (ee) is preferably 90% or more, and 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 formula (AII).

In the formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent (preferably having 1 to 4 carbon atoms).

Examples of preferred substituents of the alkyl group of Rb ₀ include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb _{0 is} preferably a hydrogen atom, a methyl group, a methylol group, and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group or a divalent linking group obtained by a combination thereof. Ab is preferably a single bond and a divalent linking group represented by -Ab ₁ -CO ₂ -.

Ab ₁ is a linear or branched alkyl group and a monocyclic or polycyclic cycloalkyl group, and is preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group, and a norbornyl group.

V represents a group having a lactone structure or a sultone structure. Specifically, V represents a group having a structure represented by, for example, the formula (LC1-1) to the formula (LC1-17) and the formula (SL1-1) to the formula (SL1-3).

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 preferably 0.5 mol based on all the repeating units of the resin (A). The range of the ear % to 80 mol%, more preferably in the range of 1 mol% to 65 mol%, more preferably in the range of 5 mol% to 60 mol%, particularly preferably 3 mol. It is in the range of % to 50 mol% and most preferably in the range of 10 mol% to 50 mol%.

The repeating unit having a lactone structure or a sultone structure may be used singly or in combination of two or more thereof.

Hereinafter, a specific example of a repeating unit having a lactone structure or a sultone structure will be described, but the present invention is not limited to the examples.

(In the formula below, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ )

(In the formula below, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ )

(In the formula below, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ )

[Chemical Formula 15]

(In the formula below, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ )

The resin (A) may have a repeating unit containing a hydroxyl group or a cyano group. Therefore, the adhesion to the substrate and the affinity for the developer are improved. Has a hydroxyl group or a cyano group The repeating unit is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and is preferably an acid-free decomposable group.

Further, it is preferred that the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is different from the repeating unit represented by the formula (AII).

In the alicyclic hydrocarbon structure in the hydroxy or cyano substituted alicyclic hydrocarbon structure, the alicyclic hydrocarbon structure is preferably an adamantyl group, a diadamantyl group or a norbornyl group. The alicyclic hydrocarbon structure preferably substituted by a hydroxyl group or a cyano group is preferably a partial structure represented by the following formula (VIIa) to formula (VIId).

In the formulae (VIIa) to (VIIc), R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R _2c to R _4c represents a hydroxyl group or a cyano group. Preferably, one or both of R _2c to R _4c are hydroxyl groups, and the remainder are all hydrogen atoms. In the formula (VIIa), more preferably, both of R _2c to R _4c are a hydroxyl group, and the balance is a hydrogen atom.

Examples of the repeating unit having a partial structure represented by the formula (VIIa) to the formula (VIId) include a repeating unit represented by the following formula (AIIa) to formula (AIId).

In the formula (AIIa) to the formula (AIId), R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

The same as R _2c to R _4c the meaning as in formula (Vila) to formula (VIIc) R _2c to R _4c.

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, it has a hydroxyl group in terms of all repeating units in the resin (A) The content of the repeating unit of the cyano group is preferably from 1 mol% to 40 mol%, more preferably from 3 mol% to 30 mol%, and still more preferably from 5 mol% to 25 mol%.

Specific examples of the repeating unit having a hydroxyl group or a cyano group will be described below, but the invention is not limited to the examples.

The resin (A) may have a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a sulfonylamino group, a sulfonimido group, a bissulfonimide group, and an aliphatic alcohol substituted with an electron withdrawing group at the α position (for example, a hexafluoroisopropanol group) (for example, hexafluorocarbon) Isopropanol group), and more preferably, the resin has a repeating unit containing a carboxyl group. By containing a repeating unit having an acid group, the resolution is increased when a contact hole is used. As for the repeating unit having an acid group, the acid group is directly bonded to a repeating unit of the resin main chain (such as a repeating unit of acrylic acid or methacrylic acid) or the acid group is bonded to the repeating unit of the resin main chain via a linking group to And a repeating unit which introduces an acid group into a polymer chain terminal by using a polymerization initiator or a chain transfer agent having an acid group at the time of polymerization, and the linking group may have a monocyclic or polycyclic hydrocarbon group structure. Repeating units of acrylic acid or methacrylic acid are especially preferred.

The resin (A) may or may not contain a repeating unit having an acid group, but in the case of containing a repeating unit having an acid group, the content ratio of the repeating unit having an acid group is calculated by all the repeating units in the resin (A) Preferably, it is 15% by mole or less than 15% by mole, and more preferably 10% by mole or less. When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more than 1 mol%.

Specific examples of the repeating unit having an acid group will be described below, but the invention is not limited to the examples.

In specific examples, Rx represents H, CH _3, CH ₂ OH or CF _3.

The resin (A) of the present invention may have a repeating unit having an alicyclic hydrocarbon structure and exhibiting no acid decomposability, and the alicyclic hydrocarbon structure does not have a polar group (for example, an acid group, a hydroxyl group, and a cyano group). Therefore, the dissolution of the low molecular component from the resist film into the immersion liquid at the time of the immersion exposure can be reduced, and further, the solubility of the resin at the time of development using the developer containing the organic solvent can be appropriately adjusted. Examples of repeating units include tables of formula (IV) Repeat unit shown.

In the 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 above formula, Ra ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Ra is preferably a hydrogen atom, a methyl group, a methylol group, and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.

R ₅ has a cyclic structure comprising a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group) and a cycloalkenyl group having 3 to 12 carbon atoms (such as Cyclohexenyl). The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group contains a ring-combined hydrocarbon group and a cross-linked cyclic hydrocarbon group, and examples of the ring-combined hydrocarbon group include a dicyclohexyl group, a perhydronaphthyl group, and the like. Examples of the cross-linked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring such as a decane ring, a norbornane ring, a norbornane ring, a norbornane ring, and a bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2. 1] octane ring and similar ring); tricyclic hydrocarbon ring, such as homobrane ring, adamantane ring, tricyclo[5.2.1.0 ^2,6 ]decane ring and tricyclo[4.3.1.1 ^2,5 ] a monocyclic hydrocarbon ring; such as a tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ldodecane) and all hydrogen-1 , 4-methylene-5,8-methylenenaphthalene ring, and similar rings. Further, the crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a condensed ring obtained by condensation of a plurality of 5- to 8-membered cycloalkane rings, such as a perhydronaphthalene (decalin) ring, a perhydroindene ring, All hydrogen phenanthrene ring, perhydroanthracene ring, perhydroindole ring, perhydroindole ring and perhydroindole ring.

Preferred examples of the crosslinked cyclic hydrocarbon ring include norbornylalkyl, adamantyl, and bicyclooctyl, tricyclo[5,2,1,0 ^2,6 ]fluorenyl. More preferred examples of crosslinked cyclic hydrocarbon rings include norbornyl and adamantyl.

The alicyclic hydrocarbon group may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amine group substituted with a hydrogen atom, and the like. Preferred examples of the halogen atom include a bromine atom, a chlorine atom and a fluorine atom, and preferred examples of the alkyl group include a methyl group, an ethyl group, a butyl group or a tert-butyl group. The above alkyl group may have a more substituent, and examples of the substituent which the alkyl group may further have include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amine group substituted with a hydrogen atom.

Examples of the substituent of the hydrogen atom include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkoxycarbonyl group. Preferred examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, and preferred examples of the substituted methyl group include a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, and a Examples of the ternoxymethyl group and the 2-methoxyethoxymethyl group, and the substituted ethyl group include 1-ethoxyethyl group and 1-methyl-1-methoxyethyl group. Preferred examples include an aliphatic fluorenyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group, a pentylene group, and an alkoxycarbonyl group. Examples include alkoxycarbonyl groups having from 1 to 4 carbon atoms and the like.

The resin (A) may or may not contain a repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposability, but in the case of containing the repeating unit, the content ratio of the repeating unit It is preferably from 1 mol% to 40 mol%, and more preferably from 1 mol% to 20 mol%, based on all the repeating units in the resin (A).

Specific examples of the repeating unit having an alicyclic hydrocarbon structure free of a polar group and exhibiting no acid decomposability will be described below, but the present invention is not limited to the examples. In the following formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

In addition to the above repeating structural unit, the resin (A) used in the composition of the present invention may have various repeating structural units for the purpose of controlling dry etching resistance, suitability to a standard developer, adhesion to a substrate, and adhesion to a substrate. And the resist profile and further control of resolution, heat resistance, sensitivity, and the like, which are properties typically required for resists.

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

Therefore, it is possible to precisely adjust the performance required for the resin used in the composition of the present invention, in particular, (1) solubility in a coating solvent, (2) film formation characteristics (glass transition temperature), and (3) alkali Developability, (4) film reduction (selection of hydrophilic, hydrophobic or alkali-soluble groups), (5) Adhesion of the unexposed portion to the substrate, (6) dry etching resistance, and the like.

Examples of the monomer include an unsaturated bond having an addition polymerization which is selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, allyl compound, vinyl ether, vinyl ester and the like. Compound.

In addition to these, an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to each of the above various repeating structural units can be copolymerized.

In the resin (A) used in the composition of the present invention, the molar ratio of the respective repeating structural units is appropriately set to control the dry etching resistance of the resist, the suitability to the standard developer, and the substrate. Adhesion and resist profile and further control of resolution, heat resistance, sensitivity, and similar performance, which are generally desirable for resists.

The resin (A) in the present invention may be in any form of a random type, a block type, a comb type, and a star type. The resin (A) can be synthesized, for example, by polymerizing a radical, a cation or an anion corresponding to an unsaturated monomer of each structure. In addition, it is possible to obtain a target resin by performing polymerization using an unsaturated monomer corresponding to the precursor of each structure, and then performing a polymer reaction.

When the composition of the present invention is used for ArF exposure, the resin (A) used in the composition of the present invention is preferably substantially free of aromatic rings from the viewpoint of transparency of ArF light (specifically, aryl in the resin) The ratio of the repeating unit of the group is preferably 5 mol% or less than 5 mol%, more preferably 3 mol% or less than 3 mol%, and desirably 0 mol%, that is, the resin does not have a fragrance The group (B) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

Further, the CLogP value of the resin (A) is not particularly limited, but is preferably from 0 to 6, more preferably from 1 to 5, and further preferably from the viewpoint of exhibiting the effect of the resin (D) described below. It is 1 to 4.

The absolute value of the difference between the CLogP value of the resin (A) and the CLogP value of the resin (D) is preferably more than 0, more preferably 1 or more and more preferably 2 or more.

When the absolute value of the difference between the CLogP value of the resin (A) and the CLogP value of the resin (D) is large, the resin (D) may be easily separated on the surface of the resist film when the resist film is formed and The effect of the present invention (film thickness uniformity as well as bridging defects and watermark defects reduction) can be enhanced.

Here, as for the method of calculating the CLogP value of the resin (A), refer to the description of the calculation method in the resin (D) described below.

Further, from the viewpoint of different viewpoints, when the composition of the present invention contains the resin (E) described below, the resin (A) is preferred from the viewpoint of compatibility with the resin (E). It does not contain fluorine atoms or germanium atoms.

The resin (A) used in the composition of the present invention is preferably a resin in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units used may be any methacrylate repeating unit, acrylate repeating unit, or methacrylate repeating unit and acrylate repeating unit, but in all repeating units, The acrylate-based repeating unit is preferably present in an amount of 50 mol% or less than 50 mol%. Further, (meth) acrylate-containing repeating unit having 20 mol% to 50 mol% of an acid-decomposable group, 20 mol% to 50 mol% of a (meth) acrylate having a lactone group Recurring-like unit, 5 mol% to 30 mol% (meth) acrylate repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group, and 0 mol% to 20 mol% other (methyl) Copolymerizable polymerization of acrylate repeating units Combinations are also preferred.

When a KrF excimer laser light, an electron beam, an X-ray or a high energy beam (EUV and the like) having a wavelength of 50 nm or less (EUV and the like) is irradiated onto the composition of the present invention, the resin (A) is preferably further. It has a hydroxystyrene repeating unit. The resin (A) more preferably has a hydroxystyrene-based repeating unit and an acid-decomposable repeating unit such as a hydroxystyrene-based repeating unit protected with an acid-decomposable group, a tertiary alkyl (meth)acrylate, and the like.

Preferred examples of the hydroxystyrene repeating unit having an acid-decomposable group include a third butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene, and a tertiary alkyl (meth)acrylate. And repeating units consisting of analogs, and repeating units consisting of 2-alkyl-2-adamantyl (meth)acrylate and dialkyl (1-adamantyl)methyl (meth)acrylate are more preferred of.

The resin (A) of the present invention can be synthesized by a typical method such as radical polymerization. Examples of general synthetic methods include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent and a solution is heated to carry out polymerization; a dropping polymerization method in which 1 hour to 10 hours are passed A solution containing a monomer substance and a starter is added dropwise to the heated solvent, and the like, and a drop-in polymerization method is preferred. Examples of the reaction solvent include tetrahydrofuran, 1,4-dioxane; ether such as diisopropyl ether; ketone such as methyl ethyl ketone and methyl isobutyl ketone; ester solvent such as ethyl acetate; guanamine solvent For example, dimethylformamide and dimethylacetamide; and solvents described below capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. The polymerization is preferably carried out using the same solvent as that used in the photosensitive composition of the present invention. Therefore, particle generation during storage can be suppressed.

The polymerization is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, polymerization is started using a commercially available radical initiator (azo initiator, peroxide, and the like). The radical initiator is preferably an azo initiator, and an azo initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl ester, and the like. If necessary, the initiator is added in addition or in portions, and after the reaction is completed, the reaction product is poured into a solvent, and the desired polymer is recovered by a powder or solid recovery method or the like. The reactant concentration is from 5% by mass to 50% by mass, and preferably from 10% by mass to 30% by mass.

The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 ° C to 100 ° C.

After the reaction was completed, the reaction solution was cooled to room temperature and purified. Purification can be carried out by typical methods, such as liquid-liquid extraction, in which water washing or combined water washing with a suitable solvent to remove residual monomer or oligomer components; purification of the solution state, such as by means of extraction only Removing ultrafiltration of a polymer having a molecular weight not greater than a specific molecular weight; a reprecipitation method in which a resin solution is added dropwise to a poor solvent to solidify the resin in a poor solvent, thereby removing residual monomers and the like; solid-state purification method Such as washing a resin slurry by filtration with a poor solvent, and the like. For example, the resin is precipitated as a solid by contacting the reaction solution with a solvent (poor solvent) of a sparingly soluble or insoluble resin, wherein the volume of the solvent is 10 times or less and preferably 10 times to 5 times the reaction solution. Times.

If the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution is a poor solvent for the polymer, it may be sufficient, and the solvent may be appropriately halogenated according to the kind of the polymer. Hydrocarbons, nitro compounds, ethers, Ketones, esters, carbonates, alcohols, carboxylic acids, water, and mixed solvents containing these solvents are selected and used. Among these solvents, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferred as a precipitation or reprecipitation solvent.

The amount of the precipitation or reprecipitation solvent to be used can be appropriately selected by considering the efficiency, the yield, and the like, but generally, the amount is from 100 parts by mass to 10,000 parts by mass based on 100 parts by mass of the polymer solution. It is preferably from 200 parts by mass to 2,000 parts by mass, and more preferably from 300 parts by mass to 1,000 parts by mass.

The temperature at the time of precipitation or reprecipitation can be appropriately selected by considering efficiency or operability, but is usually about 0 ° C to 50 ° C, and preferably close to room temperature (for example, about 20 ° C to 35 ° C). The precipitation or reprecipitation operation can be carried out by a known method such as a batch system and a continuous system using a conventional mixing vessel such as a stirring tank.

The precipitated or reprecipitated polymer is typically subjected to conventional solid-liquid separation, such as filtration and centrifugation, followed by drying and use. Filtration is carried out by using a solvent resistant filter member and preferably under pressure. Drying is carried out at atmospheric pressure or reduced pressure (preferably under reduced pressure) at a temperature of from about 30 ° C to 100 ° C, and preferably at a temperature of from about 30 ° C to 50 ° C.

Further, after the resin is precipitated and separated, the resin may be redissolved in a solvent and then contacted with a solvent of a sparingly soluble or insoluble resin. That is, a method comprising the steps of: contacting the polymer with a solvent of a sparingly soluble or insoluble polymer to precipitate the resin after the completion of the radical polymerization reaction (step a), separating the resin from the solution (step b), The resin is dissolved in a solvent to prepare a resin solution A (step c), and then the resin solution A and the sparingly soluble or insoluble resin are used and the volume is less than 10 times that of the resin solution A (the volume is preferably 5 times or less than 5 times) The solvent is contacted to precipitate the resin solid (step d), and the precipitated resin is separated (step e).

Further, in order to suppress the aggregation of the resin after the preparation of the composition or the like, as described in, for example, Japanese Patent Application Laid-Open No. 2009-037108, the following steps may be added: the synthetic resin is dissolved in a solvent to prepare a solution and The solution is heated at about 30 ° C to 90 ° C for about 30 minutes to 4 hours.

The weight average molecular weight of the resin (A) used in the composition of the present invention is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, still more preferably from 3,000 to 70,000, as measured by a GPC method. It is particularly preferably from 5,000 to 50,000. By setting the weight average molecular weight in the range of 1,000 to 200,000, it is possible to prevent deterioration of heat resistance or dry etching resistance, and it is possible to prevent film formation characteristics from being deteriorated due to impaired developability or increased viscosity.

The polydispersity (molecular weight distribution) is usually in the range of 1.0 to 3.0. The polydispersity is preferably in the range of 1.0 to 2.6, more preferably in the range of 1.1 to 2.5, still more preferably in the range of 1.4 to 2.4, particularly preferably in the range of 1.3 to 2.2, and particularly preferably 1.4. To the range of 2.0. When the molecular weight distribution satisfies the above range, the resolution and the resist shape are excellent, and the side walls of the resist pattern are smooth and excellent in roughness.

In the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably from 30% by mass to 99% by mass based on the total solid content of the composition of the resin (A). %, and more preferably 60% by mass to 95% by mass.

Further, the resin (A) of the present invention may be used singly or in combination of many thereof.

[2] A compound capable of generating an acid after irradiation with actinic rays or radiation (B)

The composition of the present invention contains a compound (B) (hereinafter also referred to as "acid generator") capable of generating an acid after irradiation with actinic rays or radiation. The compound (B) capable of generating an acid after irradiation with actinic rays or radiation is preferably a compound capable of producing an organic acid after irradiation with actinic rays or radiation.

The acid generator may suitably be a photo-polymerized photoinitiator, a photopolymerizable photoinitiator, a photodegradant of a dye, a photodecolorizer, an acid which can be generated after irradiation with actinic rays or radiation. Known compounds for microresist or the like, as well as mixtures thereof, are selected and available for use.

Examples thereof include a diazonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, a sulfonium iminosulfonate, an anthracenesulfonate, a diazodiazine, a dihydrazine, and an o-nitrophenylmethylsulfonate.

Among the acid generators, preferred compounds include compounds represented by the following formula (ZI), formula (ZII) and formula (ZIII).

In the formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, and preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of the group formed by a combination of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (e.g., a butyl group and a pentyl group).

Z ^- represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ^- containing include a sulfonate anion, a carboxylate anion, a sulfonimide anion, a bis(alkylsulfonyl)phosphonium anion, and a tris(alkylsulfonyl)methyl anion. And similar anions.

The non-nucleophilic anion is an anion which has an extremely low ability to cause a nucleophilic reaction and is capable of suppressing decomposition which occurs over time due to an intramolecular nucleophilic reaction. Therefore, the stability of the sensitized ray-sensitive or radiation-sensitive resin composition over time is improved.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, and the like.

Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkylcarboxylate anion, and the like.

The aliphatic moiety of the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and is preferably an alkyl group having 1 to 30 carbon atoms and having 3 to 30 carbon atoms. Cycloalkyl, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, fluorene Base, fluorenyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Eicosyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, borneol and the like.

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

The alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion may have a substituent. Aliphatic sulfonate anion and aromatic sulfonate anion Examples of the substituent of the alkyl group, the cycloalkyl group and the aryl group include a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a carboxyl group, a hydroxyl group, an amine group, a cyano group, and an alkoxy group ( Preferably having from 1 to 15 carbon atoms), a cycloalkyl group (preferably having from 3 to 15 carbon atoms), an aryl group (preferably having from 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), mercapto group (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), alkylthio group (preferably) Having 1 to 15 carbon atoms), alkylsulfonyl (preferably having 1 to 15 carbon atoms), alkylimidosulfonyl (preferably having 1 to 15 carbon atoms), aromatic Oxydodecyl (preferably having 6 to 20 carbon atoms), alkyl aryloxysulfonyl (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl (more Preferably having 10 to 20 carbon atoms), an alkoxyalkoxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkoxy alkoxy group (preferably having 8 to 20 carbon atoms) And similar groups. The aryl group and the ring structure which each group has may further have an alkyl group (preferably having 1 to 15 carbon atoms) or a cycloalkyl group (preferably having 3 to 15 carbon atoms) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthalene group. A butyl group and the like.

The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylate anion, the aromatic carboxylate anion, and the aralkylcarboxylate anion may have a substituent. Examples of the 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 sulfonimide anion include a saccharin anion.

Bis(alkylsulfonyl) quinone imine anion and tris(alkylsulfonyl) methylation The alkyl group in the anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a second butyl group. , pentyl, neopentyl and the like. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonate group. Alkyl groups and the like, and an alkyl group substituted with a fluorine atom are preferred.

Examples of other non-nucleophilic anions include phosphorus fluoride (e.g., PF ₆ ^- ), boron fluoride (e.g., BF ₄ ^- ), cesium fluoride (e.g., SbF ₆ ^- ), and the like.

Z ^- aliphatic sulfonate anion of a non-nucleophilic anion preferably a substituted sulfonic α position is a fluorine atom, the fluorine atom or an aromatic sulfonate anion having a substituent group of the fluorine atom, bis (alkyl sulfonate A mercapto) anthracene anion (wherein the alkyl group is substituted by a fluorine atom) or a tris(alkylsulfonyl)methide anion (wherein the alkyl group is substituted by a fluorine atom). The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms and a benzenesulfonate anion having a fluorine atom, and more preferably a nonafluorobutanesulfonate anion or perfluorooctane A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis(trifluoromethyl)benzenesulfonate anion.

The acid generator is preferably a compound capable of producing an acid represented by the following formula (III) or formula (IV) after irradiation with actinic rays or radiation. By the compound capable of producing an acid represented by the following formula (III) or formula (IV), the compound has a cyclic organic group and thus the resolution and the roughness efficiency can be excellent.

The non-nucleophilic anion may be an anion capable of producing an organic acid represented by the following formula (III) or formula (IV).

In the above formula, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group.

Each L independently represents a divalent linking group.

Cy represents a cyclic organic group.

Rf is a group containing a fluorine atom.

x represents an integer from 1 to 20.

y represents an integer from 0 to 10.

z represents an integer from 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably from 1 to 10, and more preferably from 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ Or CH ₂ CH ₂ C ₄ F ₉ , and more preferably a fluorine atom or CF ₃ . In particular, it is preferred that two Xf are fluorine atoms.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group may have a substituent (preferably a fluorine atom) and preferably has 1 to 4 carbon atoms. The alkyl group is more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ₁ and R ₂ include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ , and wherein CF _{3 is} preferred.

L represents a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene ( Preferably having from 1 to 6 carbon atoms), a cycloalkyl group (preferably having from 3 to 10 carbon atoms), an alkenyl group (preferably having from 2 to 6 carbon atoms), by combining these members A divalent linking group and the like formed by a plurality of members. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH- Alkyl- or -NHCO-alkylene-preferably, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene--more preferably .

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 can be a monocyclic or polycyclic group. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, adamantyl, and groups having a steroid skeleton. Among them, from the viewpoint of suppressing diffusion in the film during the post-exposure baking (PEB) step and improving the mask error enhancement factor (MEEF), it has a large structure and has 7 or An alicyclic group having more than 7 carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclononyl group, a tetracyclododecyl group, an adamantyl group, and a steroid skeleton is preferred.

The steroid skeleton usually contains a substituent such as a carbonyl group and a hydroxyl group, optionally Substituting the structure on the carbon skeleton shown below, and capable of producing an organic acid represented by the formula (III) or (IV) (where Cy represents a group having a steroid skeleton) after irradiation with actinic rays or radiation. Examples of anions include the anionic structures contained in the four compounds exemplified in paragraph [0036] of U.S. Patent Application Publication No. 2011/0250537 A1.

The aryl group can be a monocyclic or polycyclic group. Examples of aryl groups include phenyl, naphthyl, phenanthryl and anthracenyl. Among them, a naphthyl group having a relatively low absorbance at 193 nm is preferred.

The heterocyclic group may be a monocyclic or polycyclic group, but the polycyclic heterocyclic group may inhibit acid diffusion more effectively. Further, the heterocyclic group may have an aromaticity or may not have an aromaticity. Examples of the aromatic heterocyclic ring 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 having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring. Further, examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above resin (A).

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be a linear or branched chain and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic, polycyclic or spiro ring and preferably has 3 to 20) Carbon atom), aryl (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, decylamino group, urethane group, ureido group, thioether group, sulfonamide And sulfonate groups. In addition, the composition of the ring The carbon of the organic group (the carbon which contributes to the formation of a ring) may be a carbonyl carbon.

x is preferably from 1 to 8, and more preferably from 1 to 4, and particularly preferably 1. y is preferably from 0 to 4, and more preferably 0. z is preferably from 0 to 8, and among them, preferably from 0 to 4.

Examples of the group having 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.

The alkyl group, the cycloalkyl group and the aryl group may be substituted by a fluorine atom or may be substituted by 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, an example of another substituent containing a fluorine atom includes an alkyl group substituted with at least one fluorine atom.

Further, the alkyl group, the cycloalkyl group, and the aryl group may be substituted with a substituent not containing a fluorine atom. Examples of the substituent include a substituent which does not contain a fluorine atom in the substituent described above for Cy.

Examples of the alkyl group having at least one fluorine atom represented by Rf include the same alkyl group as the above-described example of the alkyl group substituted by 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.

As the non-nucleophilic anion, a sulfonate anion represented by the following formula (B-1) is also preferable.

In the formula (B-1), each R _b1 independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).

n represents an integer from 0 to 4.

n is preferably an integer of 0 to 3, more preferably 0 or 1.

X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate bond (-OSO ₂ - or -SO ₃ -), or a combination thereof.

X _{b1 is} preferably an ester bond (-OCO- or -COO-) or a sulfonate bond (-OSO ₂ - or -SO ₃ -), more preferably an ester bond (-OCO- or -COO-).

R _b2 represents an organic group having a carbon number of 6 or more.

The organic group having a carbon number of 6 or more of R _b2 is preferably a large group, and examples thereof include an alkyl group having an carbon number of 6 or more, an alicyclic group, an aryl group, and a heterocyclic group.

The alkyl group having 6 or more carbon atoms of R _b2 may be a linear or branched alkyl group and is preferably a linear or branched alkyl group having a carbon number of 6 to 20, and examples thereof include a straight chain or a branched chain. Hexyl, linear or branched heptyl and straight or branched octyl. Branched-chain alkyl groups are preferred in view of bulkiness.

The alicyclic group having a carbon number of 6 or more of R _b2 may be a monocyclic or polycyclic group. The monocyclic alicyclic group includes, for example, a monocyclic cycloalkyl group such as a cyclohexyl group and a cyclooctyl group. The polycyclic alicyclic group includes, for example, a polycyclic cycloalkyl group such as norbornyl group, tricyclodecyl group, tetracyclodecyl group, tetracyclododecyl group, and adamantyl group. In particular, from the standpoint of suppressing diffusion in the film during the post-exposure baking (PEB) step and improving the mask error enhancement factor (MEEF), it has a large structure and a carbon number of 7 Or an alicyclic group of greater than 7, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl, is preferred.

The aryl group having a carbon number of 6 or more of R _b2 may be a monocyclic or polycyclic group. Examples of such aryl groups include phenyl, naphthyl, phenanthryl and anthracenyl. Among them, a naphthyl group having a relatively low absorbance at 193 nm is preferred.

The heterocyclic group having a carbon number of 6 or more in R _b2 may be a monocyclic or polycyclic group, but the use of a polycyclic heterocyclic group may further inhibit acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocyclic ring include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The above substituent having a carbon number of 6 or more of R _b2 may have a more substituent. Examples of other substituents include an alkyl group (which may be a linear or branched chain, preferably having a carbon number of 1 to 12), a cycloalkyl group (which may be a monocyclic, polycyclic or spiro ring, preferably a carbon number of 3 to 20). , aryl (preferably having a carbon number of 6 to 14), hydroxy, alkoxy, ester, decyl, urethane, ureido, thioether, sulfonylamino and sulfonate base. Incidentally, the carbon constituting the alicyclic group, the aryl group or the heterocyclic group (the carbon which contributes to ring formation) may be a carbonyl carbon.

Specific examples of the sulfonate anion structure represented by the formula (B-1) are explained below, but the invention is not limited to the examples.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound (ZI-4) described below. Corresponding group.

Further, a compound having a plurality of structures represented by the formula (ZI) can be used. For example, it is possible to use a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ in the compound represented by the formula (ZI) is bonded to the formula (ZI) via a single bond or a bonded group. Another compound of at least one of R ₂₀₁ to R ₂₀₃ .

Examples of the more preferred (ZI) component include the compound (ZI-1) described below, Compound (ZI-2), compound (ZI-3), and compound (ZI-4).

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in the formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.

In the arylsulfonium compound, R ₂₀₁ to R ₂₀₃ may each be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the balance is an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound.

The aryl group in the arylsulfonium compound is preferably a phenyl group and a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing 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 anthracene residue, a benzofuran residue, a benzothiophene residue, and the like. When the arylsulfonium compound has two or more than two aryl groups, each aryl group may be the same as or different from each other aryl group.

The aryl hydrazine compound preferably has an alkyl group or a cycloalkyl group as a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, and Examples include methyl, ethyl, propyl, n-butyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ may have the following substituents: an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms). An aryl group (for example having 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. The substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched chain having 1 to 12 carbon atoms or A cyclic alkoxy group, and more preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any of R ₂₀₁ to R ₂₀₃ or may be substituted on all three. Further, when R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the para position of the aryl group.

Subsequently, the compound (ZI-2) will be described below.

The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represents an aromatic ring-free organic group. Here, the aromatic ring also contains an aromatic ring containing a hetero atom.

The aromatic group-free organic group as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ each independently preferably represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-sided oxyalkyl group, a 2-sided oxycycloalkyl group, and Alkoxycarbonylmethyl, and particularly preferably represents a straight-chain or branched 2-sided oxyalkyl group.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R _{203 are} preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group) and having A cycloalkyl group of 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbornyl group). The alkyl group is more preferably a 2-sided oxyalkyl group and an alkoxycarbonylmethyl group. The cycloalkyl group is more preferably a 2-sided oxycycloalkyl group.

The 2-sided oxyalkyl group may be a straight chain or a branched chain, and preferably has a group of >C=O at the 2-position of the above alkyl group.

The 2-sided oxycycloalkyl group preferably has a group of >C=O at the 2-position of the above cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group preferably has from 1 to 5 carbon atoms. Alkoxy (methoxy, ethoxy, propoxy, butoxy and pentyloxy).

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

Subsequently, the compound (ZI-3) will be described.

The compound (ZI-3) is a compound represented by the following formula (ZI-3), and a compound having a benzamidine methyl phosphonium salt structure.

In the formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, A cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

R _6c and R _7c each independently represent 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 represent an alkyl group, a cycloalkyl group, a 2-sided oxyalkyl group, a 2-sided oxycycloalkyl 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 each other to form a ring structure and The ring structure may comprise an oxygen atom, a sulfur atom, a ketone group, an ester bond or a guanamine bond.

Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring formed by a combination of two or more of these rings. The ring structure comprises a 3 to 10 member ring and preferably a 4 to 8 member ring, and more preferably a 5 or 6 member ring.

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 butyl group, a pentyl group, and the like.

The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkyl group, and examples of the alkyl group include a methylene group, an ethyl group and the like.

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

The alkyl group as R _1c to R _7c may be a straight chain or a branched chain, and examples thereof include an alkyl group having 1 to 20 carbon atoms, and preferably a straight chain or branch having 1 to 12 carbon atoms. Alkenyl (for example, methyl, ethyl, linear or branched propyl, straight or branched butyl, and linear or branched pentyl), and examples of cycloalkyl include from 3 to 10 carbons A cycloalkyl group of an atom (for example, a cyclopentyl group and a cyclohexyl group).

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 a straight chain, a branched chain or a cyclic group, and examples thereof include an alkoxy group having 1 to 10 carbon atoms, preferably having 1 to 5 carbon atoms. a linear or branched alkoxy group (for example, a methoxy group, an ethoxy group, a linear or branched chain propoxy group, a linear or branched chain butoxy group, and a linear or branched pentyloxy group) and having 3 to A cyclic alkoxy group of 10 carbon atoms (e.g., cyclopentyloxy group and cyclohexyloxy group).

As specific examples of the alkoxycarbonyl group of R _1c to R _5c in the alkoxy group are a particular example of R _1c to R _5c alkoxy same.

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

As specific examples of R _1c to R _5c Cycloalkylcarbonyloxy in the specific examples of the cycloalkyl group as R _1c to R _5c is the same as the cycloalkyl group.

As R _1c to R _5c, and specific examples of the aryloxy group are an aryl group of the aryl group are the same as the specific examples of R _1c to R _5c aryl group.

Any one of R _1c to R _5c is preferably a linear or branched alkyl group, a cycloalkyl group or a linear chain, a branched chain or a cyclic alkoxy group, and the total carbon number of R _1c to R _5c is more preferably Preferably 2 to 15. Therefore, the solvent solubility is further improved and thus the generation of particles during storage is suppressed.

Examples of the ring structure which may be formed by combining any two or more of R _1c to R _5c with each other preferably comprise a 5-membered or 6-membered ring, and more preferably a 6-membered ring (e.g., a benzene ring).

Examples of the ring structure which can be formed by combining R _5c and R _6c with each other include a combination of R _5c and R _6c to form a single bond or an alkyl group (such as a methylene group or an ethyl group) and a carbonyl group in the formula (I). A ring of 4 or more members formed by a carbon atom and a carbon atom (particularly preferably a 5-member or 6-membered ring).

The aryl group as R _6c to R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

It is preferred that both R _6c and R _7c are in the form of an alkyl group. Specifically, it is particularly preferable that each of R _6c and R _7c is a linear or branched alkyl group having 1 to 4 carbon atoms, and both of them are methyl groups.

Further, when R _6c and R _7c are combined with each other 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, and examples thereof include an ethyl group extending, Propyl, butyl, pentyl, hexyl and the like. Further, a 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 of R _x and R _y and the cycloalkyl group are the same as the examples of the alkyl group in R _1c to R _7c and the cycloalkyl group.

Examples of the 2-sided oxyalkyl group and the 2-sided oxycycloalkyl group as R _x and R _y are contained in the alkyl group as R _1c to R _{7c and} the group having >C=O at the 2-position of the cycloalkyl group. group.

Examples of the alkoxy group in the alkoxycarbonylalkyl group of R _x and R _{y are} the same as the alkoxy group in R _1c to R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms. And preferably a linear alkyl group having 1 to 5 carbon atoms (e.g., a methyl group and an ethyl group).

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

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

Examples of the ring structure which can be formed by combining R _5c and R _x with each other include a combination of R _5c and R _x to form a single bond or an alkyl group (methylene group, ethyl group or the like) and formula (I) A ring of 5 or more members (particularly preferably a 5-membered ring) formed by a sulfur atom and a carbonyl carbon atom.

Examples of the ring structure which can be formed by combining R _x and R _y with each other include divalent R _x and R _y (for example, methylene, ethyl, propyl and the like) and formula (ZI-3) The 5-membered or 6-membered ring formed by the sulfur atom together preferably contains a 5-membered ring (i.e., a tetrahydrothiophene ring).

R _x and R _y are each preferably an alkyl group or a ring having 4 or more carbon atoms, more preferably 6 or more carbon atoms and more preferably 8 or more carbon atoms. alkyl.

R _1c to R _7c and R _x and R _y each may have a more substituent, and examples of the substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, and an aromatic group. Alkyl, alkoxy, aryloxy, decyl, arylcarbonyl, alkoxyalkyl, aryloxyalkyl, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyl Oxyl and the like.

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

Examples of the cation of the compound (ZI-2) or the compound (ZI-3) of the present invention include paragraphs [0130] to [0134] of Japanese Patent Application Laid-Open No. 2010-256842, Japanese Patent Application No. The cations and similar cations described in paragraphs [0136] to [0140] of the Japanese Patent Publication No. 2011-76056.

Subsequently, the compound (ZI-4) will be described.

The compound (ZI-4) is represented by the following formula (ZI-4).

In the 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 a plurality of R ₁₄ are present, each R ₁₄ independently represents hydroxy, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl or has a ring A group of an alkyl group. These groups may have a substituent.

Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. The two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents a non-nucleophilic anion, and an example thereof is the same as a non-nucleophilic anion of Z ^{- in} the formula (ZI).

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and preferred examples thereof include a methyl group and a B group. Base, n-butyl, tert-butyl and the like.

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and a cyclopropyl group, a cyclopentyl group, Cyclohexyl, cycloheptyl and cyclooctyl are especially preferred.

The alkoxy group of R ₁₃ and R ₁₄ is preferably a linear or branched alkoxy group having 1 to 10 carbon atoms, and preferred examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, and a positive group. Butoxy and similar groups.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is preferably a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, and preferred examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group and the like. Group.

Examples of the cycloalkyl group of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and examples thereof include a single ring or more Cycloalkoxy and alkoxy having a monocyclic or polycyclic cycloalkyl group. These groups may have more substituents.

The monocyclic or polycyclic cycloalkoxy group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably 7 to 15, and preferably has a monocyclic cycloalkyl group. The monocyclic cycloalkoxy group having a total carbon number of 7 or more represents a monocyclic cycloalkoxy group, wherein a cycloalkoxy group (such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group). , cycloheptyloxy, cyclooctyloxy and cyclododecyloxy) optionally have a substituent such as an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl , dodecyl, 2-ethylhexyl, isopropyl, t-butyl, tert-butyl and isopentyl), hydroxyl, halogen (fluorine, chlorine, bromine and iodine), nitro, cyanide Alkyl, amidino, sulfonylamino, alkoxy (such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy), alkoxycarbonyl (such as a Oxycarbonyl and ethoxycarbonyl), mercapto (such as formazan, ethenyl and benzhydryl), anthracene (such as ethoxylated and butyloxy), carboxyl and the like, And the total carbon number including the carbon number of any substituent on the cycloalkyl group is 7 or more.

Further, examples of the polycyclic cycloalkoxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecyloxy group, a tetracyclodecyloxy 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, and the total carbon number is more preferably in the range of 7 to 15, and preferably has Alkoxy group of a monocyclic cycloalkyl group. The alkoxy group having a total carbon number of 7 or more and having a monocyclic cycloalkyl group means an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentyloxy group. , hexyloxy, heptyloxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, second butoxy, tert-butoxy and isopentyloxy) The above monocyclic cycloalkyl group which may have a substituent, and the total carbon number including the carbon number of the substituent is 7 or more. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferred.

Further, examples of the alkoxy group having a total carbon number of 7 or more and having a polycyclic cycloalkyl group include a norbornylalkylmethoxy group, a norbornylalkylethoxy group, a tricyclodecylmethoxy group, and a tricyclic ring. Mercaptoethoxy, tetracyclodecylmethoxy, tetracyclodecylethoxy, adamantylmethoxy, adamantylethoxy, and the like, and norbornylalkyl methoxy, lower Borane alkyl ethoxy groups and the like are preferred.

Specific examples of the alkyl group in the alkylcarbonyl group of R _{14 are} the same as the above alkyl group as R ₁₃ to R ₁₅ .

The alkylsulfonyl group and the cycloalkylsulfonyl group of R _{14 are} preferably a linear, branched or cyclic alkylsulfonyl group having 1 to 10 carbon atoms, and preferred examples thereof include methanesulfonate. Base, ethanesulfonyl, n-propanesulfonyl, n-butanesulfonyl, cyclopentanesulfonyl, cyclohexanesulfonyl and the like.

Examples of the substituent which each group may have include a halogen atom (e.g., a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group. And similar groups.

Examples of the alkoxy group include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms and the like, such as a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, N-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, cyclopentyloxy and cyclohexyloxy.

Examples of the alkoxyalkyl group include a linear, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms, such as methoxymethyl, ethoxymethyl, 1-methoxyB. Base, 2-methoxyethyl, 1-ethoxyethyl and 2-ethoxyethyl.

Examples of the alkoxycarbonyl group include a linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms and the like, such as a methoxycarbonyl group, an ethoxycarbonyl group, N-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxycarbonyl, tert-butoxycarbonyl, cyclopentyloxycarbonyl and cyclic Hexyloxycarbonyl.

Examples of the alkoxycarbonyloxy group include a linear, branched or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms and the like, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group. , n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, tert-butoxycarbonyloxy, cyclopentyloxycarbonyloxy and cyclohexyloxycarbonyloxy .

Examples of the ring structure which can be formed by combining two R ₁₅ with each other include a 5-member or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the formula (ZI-4), and particularly preferably 5 members Ring (ie, tetrahydrothiophene ring) and can be condensed with an aryl or cycloalkyl group. The divalent R ₁₅ may have a substituent, and 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 alkoxycarbonyl group, an alkoxy group. A carbonyloxy group and the like. As the substituent on the ring structure, a plurality of substituents may exist, and the substituents may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, by these rings) A combination of two or more of them forms a polycyclic fused ring or a similar ring).

In the formula (ZI-4), R _{15 is} preferably a methyl group, an ethyl group, a naphthyl group, a divalent group capable of forming a tetrahydrothiophene ring structure together with a sulfur atom by combining two R ₁₅ and a similar group. group.

The substituent which 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.

r is preferably from 0 to 2.

An example package of a cation in a compound represented by the formula (ZI-4) in the present invention Japanese Patent Application Laid-Open No. 2010-256842, paragraph [0121], paragraph [0123], and paragraph [0124], Japanese Patent Application Laid-Open No. 2011-76056, paragraph [0127] [0129] The cations and similar cations described in paragraph [0130].

A preferred embodiment of the compound (ZI-4) comprises a compound represented by the following formula (ZI-4').

In the formula (ZI-4'), R ₁₃ ' represents a branched alkyl group.

When a plurality of R ₁₄ are present, R ₁₄ each independently represents hydroxy, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl or has a ring A group of an alkyl group.

Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and two R ₁₅ groups are combined with each other to form a ring.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

Z ^- represents a non-nucleophilic anion.

Examples of the branched alkyl group of R ₁₃ ' include an isopropyl group and a third butyl group, of which a third butyl group is preferred.

In the formula (ZI-4'), a group of each of R ₁₄ and R ₁₅ , a ring structure formed by combining two R ₁₅ with each other, and a specific example of Z ^- and preferred examples and those in the formula (ZI-4) The same is true.

The preferred ranges of l and r are also the same as those described in the formula (ZI-4).

Subsequently, the formula (ZII) and the formula (ZIII) will be described.

In the formula (ZII) and the formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ 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 structure of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene, and the like.

The alkyl or cycloalkyl group of R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and pentyl group) and A cycloalkyl group of 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, and norbornyl group).

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms). And 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, a phenylthio group and the like. Z ^- represents a non-nucleophilic anion, and an example thereof is the same as a non-nucleophilic anion of Z ^{- in} the formula (ZI).

Examples of the acid generator further include a compound represented by the following formula (ZIV), formula (ZV), and formula (ZVI).

In the formula (ZIV) to the formula (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl 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 of R ₂₀₁ , R ₂₀₂ and R _{203 in} the formula (ZI-1).

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the alkyl group and the cycloalkyl group of R ₂₀₁ , R ₂₀₂ and R _{203 in} the formula (ZI-2).

Examples of the alkylene group of A include an alkylene group having 1 to 12 carbon atoms (e.g., methylene, ethyl, propyl, isopropyl, butyl, isobutyl, and the like). Examples of the alkenyl group of A include an alkenyl group having 2 to 12 carbon atoms (e.g., a vinyl group, a propenyl group, a butenyl group, and the like); and an aryl group of A Examples include an extended aryl group having 6 to 10 carbon atoms (e.g., a phenyl group, a tolyl group, an anthranyl group, and the like).

Among the acid generators, the compound represented by the formula (ZI) to the formula (ZIII) is more preferable.

Further, the acid generator is preferably a compound capable of producing an acid having a sulfonic acid group or a quinone imine group, more preferably a compound capable of producing a monovalent perfluoroalkanesulfonic acid, capable of producing a monovalent fluorine atom or a fluorine atom-containing group. a compound substituted with an aromatic sulfonic acid, or a compound capable of producing an imidic acid substituted with a monovalent fluorine atom or a fluorine atom-containing group, and more preferably a fluorine-substituted alkanesulfonic acid or a fluorine-substituted benzenesulfonate. An acid, a fluorine-substituted imidic acid or a fluorine-substituted methion acid salt of a method acid. The acid generator which can be used is particularly preferably a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid or a fluorine-substituted imidic acid, wherein the acid produced has a pKa of -1 or less than -1, and spirit Sensitivity is enhanced.

Among the acid generators, particularly preferred examples will be described below.

The acid generator can be synthesized by a known method, and can be synthesized according to the method described in, for example, Japanese Patent Application Laid-Open No. 2007-161707.

The acid generator may be used singly or in combination of two or more thereof.

The content of the compound capable of generating an acid after irradiation with actinic rays or radiation is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition. The mass% to 25% by mass, more preferably 3% by mass to 20% by mass, and particularly preferably 3% by mass to 15% by mass.

Further, when the acid generator is represented by the formula (ZI-3) or the formula (ZI-4), the content thereof is preferably from 5% by mass to 35% by mass, more preferably 8% by mass based on the total solid content of the composition. From 3% to 30% by mass, more preferably from 9% by mass to 30% by mass, and particularly preferably from 9% by mass to 25% by mass.

[3] Resin (D) which is different from the resin (A) and which is substantially free of fluorine atoms and germanium atoms

The photosensitive ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (D) different from the resin (A) and substantially free of fluorine atoms and germanium atoms (hereinafter, in some cases, simply referred to as "resin ( D) (resin(D))"). Therefore, the water receding contact angle on the resist film formed in the step (a) can be further improved, and excellent film thickness uniformity as well as bridging defects and watermark defects can be achieved.

Here, the resin (D) is substantially free of a fluorine atom and a ruthenium atom, but specifically, the content of the repeating unit having a fluorine atom or a ruthenium atom is preferably 5 in terms of all the repeating units in the resin (D). Ear % or less than 5 mole %, more preferably 3 mole % or less than 3 mole %, and more preferably 1 mole % or less than 1 mole %, and ideally 0 Mole%, that is, no fluorine atom and helium atom. Further, it is preferred that the resin (D) consists essentially only of repeating units consisting only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms. More specifically, in terms of all the repeating units in the resin (D), only repeating units composed of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms are preferably 95% by mole or More than 95% by mole, more preferably 97% by mole or more than 97% by mole, more preferably 99% by mole or more than 99% by mole, and desirably 100 mole%.

The content of the resin (D) of the present invention in the composition is obtained from the viewpoint that the resin (D) is unevenly distributed in the top portion of the resist film to achieve excellent film thickness uniformity and to reduce bridging defects and watermark defects. It is preferably from 0.1% by mass to 10% by mass, more preferably from 0.2% by mass to 8% by mass, even more preferably from 0.3% by mass to 6% by mass, based on the total solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition, and It is particularly preferably from 0.5% by mass to 5% by mass.

In the present invention, it is preferred that the resin (D) has a high CLogP value.

The higher the CLogP value of the resin (D), the higher the hydrophobicity of the resin (D), and the water receding contact angle on the resist film formed in the step (a) can be further improved, and thus The watermark defect in the immersion exposure can be further suppressed.

Further, the higher the CLogP value of the resin (D), the better the solubility in the solvent, and thus the uniformity of the film thickness of the resist film can be further improved, and the bridging defects can be reduced.

Here, the CLogP value refers to a common logarithmic value of the 1-octanol/water partition coefficient P, which represents the equilibrium concentration of the compound (resin (D)) in 1-octanol and the equilibrium concentration of the resin (D) in water. ratio.

From the above point of view, the resin (D) preferably has a CLogP value of 1.5 or greater. It is 1.5, more preferably 2.5 or more, further preferably 2.8 or more, and particularly preferably 3.5 or more.

Further, the upper limit of the CLogP value of the resin (D) is not particularly limited, but is preferably 10.0 or less, and more preferably 8.0 or less than 8.0.

In the present invention, the CLogP value of the resin (D) can be calculated as follows.

When the resin (D) is composed of the repeating units D1, D2, ..., Dx, ..., and Dn, the CLogP values of the monomers corresponding to the repeating units D1, D2, ..., Dx, ..., and Dn are each defined as ClogP1, ClogP2, ..., ClogPx, ..., and ClogPn, and the molar ratios of the repeating units D1, D2, ..., Dx, ..., and Dn in the resin (D) are each defined as ω1, ω2, ..., ωx , ... and ωn, the CLogP value of the resin (D) can be calculated by the following equation.

CLogP value of resin (D) = Σ [(ω1 × ClogP1) + (ω2 × ClogP2) + ... + (ωx × ClogPx) + ... + (ωn × ClogPn)]

Furthermore, the CLogP values (ClogP1, ClogP2, ..., ClogPx, ..., and ClogPn) of the monomers corresponding to the repeating units D1, D2, ..., Dx, ..., and Dn can be used by Cambridge Software Corporation (Cambridgesoft) Chemical drawing software (ChemDraw Ultra) (version 8.0) manufactured by Corp.

From the viewpoint of the ClogP value of the self-reinforced resin (D), the resin (D) preferably contains a repeating unit corresponding to a monomer having a ClogP value of 2.5 or more, and more preferably contains a ClogP value of 2.8 or more. The repeating unit of the monomer, and further preferably contains a repeating unit corresponding to a monomer having a ClogP value of 3.5 or more.

The upper limit of the ClogP value of the monomer corresponding to the repeating unit contained in the resin (D) is not particularly limited, but is preferably 10.0 or less, and more preferably 8.0 or less than 8.0.

Specific examples of the specific examples of the respective repeating units which can constitute the resin (D) and the CLogP value of the monomer corresponding to the repeating unit will be described below, but the present invention is not limited to the examples.

Specific examples of the resin (D) and specific examples of the CLogP value thereof will be described below, but the invention is not limited to the examples.

Further, in the resin (D), the mass content ratio of the CH ₃ partial structure in the side chain portion in the resin (D) is preferably 12.0% or more, and more preferably 18.0% or more than 18.0%. Therefore, low surface free energy can be achieved and the uneven distribution of the resin (D) in the top portion of the resist film can be further improved and, therefore, uniformity of film thickness can be improved, and bridging defects during immersion exposure can be made and Watermark defects are reduced.

Further, the upper limit of the mass content ratio of the CH ₃ partial structure in the side chain portion in the resin (D) is preferably 50% or less, and more preferably 40% or less.

Here, the methyl group directly bonded to the main chain of the resin (D) (for example, α-methyl group having a repeating unit of a methacrylic acid structure) slightly contributes to uneven distribution of the surface of the resin (D) due to the influence of the main chain. And therefore not included in the CH ₃ partial structure of the present invention and not counted. More specifically, when the resin (D) contains 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 formula (M)) and when R ₁₁ to R _{14 When} "as it is" is CH ₃ , the CH ₃ does not contain (not count) the CH ₃ partial structure of the present invention which is present in the side chain portion.

At the same time, the CH ₃ partial structure present via any atom in the CC backbone is counted as a CH ₃ partial structure. For example, when R ₁₁ is ethyl (CH ₂ CH ₃ ), R ₁₁ is counted to have a "one" structure of the CH ₃ moiety of the present invention.

In the formula (M), R ₁₁ to R ₁₄ each independently represent a side chain moiety.

Examples of R ₁₁ to R ₁₄ in the side chain moiety include a hydrogen atom, a monovalent organic group, and the like.

Examples of the monovalent organic group of R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylamino group. Carbonyl, arylaminocarbonyl and the like.

The monovalent organic group may have a more substituent, and examples of the substituent are the same as the specific examples of the substituent which the aromatic group Ar ₂₁ in the formula (II) can have, and preferred examples thereof.

In the present invention, the side chain portion of the resin (D) in the portion having the structure CH ₃ (hereinafter, simply referred to as "side chain the partial structure CH ₃ (side chain CH ₃ partial structure)" in some cases) containing ethyl The propyl group and the like have a CH ₃ moiety structure.

Hereinafter, the mass content ratio of the CH ₃ partial structure which the side chain portion in the resin (D) has in the resin (D) will be described (hereinafter, in some cases, simply referred to as "the side chain CH _{3 in the} resin (D)) Mass content ratio of the side chain CH3 partial structure in the resin (D))).

Here, the mass content ratio of the side chain CH ₃ partial structure in the resin (D) will be described by exemplifying the case where the resin (D) is composed of the repeating units D1, D2, ..., Dx, ..., and Dn. Further, the molar ratios of the repeating units D1, D2, ..., Dx, ..., and Dn in the resin (D) are ω1, ω2, ..., ωx, ..., and ωn, respectively.

(1) First, the mass content ratio (MCx) of the side chain CH ₃ partial structure of the repeating unit Dx can be calculated by the following equation: "100 × 15.03 × (the CH ₃ partial structure in the side chain portion in the repeating unit Dx) Number) / molecular weight (Mx) of repeating unit Dx.

Here, the number of CH ₃ partial structures in the side chain moiety in the repeating unit Dx does not include the number of methyl groups directly bonded to its main chain.

(2) Next, by the following equation can, by using the calculated ratio of the mass content of the partial structure of the side chain CH ₃ calculated sum of the repeating unit (D) in the side chain CH ₃ mass content ratio of the partial structure of the resin.

Mass content ratio of side chain CH ₃ partial structure in resin (D): DMC = Σ [(ω1 × MC1) + (ω2 × MC2) + ... + (ωx × MCx) + ..... .+(ωn×MCn)]

The resin (D) contains a repeating unit preferably having 2 or more CH ₃ moiety structures in its side chain, more preferably 3 or more 3 CH ₃ in its side chain. The partial structure further preferably has 3 to 10 CH ₃ moiety structures in its side chain, and particularly preferably has 3 to 8 CH ₃ moiety structures in its side chain.

Due to the configuration, the mass content of the CH ₃ partial structure in the side chain of the resin (D) is increased, and the surface free energy of the resin (D) becomes lower than the surface free energy of the resin (A). Thereby, it is expected that the positioning of the resin (D) at the surface portion of the resist film is enhanced. And then, the resist thickness uniformity is improved, bridging defects are reduced during immersion exposure, and watermark defects are reduced.

From the viewpoint of preferably improving the water back-off contact angle on the resist film formed in the step (a) and more reliably achieving excellent film thickness uniformity and reducing bridging defects and watermark defects, a resin is preferred. (D) having at least one repeating unit represented by the following formula (II) or formula (III), and more preferably the resin (D) consisting only of at least one repeating unit represented by the following formula (II) or formula (III) composition.

In the formula (II), R ₂₁ to R ₂₃ each independently represent a hydrogen atom or an alkyl group.

Ar ₂₁ represents an aromatic group. R ₂₂ and Ar ₂₁ may form a ring, and in the above case, R ₂₂ represents an alkylene group.

In the formula (III), R ₃₁ to R ₃₃ each independently represent a hydrogen atom or an alkyl group.

X ₃₁ represents -O- or -NR ₃₅ -. R ₃₅ represents a hydrogen atom or an alkyl group.

R ₃₄ represents an alkyl group or a cycloalkyl group.

In the formula (II), the alkyl group of R ₂₁ to R ₂₃ is preferably an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, propyl and butyl), more preferably methyl or ethyl. A base, and particularly preferably a methyl group.

When R ₂₂ forms a ring with Ar ₂₁ , examples of the alkyl group include a methylene group, an ethyl group and the like.

R ₂₁ to R ₂₃ in the formula (II) are particularly preferably a hydrogen atom or a methyl group.

The aromatic group of Ar ₂₁ in the formula (II) may have a substituent, and examples thereof include an aryl group having 6 to 14 carbon atoms, such as a phenyl group and a naphthyl group, or an aromatic group containing a heterocyclic ring, such as Thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole, but may have a substituent and have 6 to 14 carbon atoms The aryl groups such as phenyl and naphthyl are preferred.

Examples of the substituent which the aromatic group Ar ₂₁ may have include an alkyl group, an alkoxy group, an aryl group, and the like, but from the viewpoint of the CLogP value of the modified resin (D) and the hydrophobicity to improve the receding contact angle, The alkyl group and the alkoxy group are preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group, and a methyl group, an isopropyl group, a tert-butyl group and a third butoxy group are particularly preferred.

Further, the aromatic group of Ar ₂₁ may have two or more than two substituents.

In the formula (III), the alkyl group of R ₃₁ to R ₃₃ and R ₃₅ is preferably an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group and butyl group), more preferably A. A base and an ethyl group, and particularly preferably a methyl group. R ₃₁ to R ₃₃ in the formula (III) are each independently preferably a hydrogen atom and a methyl group.

X ₃₁ in the formula (III) is preferably -O- and -NH- (that is, when R ₃₅ in -NR ₃₅ - is a hydrogen atom), and particularly preferably -O-.

In the formula (III), the alkyl group of R ₃₄ may be a straight chain or a branched chain, and examples thereof include a linear alkyl group (for example, methyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, and positive tenth). Dialkyl and similar groups), branched alkyl groups (eg isopropyl, isobutyl, tert-butyl, methylbutyl, dimethylpentyl and the like), but self-modified resins (D CLogP value and hydrophobicity, from the viewpoint of improving the receding contact angle, a branched alkyl group is preferred, a branched alkyl group having 3 to 10 carbon atoms is more preferable, and has 3 to 8 carbons. A branched alkyl group of an atom is particularly preferred.

In the formula (III), the cycloalkyl group of R ₃₄ may have a substituent, and examples thereof include a monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and a polycyclic cycloalkyl group such as norbornene. An alkyl group, a tetracyclic fluorenyl group, and an adamantyl group, but a monocyclic cycloalkyl group is preferred, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a cyclohexyl group is particularly preferable.

Examples of the substituent which R ₃₄ may have include an alkyl group, an alkoxy group, an aryl group and the like, but from the viewpoint of the CLogP value of the modified resin (D) and the hydrophobicity to improve the receding contact angle, the alkyl group and The alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group, and a methyl group, an isopropyl group, a tert-butyl group and a third butoxy group are particularly preferred.

Further, the alkyl group of R ₃₄ and the cycloalkyl group may have two or more than two substituents.

It is preferred that R _{34 is} not a group capable of decomposing and leaving under the action of an acid, that is, the repeating unit represented by the formula (III) is not a repeating unit having an acid-decomposable group.

In the formula (III), R _{34 is} most preferably a cyclohexyl group substituted with a branched alkyl group having 3 to 8 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group.

In the formula (II) and the formula (III), as mentioned above, from the viewpoint of improving the mass content of the CH ₃ partial structure in the side chain of the resin (D), the resin (D) contains the following repeating unit, The repeating unit preferably has 2 or more than 2 CH ₃ moiety structures in its side chain, more preferably ₃ or more 3 CH ₃ moiety structures in its side chain, and more preferably in its side chain. It contains 3 to 10 CH ₃ moiety structures, and particularly preferably has 3 to 8 CH ₃ moiety structures in its side chain.

Specific examples of the repeating unit represented by the formula (II) or the formula (III) will be described below, but the invention is not limited to the examples.

When the resin (D) has a repeating unit represented by the formula (II) or the formula (III), the CLogP value of the modified resin (D) and the hydrophobicity are improved to improve the receding contact angle, thereby achieving the effect of the present invention. The content of the repeating unit represented by the formula (II) or the formula (III) is preferably in the range of 50 mol% to 100 mol%, more preferably 65 mol, based on all the repeating units in the resin (D). The ear is in the range of from 100% by mole to 100% by mole, and particularly preferably in the range of from 80% by mole to 100% by mole.

The resin (D) may more suitably have a repeating unit containing an acid-decomposable group, a repeating unit having a lactone structure, a repeating unit having a hydroxyl group or a cyano group, a repeating unit having an acid group (alkali-soluble group), and having Alicyclic hydrocarbon knots without polar groups A repeating unit which does not exhibit acid decomposability, which is the same as that described above for the resin (A).

Specific examples of the respective repeating units which the resin (D) may have and preferred examples are the same as the specific examples and preferred examples of the respective repeating units described above for the resin (A).

However, from the viewpoint of more reliably achieving the action of the present invention, it is more preferred that the resin (D) does not have a repeating unit containing an acid-decomposable group, an alkali-soluble repeating unit, and a repeating unit having a lactone structure.

The weight average molecular weight of the resin (D) related to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 3,000 to 100,000, more preferably in the range of 6,000 to 70,000, and particularly preferably in the range of 10,000 to 40,000. In the range. In particular, by adjusting the weight average molecular weight in the range of 10,000 to 40,000, the uniformity of the film thickness at the time of forming a fine pattern is excellent, and the defect reduction efficiency is excellent at the time of immersion exposure. Here, the weight average molecular weight of the resin means a molecular weight according to polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

Further, the polydispersity (Mw/Mn) is preferably from 1.00 to 5.00, more preferably from 1.03 to 3.50, and still more preferably from 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and the shape of the resist pattern.

The resin (D) according to the present invention may be used singly or in combination of two or more thereof.

As the resin (D), various commercially available products can be used, and the resin (D) can be synthesized by a typical method such as radical polymerization. Examples of general synthetic methods include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent and added a hot solution to carry out polymerization; a drop-in polymerization method in which a solution containing a monomer substance and a starter is added dropwise to a heated solvent over 1 hour to 10 hours, and the like, and a dropping polymerization method Preferably.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, and the like) and the purification method after the reaction are the same as those described in the resin (A), but in the synthetic resin (D), the reactant concentration is preferably It is 10% by mass to 50% by mass.

Specific examples of the resin (D) will be described below, but the invention is not limited to the examples.

[4] a combination of at least one of a fluorine atom and a ruthenium atom and different from the resin (A) and the resin (D) (E)

The sensitizing ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a hydrophobic resin having at least one of a fluorine atom and a ruthenium atom and different from the resin (A) and the resin (D) (hereinafter, in some In the case, it is called "combined hydrophobic resin (E)" or simply "resin (E) (resin (E))"), especially when the composition is applied to immersion exposure. Therefore, when the combined hydrophobic resin (E) is unevenly distributed in the top layer of the film and the impregnation medium is water, the static/dynamic contact angle of water on the surface of the resist film can be improved to improve the immersion tracking property.

It is preferred that the combined hydrophobic resin (E) is designed to be unevenly distributed on the interface as described above, but unlike the surfactant, the combined hydrophobic resin (E) does not need to have a hydrophilic group in the molecule and may Does not contribute to the uniform mixing of polar / non-polar substances.

The combined hydrophobic resin (E) contains a fluorine atom and/or a ruthenium atom. The fluorine atom and/or the ruthenium atom in the combined hydrophobic resin (E) may be contained in the resin main chain or may be It is included in its side chain.

When the combined hydrophobic resin (E) contains a fluorine atom, a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group as a partial structure having a fluorine atom is preferred.

An alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, and more preferably having 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 It has a substituent other than a fluorine atom.

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.

The aryl group having a fluorine atom is an aryl group in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

Preferable 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 a group represented by the following formula (F2) to formula (F4), but the invention is not limited to the above Example.

In the formulae (F2) to (F4), R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched chain). 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 each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom ( It preferably has from 1 to 4 carbon atoms).

R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are each preferably a fluorine atom. R ₆₂ , R ₆₃ and R _{68 are} preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom (preferably having 1 to 4 carbon atoms), and more preferably a perfluoro group having 1 to 4 carbon atoms. alkyl. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

Specific examples of the group represented by the formula (F2) include p-fluorophenyl group, pentafluorophenyl group, 3,5-bis(trifluoromethyl)phenyl group and the like.

Specific examples of the group represented by the formula (F3) include trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro (2- Methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluoro-tert-butyl, perfluoroisopentyl, perfluorooctyl, perfluoro(trimethyl)hexyl, 2,2,3,3-tetrafluorocyclobutyl, perfluorocyclohexyl and the like. Hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluoro-tert-butyl and perfluoroisopentyl are preferred, and six Fluoroisopropyl and heptafluoroisopropyl are more preferred.

Specific examples of the group represented by the formula (F4) include -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, and -C(CF ₃ ) ₂ OH is preferred.

The partial structure containing a fluorine atom may be directly bonded to the main chain or may be further bonded to the main chain via a group selected from the group consisting of an alkyl group, a phenyl group, an ether bond, a thioether bond, a carbonyl group, An ester bond, a guanamine bond, a urethane bond, and a ureylene bond, or a group formed by combining two or more of these groups.

Hereinafter, a specific example of a repeating unit having a fluorine atom will be described, but the present invention is not limited to the examples.

In a particular example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

The combined hydrophobic resin (E) may contain a ruthenium atom. As the partial structure having a ruthenium atom, a resin having an alkyl fluorenyl structure (preferably a trialkyl decyl group) or a cyclic siloxane structure is preferred.

Specific examples of the alkyl fluorenyl structure or the cyclic siloxane structure include a group represented by the following formula (CS-1) to formula (CS-3) and the like.

In the formulae (CS-1) to (CS-3), R ₁₂ to R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (compared Good with 3 to 20 carbon atoms).

L ₃ to L ₅ each represents a single bond or a divalent linking group. Examples of the divalent linking group include a single member selected from the group consisting of two or a combination of two or more members (total carbon number is preferably 12 or less): alkylene group, phenylene group , an ether bond, a thioether bond, a carbonyl group, an ester bond, a guanamine bond, a urethane bond, and a urea bond.

n represents an integer from 1 to 5. n is preferably an integer of 2 to 4.

Hereinafter, a specific example of a repeating unit having a group represented by the formula (CS-1) to the formula (CS-3) will be described, but the present invention is not limited to the examples. Also, in a specific example, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

Further, the combined hydrophobic resin (E) may have at least one group selected from the group of (x) to (z): (x) an acid group (y) having a lactone structure, an acid anhydride group or an anthracene group An imido group, and (z) a group capable of decomposing under 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 sulfonylamino group, a sulfonimide group, an (alkylsulfonyl) (alkylcarbonyl) group , (alkylsulfonyl) (alkylcarbonyl) fluorenylene, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)indolylene, bis(alkylsulfonyl) methylene A bis(alkylsulfonyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, and the like.

Preferred examples of the acid group include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, and a bis(alkylcarbonyl)methylene group.

Examples of the repeating unit having an acid group (x) include a repeating unit in which an acid group is directly bonded to a resin main chain, such as a repeating unit of acrylic acid or methacrylic acid, and an acid group is bonded to the resin main chain via a linking group The unit is repeated, and the acid group can also be introduced into the end of the polymer chain by using a polymerization initiator or a chain transfer agent having an acid group at the time of polymerization, and thus all of these conditions are preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a germanium atom.

The content of the repeating unit having an acid group (x) is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 35 mol%, based on all the repeating units in the combined hydrophobic resin (E). More preferably, it is 5 mol% to 20 mol%.

Specific examples of the repeating unit having an acid group (x) will be described below, but the invention is not limited to the examples. In the following formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

As the group (y) having a lactone structure, an acid anhydride group or a quinone imine group, a group having a lactone structure is particularly preferable.

Examples of the repeating unit containing these groups include a repeating unit in which the group is directly bonded to a resin main chain, such as a repeating unit of acrylate or methacrylate. Further, the repeating unit may be a repeating unit in which the group is bonded to the resin main chain via a linking group. Further, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization.

Examples of the repeating unit having a group having a lactone structure are the same as those of the repeating unit having a lactone structure described in the paragraph of the acid-decomposable resin (A).

The content of the repeating unit having a group having a lactone structure, an acid anhydride group or a quinone imine group is preferably from 1 mol% to 100 mol% based on all the repeating units in the combined hydrophobic resin (E), more preferably 3 moles to 98 mole%, and more preferably 5 mole% to 95 mole%.

Examples of the repeating unit having a group (z) capable of decomposing under the action of an acid in the hydrophobic resin (E) are the same as those of the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having (z) a group capable of decomposing under the action of an acid may have at least one of a fluorine atom and a deuterium atom. In the hydrophobic resin (E), the content of the repeating unit having (z) a group capable of decomposing under the action of an acid is preferably from 1 mol% to 80 mol% based on all the repeating units in the resin (E). More preferably, it is 10 mol% to 80 mol%, and more preferably 20 mol% to 60 mol%.

The combined hydrophobic resin (E) may further have a repeating unit represented by the following formula (III):

In the formula (III), Rc ₃₁ represents a hydrogen atom, an alkyl group (which may be substituted by a fluorine atom or the like), a cyano group or a -CH ₂ -O-Rac ₂ group. In the above formula, Rac ₂ represents a hydrogen atom, an alkyl group or a fluorenyl group. Rc _{31 is} preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.

Rc ₃₂ 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 by a fluorine atom or a group containing a halogen atom.

Lc ₃ represents a single bond or a divalent linking group.

In the formula (III), the alkyl group of 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, and more preferably a phenyl group or a naphthyl group, and these groups may have a substituent.

Rc _{32 is} preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom.

The divalent linking group of Lc ₃ is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenyl group or an ester bond (a group represented by -COO-).

The content of the repeating unit represented by the formula (III) is preferably from 1 mol% to 100 mol%, more preferably 10 mol%, based on all the repeating units in the hydrophobic resin. 90% by mole, and more preferably 30% by mole to 70% by mole.

It is also preferred that the combined hydrophobic resin (E) further has a repeating unit represented by the following formula (CII-AB):

In the formula (CII-AB), R _c11 ' and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z _c ' represents an atomic group for forming an alicyclic structure, and the alicyclic structure contains two carbon atoms (CC) to which Z _c ' is bonded.

The content of the repeating unit represented by the formula (CII-AB) is preferably from 1 mol% to 100 mol%, more preferably from 10 mol% to 90 mol%, more preferably from 10 mol% to 90 mol%, based on all the repeating units in the hydrophobic resin. Good is 30% to 70% by mole.

Hereinafter, specific examples of the repeating unit represented by the formula (III) and the formula (CII-AB) are described below, but the invention is not limited to the examples. In the formula below, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When the combined hydrophobic resin (E) has a fluorine atom, the fluorine atom content is preferably from 5% by mass to 80% by mass, and more preferably from 10% by mass to 80% by mass, based on the weight average molecular weight of the combined hydrophobic resin (E). . Further, the repeating unit containing a fluorine atom is preferably from 10 mol% to 100 mol%, and more preferably from 30 mol% to 100 mol%, based on all the repeating units contained in the combined hydrophobic resin (E).

When the combined hydrophobic resin (E) has a ruthenium atom, the ruthenium atom content is preferably from 2% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass, based on the weight average molecular weight of the combined hydrophobic resin (E). . Further, the repeating unit containing a ruthenium atom is preferably from 10 mol% to 100 mol%, and more preferably from 20 mol% to 100 mol%, based on all the repeating units contained in the combined hydrophobic resin (E).

The standard polystyrene-equivalent weight average molecular weight of the combined hydrophobic resin (E) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 15,000.

Further, the combined hydrophobic resin (B) may be used singly or in combination of many thereof.

The content of the hydrophobic resin (E) is combined in the composition to the composition of the present invention. The total solid content is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, and still more preferably from 0.1% by mass to 5% by mass.

In the combination of the hydrophobic resin (E), similarly to the resin (A), the content of impurities such as metals should of course be small, but the content of the residual monomer or oligomer component is preferably from 0.01% by mass to 5% by mass. More preferably, it is 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass. Therefore, it is possible to obtain a sensitized ray-sensitive or radiation-sensitive resin composition in which the liquid does not contain foreign matter and the sensitivity and the like do not change with time. Further, in view of resolution, resist shape, sidewall of the resist pattern, roughness, and the like, the molecular weight distribution (Mw/Mn, also referred to as "polydispersity") is preferably from 1 to 5. Within the range, it is more preferably in the range of 1 to 3, and more preferably in the range of 1 to 2.

As the combined hydrophobic resin (E), various commercially available products can be used, and the resin (E) can be synthesized by a typical method such as radical polymerization. Examples of general synthetic methods include: a batch polymerization method in which a monomer substance and an initiator are dissolved in a solvent and the solution is heated to carry out polymerization; a dropping polymerization method in which a heated solvent is passed for 1 hour to 10 hours A solution containing a monomer substance and a starter is added dropwise, and the like, and a dropping type polymerization method is preferred.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, and the like) and the purification method after the reaction are the same as those described in the resin (A), but in the synthesis of the combined hydrophobic resin (E), the reactant The concentration is preferably from 30% by mass to 50% by mass.

Specific examples of combining the hydrophobic resin (E) will be described below. Further, the molar ratio, weight average molecular weight, and polydispersity of the repeating unit of each resin (corresponding to the repeating unit from the left) are shown in Tables 1 and 2 below.

[5] Solvent (C)

Preparation of the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention Examples of the solvent which can be used include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, and cyclic lactone. Preferably, it has from 4 to 10 carbon atoms, a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), an alkylene carbonate, an alkyl alkoxyacetate and an alkyl pyruvate.

Specific examples of such solvents include the solvents described in paragraphs [0441] to [0455] of U.S. Patent Application Publication No. 2008/0187860.

From the viewpoint of reducing bridging defects and watermark defects in immersion exposure, it is preferred that the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a mixed solvent composed of two or more solvents. The solvent contains at least one solvent having a standard boiling point (hereinafter, referred to as "boiling point" in some cases) of 200 ° C or more.

As described above, it is assumed that the factor of bridging defects may be a resin component which is slightly soluble in the developer containing the organic solvent on the surface of the resist film.

It is also assumed that by using a mixed solvent containing a solvent having a high boiling point (for example, a boiling point of 200 ° C or more), the component having a lower surface free energy in the sensitized ray-sensitive or radiation-sensitive resin composition tends to be further positioned. The surface of the resist film.

The solubility of the resin (D) of the present invention in an organic solvent tends to be excellent and tends to have low surface free energy.

Therefore, it is assumed that by using a mixed solvent containing a high boiling point solvent, the content of the resin (D) in the surface portion of the resist film is increased, and the solubility of the surface of the resist pattern in the developer containing the organic solvent is enhanced, and thereby The component which is slightly soluble in the organic solvent-containing developer which can be a factor of bridging defects can be dissolved and removed.

And, by using the above mixed solvent, the resist film of the resin (D) The uneven distribution of the surface is improved, and thus the receding contact angle can be improved. Therefore, watermark defects can be reduced during immersion exposure.

The content of the solvent having a standard boiling point of 200 ° C or more in the mixed solvent is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 3% by mass, and still more preferably 5% by mass. Further, the content thereof is 100% by mass or less, preferably 50% by mass or less, and more preferably 20% by mass or less. By adjusting the content within the range, bridging defects as well as watermark defects can be further reduced.

The solvent having a standard boiling point of 200 ° C or more is preferably represented by any one of the following formulas (S1) to (S3).

In the formulae (S1) to (S3), R ₁ to R ₄ and R ₆ to R ₈ each independently represent an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ , R ₃ and R ₄ or R ₇ and R ₈ may be bonded to each other to form a ring.

It is preferred that in the formulae (S1) to (S3), R ₁ to R ₄ and R ₆ to R ₈ are an alkyl group, and more preferably R ₁ and R ₂ , R ₃ and R ₄ and R ₇ And R ₈ are respectively bonded to each other to form a ring.

Further, the solvent having the structure represented by the formula (S1) to the formula (S3) is more preferably a solvent represented by the formula (S1) or the formula (S2), and most preferably a solvent represented by the formula (S1).

A preferred embodiment of a solvent having a structure represented by the formula (S1) to the formula (S3) Examples include a solvent having a lactone structure such as γ-butyrolactone (standard boiling point: 203 ° C); a solvent having an alkylene carbonate structure such as ethyl carbonate (standard boiling point: 244 ° C), propyl carbonate ( Standard boiling point: 242 ° C) and butyl carbonate (standard boiling point: 251 ° C); N-methylpyrrolidone (standard boiling point: 203 ° C) and the like. Among them, the solvent is more preferably a solvent having a lactone structure and a solvent having a alkyl carbonate structure, and particularly preferably γ-butyrolactone and propylene carbonate, and most preferably propyl carbonate.

In the present invention, the solvent in which the solvent (C) may have a standard boiling point of less than 200 ° C is not particularly limited, but examples thereof include the following solvent containing a hydroxyl group, a solvent containing no hydroxyl group, and the like.

Examples of the solvent containing a hydroxyl group include an alkylene glycol monoalkyl ether, an alkyl lactate, and the like, and, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (propylene) Glycol monomethyl ether; PGME, another name: 1-methoxy-2-propanol), propylene glycol monoethyl ether, ethyl lactate, and the like are preferred, and propylene glycol monomethyl ether and ethyl acetate are particularly preferred. .

Examples of the solvent containing no hydroxyl group include alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate, and the like, and, for example, propylene glycol Propylene glycol monomethyl ether acetate (PGMEA, another name: 1-methoxy-2-ethenyloxypropane), ethyl ethoxypropionate, 2-heptanone, cyclohexanone , butyl acetate, N,N-dimethylacetamide, dimethyl hydrazine and the like are preferred, and wherein propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone More preferably, cyclohexanone and butyl acetate are preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, and cyclohexanone are most preferred.

Mixing ratio of solvent containing hydroxyl group to solvent containing no hydroxyl group (by mass) The ratio is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40. In view of coating uniformity, a mixed solvent containing no hydroxyl group-containing solvent content of 50% by mass or more and more than 50% by mass is particularly preferable.

The solvent (C) preferably contains propylene glycol monomethyl ether acetate. The solvent (C) is more preferably a mixed solvent comprising a solvent having a normal boiling point of 200 ° C or more, a solvent containing a hydroxyl group, and a solvent containing no hydroxyl group; and more preferably a mixed solvent comprising the following: a standard boiling point of 200 Solvent at temperatures above 200 ° C, alkylene glycol monoalkyl ether acetate and alkylene glycol monoalkyl ether.

[6-1] Basic compound or ammonium salt compound (N) with reduced alkalinity after irradiation with actinic rays or radiation

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound or an ammonium salt compound having a reduced alkalinity after irradiation with actinic rays or radiation (hereinafter also referred to as "compound (N)). (compound(N))").

The compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group capable of generating an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group capable of generating an acidic functional group after irradiation with actinic rays or radiation, or having an ammonium group and capable of using actinic rays or An ammonium salt compound which produces a group of an acidic functional group upon irradiation with radiation.

In particular, examples thereof include a compound in which a salt is formed from an anion with a phosphonium cation and the like, which is produced by eliminating a proton from an acidic functional group of a compound having a basic functional group or an ammonium group and an acidic functional group.

Here, examples of the basic functional group include an atom containing a structure such as a crown ether, a primary to tertiary amine, and a nitrogen-containing heterocyclic ring (pyridine, imidazole, pyrazine, and the like). group. Further, examples of preferred structures of the ammonium group include atomic groups containing a primary to tertiary ammonium structure, a pyridinium structure, an imidazolium structure, a pyrazinium structure, and the like. Further, the basic functional group is preferably a functional group having a nitrogen atom, and more preferably a structure having a primary to tertiary amino group or a nitrogen-containing heterocyclic structure. In these structures, from the viewpoint of improving the alkalinity, it is preferred that all of the atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. Further, from the viewpoint of improving the alkalinity, it is preferred that the electron-donating functional group (carbonyl group, sulfonyl group, cyano group, halogen atom and the like) is not directly bonded to the nitrogen atom.

Examples of the acidic functional group include a carboxylic acid group, a sulfonic acid group, a group having a structure of -X-NH-X-(X=CO or SO ₂ ), and the like.

Examples of phosphonium cations include phosphonium cations, phosphonium cations, and the like. More specific examples thereof include cations and similar cations described as the acid moiety (ZI) and the cationic portion of formula (ZII).

More specific examples of the compound which is produced by decomposition of the compound (N) or the compound (N-1) after irradiation with actinic rays or radiation and whose alkalinity is lowered include the following formula (PA-1), formula (PA-II) Or a compound represented by the formula (PA-III), and expressed by the formula (PA-II) or the formula (PA-III) from the viewpoint of the superior effect of the height enhancement on the LWR, the uniformity of the local pattern size, and the DOF point of view. The compounds are especially preferred.

First, a compound represented by the formula (PA-I) will be described.

QA ₁ -(X) _n -BR (PA-I)

In the 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 which is generated after 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.

The divalent linking group in A ₁ is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group, a phenylene group, and the like. The alkyl group having at least one fluorine atom is more preferably, and its carbon number is preferably from 2 to 6, more preferably from 2 to 4. The alkyl chain may have a linking group such as an oxygen atom and a sulfur atom. The alkylene group is preferably an alkylene group in which a hydrogen atom of 30% to 100% is substituted by a fluorine atom, and more preferably an alkyl group having a fluorine atom bonded to a carbon atom bonded to the Q site. Further, a perfluoroalkylene group is preferred, and a perfluoroextended ethyl group, a perfluoroextended propyl group, and a perfluorobutylene group are more preferred.

The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and the like.

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

Further, examples of the alkyl group having a substituent include, in particular, a group in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, camphor residue, and Similar group).

The cycloalkyl group in Rx may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

The aryl group in Rx may have a substituent, and preferably has 6 to 14 An aryl group of a carbon atom.

The aralkyl group in Rx may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms.

The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at any position of the alkyl group exemplified as Rx.

Examples of preferred partial structures of the basic functional group include structures such as crown ethers, primary to tertiary amines, and nitrogen-containing heterocyclic rings (pyridine, imidazole, pyrazine, and the like).

Examples of preferred partial structures of the ammonium group include a primary to tertiary ammonium structure, a pyridinium structure, an imidazolium structure, a pyrazinium structure, and the like.

Further, the basic functional group is preferably a functional group having a nitrogen atom, and more preferably a structure having a primary to tertiary amino group or a nitrogen-containing heterocyclic structure. In these structures, from the viewpoint of improving the alkalinity, it is preferred that all of the atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. Further, from the viewpoint of improving the alkalinity, it is preferred that the electron-donating functional group (carbonyl group, sulfonyl group, cyano group, halogen atom and the like) is not directly bonded to the nitrogen atom.

The monovalent organic group in the monovalent organic group (group R) comprising the structure preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. And similar groups, and each group may have a substituent.

An alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an alkyl group in the R, which are represented by Rx. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group are the same.

Examples of the substituent which each group may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably having 6). Up to 14 carbon atoms), alkoxy (preferably having 1 to 10 carbon atoms), fluorenyl (preferably having 2 to 20 carbon atoms), decyloxy (preferably having 2 to 10 carbon atoms), alkoxycarbonyl (preferably having 2 to 20 carbons) Atom), an amine fluorenyl group (preferably having 2 to 20 carbon atoms) and the like. The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having 1 to 20 carbon atoms) as a substituent. The amine fluorenyl group may have one or two alkyl groups (preferably having 1 to 20 carbon atoms) as a substituent.

When B is -N(Rx)-, R and Rx are preferably bonded to each other to form a ring. By forming a ring structure, stability is improved, and the storage stability of the composition using the same is improved. The number of carbon atoms forming the ring is preferably from 4 to 20, and the ring may be monocyclic or polycyclic and may contain an oxygen atom, a sulfur atom or a nitrogen atom in the ring. Examples of monocyclic structures include a 4- to 8-membered ring containing a nitrogen atom. Examples of polycyclic structures include structures composed of two single ring structures or a combination of three or more than three single ring structures.

The monocyclic structure and the polycyclic structure may have a substituent, and preferred examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group. (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), a fluorenyl group (preferably having 2 to 15 carbon atoms), a decyloxy group (preferably) It has 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), an amine fluorenyl group (preferably having 2 to 20 carbon atoms), and the like. The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent. The amine fluorenyl group may have one or two alkyl groups (preferably having 1 to 15 carbon atoms) as a substituent.

Among the compounds represented by the formula (PA-I), a compound having a Q site of a sulfonic acid can be synthesized by using a general sulfoximation reaction. For example, a compound can be used The following method obtains: a method of selectively reacting one sulfonyl halide moiety of a bissulfonyl halide compound with an amine compound to form a sulfonamide bond, and then partially hydrolyzing another sulfonyl halide; or A method in which a cyclic sulfonic anhydride is opened by reaction with an amine compound.

Then, the compound represented by the formula (PA-II) will be described.

Q ₁ -X ₁ -NH-X ₂ -Q ₂ (PA-II)

In the formula (PA-II), Q ₁ and Q ₂ each independently represent a monovalent organic group. However, Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may be bonded to each other to form a ring, and the ring formed may have a basic functional group.

X ₁ and X ₂ each independently represent -CO- or -SO ₂ -. Further, -NH- corresponds to an acidic functional group which is generated after irradiation with actinic rays or radiation.

The monovalent organic group as Q ₁ and Q _{2 in} the formula (PA-II) preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. And similar groups.

The alkyl group in Q ₁ and Q ₂ may have a substituent and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and the alkyl chain may have an oxygen atom, a sulfur atom or a nitrogen atom.

The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom and a nitrogen atom in the ring.

The aryl group in Q ₁ and Q ₂ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

The aralkyl group in Q ₁ and Q ₂ may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms.

The alkenyl group in Q ₁ and Q ₂ may have a substituent, and examples thereof include a group having a double bond at any position of the alkyl group.

Examples of the substituent which each group may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably having 6). Up to 14 carbon atoms), alkoxy (preferably having 1 to 10 carbon atoms), fluorenyl (preferably having 2 to 20 carbon atoms), decyloxy (preferably having 2 to 10) A carbon atom), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), an amine fluorenyl group (preferably having 2 to 10 carbon atoms), and the like. The cyclic structure in the aryl group, the cycloalkyl group and the like may further have an alkyl group (preferably having 1 to 10 carbon atoms) as a substituent. The amine fluorenyl group may have an alkyl group (preferably having 1 to 10 carbon atoms) as a substituent. Examples of the alkyl group having a substituent include a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

The preferred partial structure of the basic functional group having at least one of Q ₁ and Q ₂ is the same as the partial structure described as the basic functional group of R of the formula (PA-I).

Examples of the structure in which Q ₁ and Q ₂ are bonded to each other to form a ring and the ring formed has a basic functional group include an organic group of Q ₁ and Q ₂ further via an alkylene group, an oxy group, an imido group or the like. The structure of the bond.

In the formula (PA-II), at least one of X ₁ and X ₂ is preferably -SO ₂ -. Then, the compound represented by the formula (PA-III) will be described.

Q ₁ -X ₁ -NH-X ₂ -A ₂ -(X ₃ ) _m -BQ ₃ (PA-III)

In the formula (PA-III), Q ₁ and Q ₃ each independently represent a monovalent organic group. However, Q ₁ or Q ₃ has a basic functional group. Q ₁ and Q ₃ may be bonded to each other to form a ring, and the ring formed 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 be bonded to each other to form a ring. m represents 0 or 1.

Further, -NH- corresponds to an acidic functional group which is generated after irradiation with actinic rays or radiation.

Q ₁ in the same meaning as Q in formula (PA-II) of _1.

Examples of the organic group of Q ₃ are the same as those of the organic groups of Q ₁ and Q _{2 in} the formula (PA-II).

Further, examples in which Q ₁ and Q ₃ are bonded to each other to form a ring and the ring formed has a basic functional group include an organic group of Q ₁ and Q ₃ further via an alkylene group, an oxy group, an imido group or the like. The structure of the group bond.

The divalent linking group in A ₂ is preferably a divalent linking group having 1 to 8 carbon atoms and having a fluorine atom, and examples thereof include having 1 to 8 carbon atoms and having a fluorine atom An alkyl group, a phenyl group having a fluorine atom, and the like. The alkyl group having a fluorine atom is more preferable, and the number of carbon atoms is preferably from 2 to 6, more preferably from 2 to 4. The alkyl chain may have a linking group such as an oxygen atom and a sulfur atom. The alkylene group is preferably an alkylene group in which a hydrogen atom of 30% to 100% is substituted by a fluorine atom, preferably a perfluoroalkylene group, and particularly preferably a perfluoroextension having 2 to 4 carbon atoms. alkyl.

The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and the like. Examples of alkyl, cycloalkyl, aryl, aralkyl and alkenyl groups and formula (PA-I) The example of Rx is the same.

In the formula (PA-III), X ₁ , X ₂ and X _{3 are} preferably -SO ₂ -.

The compound (N) is preferably an onium salt compound of a compound represented by the formula (PA-I), the formula (PA-II) or the formula (PA-III) or a formula (PA-I) or a formula (PA-II). Or a phosphonium salt compound of the compound represented by the formula (PA-III), and more preferably a compound represented by the following formula (PA1) or (PA2).

In the formula (PA1), _R'201 , _R'202 and _R'203 each independently represent an organic group, and specific examples thereof and R ₂₀₁ , R ₂₀₂ and R ₂₀₃ of the formula ZI in the component (B) The examples are the same.

X ^- represents a sulfonate anion or a carboxylate anion produced by eliminating a hydrogen atom in the -SO ₃ H moiety or the -COOH moiety of the compound represented by the formula (PA-I), or by elimination of the formula (PA-II) or An anion produced by a hydrogen atom in the -NH- moiety of the compound represented by the formula (PA-III).

In formula (PA2), R _'204 and R' ₂₀₅ independently represents an aryl, alkyl or cycloalkyl group, and specific examples of component (B) of formula ZII the same as examples of R ₂₀₄ and R ₂₀₅ of.

X ^- represents a sulfonate anion or a carboxylate anion produced by eliminating a hydrogen atom in the -SO ₃ H moiety or the -COOH moiety of the compound represented by the formula (PA-I), or by elimination of the formula (PA-II) or An anion produced by a hydrogen atom in the -NH- moiety of the compound represented by the formula (PA-III).

Compound (N) decomposes after irradiation with actinic rays or radiation to produce, for example A compound represented by the formula (PA-I), the formula (PA-II) or the formula (PA-III).

The compound represented by the formula (PA-I) has a sulfonic acid group or a carboxylic acid group and a basic functional group or an ammonium group and thus has a reduced alkalinity or a loss of alkalinity or self-basicity compared to the compound (N). An acidic compound.

The compound represented by the formula (PA-II) or the formula (PA-III) has an organic sulfonimide group or an organic carbonylimino group and a basic functional group and thus has a lower alkalinity than the compound (N). Or a compound that loses alkalinity or changes from basic to acidic.

In the present invention, the decrease in alkalinity after irradiation with actinic rays or radiation means that protons of the compound (N) (acids generated after irradiation with actinic rays or radiation) are subjected to irradiation with actinic rays or radiation. After the reduction. The decrease in acceptor properties means that when an equilibrium reaction of a non-covalent bond complex in the form of a proton adduct is produced from a compound containing a basic functional group and a proton, or when a relative cation and proton of the compound containing the ammonium group is carried out When the equilibrium reaction is exchanged, the equilibrium constant of the chemical equilibrium is reduced.

In this manner, the resist film contains the compound (N) having a reduced alkalinity after irradiation with actinic rays or radiation, so that the acceptor characteristics of the compound (N) can be sufficiently exhibited in the unexposed portion. And it is possible to suppress an unintended reaction of the acid diffused from the exposed portion or the like with the resin (A), and in the exposed portion, the acceptor property of the compound (N) is lowered, and thus the acid and the expected reaction of the resin (A) are more Inevitably, and in terms of the contribution of the operating mechanism, it is assumed that a pattern excellent in line width variation (LWR), partial pattern size uniformity, focus latitude (DOF), and pattern shape can be obtained.

In addition, the alkalinity can be determined by measuring the pH, or the calculated value can be calculated by commercially available software.

In the following, it will be described that it can be produced after irradiation with actinic rays or radiation. Specific examples of the compound (N) of the compound represented by the formula (PA-I) are produced, but the invention is not limited to the examples.

These compounds can be easily used as a compound represented by the formula (PA-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide, chloride or the like of ruthenium or osmium by using an international patent application The salt exchange method described in Japanese National Publication No. H11-501909 or Japanese Patent Application Laid-Open No. 2003-246786 is incorporated. Further, the synthesis can be carried out in accordance with the synthesis method described in Japanese Patent Application Laid-Open No. H7-333851.

Hereinafter, a specific example of the compound (N) capable of producing a compound represented by the formula (PA-II) or the formula (PA-III) after irradiation with actinic rays or radiation will be described, but the present invention is not limited to the examples. .

These compounds can be easily synthesized by using a general sulfonation reaction or a sulfonylation reaction. For example, a compound can be obtained by subjecting a sulfonyl halide moiety of a bissulfonyl halide compound to an amine comprising a moiety structure represented by formula (PA-II) or formula (PA-III) a method in which an alcohol or an analog selectively reacts to form a sulfonamide bond or a sulfonate bond, and then partially hydrolyzes another sulfonyl halide; or by including a partial structure represented by the formula (PA-II) A method in which a cyclic sulfonic anhydride is opened by an amine or an alcohol. An amine or an alcohol comprising a partial structure represented by formula (PA-II) or formula (PA-III) can be obtained by reacting an amine or an alcohol with an acid anhydride such as (R'O ₂ C) ₂ O and (R'SO ₂ ) ₂ O) or an acid chloride compound such as R'O ₂ CCl, R'SO ₂ Cl (R' is methyl, n-octyl or trifluoromethyl) is synthesized by reaction under basic conditions. In particular, the synthesis can be carried out according to the synthesis examples and the like in Japanese Patent Application Laid-Open No. 2006-330098.

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

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the compound (N), but in the case of containing the compound (N), the content of the compound (N) is sensitized ray or radiation. The solid content of the resin composition is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass.

[6-2] Basic compound (N')

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may contain a basic compound (N') to reduce the change in potency with time due to exposure to heat.

Preferable examples of the basic compound include a compound having a structure represented by the following formula (A) to formula (E).

In the formulae (A) to (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may each be the same or different from all other R ²⁰⁰ , R ²⁰¹ and R ²⁰² and represent a hydrogen atom or 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 6 to 20 carbons), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each may be the same or different from all other R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ and represent an alkyl group having 1 to 20 carbon atoms.

As the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanogen having 1 to 20 carbon atoms. Alkyl group.

The alkyl group in the formula (A) to the formula (E) is more preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred examples of the compound include imidazole a compound having a structure, a diazabicyclo structure, a ruthenium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure; an alkylamine derivative having a hydroxyl group and/or an ether bond; having a hydroxyl group and/or Or an aniline derivative of an ether bond and the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the compound having a ruthenium hydroxide structure include triaryl ruthenium hydroxide, benzamidine methyl hydrazine hydroxide, ruthenium hydroxide having a 2-sided oxyalkyl group, especially triphenyl hydrazine hydroxide, and hydrazine hydroxide ( Tert-butylphenyl)anthracene, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxopropylpropylthiophene hydroxide and the like. a compound having a ruthenium carboxylate structure Examples include compounds in which an anion moiety of a compound having a ruthenium hydroxide structure is converted to a carboxylate such as acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine, tri(n-octyl)amine, and the like. Examples of the compound having an aniline structure 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, tris(methoxyethoxyethyl)amine, and the like. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline and the like.

Examples of preferred basic compounds further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group.

It is preferred that the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Further, it is preferred that the alkyl chain has an oxygen atom to form an oxyalkylene group. The number of alkylene groups in the molecule is one or more, preferably from 3 to 9, and more preferably from 4 to 6. Among the alkylene groups, a structure of -CH ₂ CH ₂ O-, CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O- is preferred.

Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group include US Patent Application Publication No. 2007/0224539 The compound (C1-1) to the compound (C3-3) exemplified in the paragraph [0066], but is not limited to the examples.

Examples of the basic compound may also include N-alkyl caprolactam. As the N-alkyl caprolactam, N-methyl caprolactam can be preferably exemplified.

Further, a nitrogen-containing organic compound having a group capable of leaving under the action of an acid can also be used as a basic compound. Examples of the compound include a compound represented by the following formula (F). Further, the compound represented by the following formula (F) exhibits an effective alkalinity in the system by eliminating a group capable of leaving under the action of an acid.

In the formula (F), each Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n=2, each of two Ra may be the same as or different from all other Ra, and two Ra may be bonded to each other to form a divalent heterocycloalkyl group (preferably having 20 or less carbon atoms) or Its derivatives.

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

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

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

In the formula (F), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by R _a and R _b each may be, for example, a hydroxyl group, a cyano group, an amine group, a pyrrolidino group, a piperidine group. The functional group, alkoxy group or halogen atom of the piperidino group, the morpholino group and the oxo group are substituted.

Examples of the alkyl, cycloalkyl, aryl or aralkyl group of R (each of which the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group may be substituted by the above functional group, alkoxy group or halogen atom) include: Derived from linear or branched paraffins (such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane and dodecane) a group derived from an alkane group substituted with one or more or one or more cycloalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl; derived from a cycloalkane such as cyclobutane, a group of cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and adamantane, a group derived from a cycloalkane via one or more or one or more straight chains or a group substituted with a branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl; derived from a group of an aromatic compound such as benzene, naphthalene and anthracene, a group derived from an aromatic compound via one or more or one or more linear or branched alkyl groups (such as methyl, ethyl, n-propyl) a group substituted with isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl); and derived from a heterocyclic compound such as pyrrolidine, piperidine, morpholine, a group derived from tetrahydrofuran, tetrahydropyran, hydrazine, porphyrin, quinoline, perhydroquinoline, oxazole, and benzimidazole, one or more or one or more groups derived from a heterocyclic compound Straight chain or a group substituted with a branched alkyl group or a group derived from an aromatic compound; a group derived from a linear or branched alkane or a group derived from a cycloalkane derived from one or more or one or more derived from a aromatic group a group substituted with a group of a compound such as a phenyl group, a naphthyl group, and an anthracenyl group; the above substituent is functional with a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and a pendant oxy group. a group substituted with a group and a similar group.

Further, examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by combining R _a with each other include derivatives derived from a heterocyclic compound (such as pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzene And triazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, carbazole, Benzimidazole, imidazo[1,2-a]pyridine, (1S,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane, 1,5,7-triaza Bicyclo[4.4.0]non-5-ene, anthracene, porphyrin, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline and 1,5,9-triazacyclodene a group derived from a heterocyclic compound; a group derived from a heterocyclic compound, one or more or one or more groups derived from a straight or branched chain group of an alkane, a group derived from a cycloalkane, and a group derived from an aromatic compound a group, a group derived from a heterocyclic compound, and a group substituted with a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and a pendant oxy group, and the like.

The nitrogen-containing organic compound of the present invention having a particularly preferred group capable of leaving under the action of an acid will be described in detail, but the present invention is not limited to the compound.

As the compound represented by the formula (F), although a commercially available product can be used, the compound can be obtained from a commercially available amine by "Protective Groups in Organic Synthesis", The method described in the 4th edition and the like are synthesized. The compound can be synthesized according to the method described in, for example, Japanese Patent Application Laid-Open No. 2009-199021, which is the most general method.

Further, as the basic compound, a compound having a fluorine atom or a ruthenium atom and having a basicity or capable of increasing the alkalinity under the action of an acid can be used, as described in Japanese Patent Application Laid-Open No. 2011-141494. Specific examples thereof include the compound (B-7) to the compound (B-18) and the like used in the examples of the patent documents. Things.

The molecular weight of the basic compound is preferably from 250 to 2,000, and more preferably from 400 to 1,000. The molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more, from the viewpoint of greatly reducing the uniformity of the LWR and the local pattern size.

These basic compounds may be used in combination with the compound (N), and may be used singly or in combination of two or more thereof.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a basic compound, but in the case of containing a basic compound, the amount of the basic compound used is sensitizing ray or radiation. The solid content of the resin composition is usually 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 5% by mass.

The ratio of the acid generator to the basic compound used in the composition is preferably an acid generator/basic compound (mol ratio) = 2.5 to 300. That is, in view of sensitivity, resolution, and the like, the molar ratio is preferably 2.5 or more, and since the self-inhibition is increased from the exposure to the heat treatment, the resist pattern is thickened with time to cause a decrease in resolution. It is preferably 300 or less. The acid generator/basic compound (mole ratio) is more preferably from 5.0 to 200, and still more preferably from 7.0 to 150.

[7] surfactant (F)

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but in the case of containing a surfactant, it is more preferable that the composition contains a fluorine-based and/or quinone-based interface. Any of the active agents (fluorinated surfactants, anthraquinone surfactants, and surfactants having fluorine atoms and germanium atoms), or two or more thereof.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, so that sensitivity is used when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used. The resolution is improved to impart a resist pattern having adhesiveness and reduced development defects.

Examples of fluorochemical and/or quinone surfactants include the surfactants described in paragraph [0276] of U.S. Patent Application Publication No. 2008/0248425, such as EFtop EF301 and EF303 (by New Manufactured by Shin-Akita Kasei Co., Ltd.; Florad FC430, 431, and 4430 (manufactured by Sumitomo 3M Inc.); Megaface ) F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC Corporation); Surfron S-382, SC101, 102, 103, 104, 105, and 106 and KH-20 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Corp.); GF-300 and GF-150 (by East Asia) Chemical Industry Co., Ltd. (manufactured by Toagosei Chemical Industry Co., Ltd.); Chevron S-393 (manufactured by Seimi Chemical Co., Ltd.); Yvesto EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, and EF601 (manufactured by JEMCO Co., Ltd.); PF636, PF656 PF6320 and PF6520 (manufactured by OMNOVA Solutions, Inc.); and FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (by NEOS Co., Ltd.) .) Manufacturing). Further, a polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a quinone type surfactant.

Further, in addition to the above-mentioned known surfactants, it is also possible to use a surfactant as a surfactant, which has a fluorinated aliphatic group derived from a fluorinated aliphatic compound and which is subjected to a short chain polymerization method (telomerization) A polymer prepared by a method (also referred to as a short chain polymer method) or an oligomerization method (also referred to as an oligomer method). The fluorinated aliphatic compound can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2002-90991.

Examples of the surfactant corresponding to the above surfactant include Megefans F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC Corporation) having C ₆ F ₁₃ a copolymer of a acrylate (or methacrylate) and a (poly(oxyalkylene)) acrylate (or methacrylate), an acrylate having a C ₃ F ₇ group (or methacrylic acid) Copolymers and analogs of (poly(oxy)ethyl) acrylate (or methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate).

Further, in the present invention, it is also possible to use a surfactant other than the fluorine-based and/or quinone-based surfactant described in [0280] of U.S. Patent Application Publication No. 2008/0248425.

These surfactants may be used singly or in combination of plural kinds thereof.

When the sensitizing ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably 0.0001% by mass based on the total amount of the sensitizing ray-sensitive or radiation-sensitive resin composition (excluding the solvent). It is 2% by mass, and more preferably 0.0005% by mass to 1% by mass.

On the other hand, the amount of the surfactant added is adjusted to 10 ppm based on the total amount of the sensitized ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Or less than 10 ppm, the surface uneven distribution of the resin D related to the present invention can be enhanced, and therefore, the surface of the resist film can be made more hydrophobic, thereby improving the tracking property of water during the immersion exposure.

[8]Other additives (G)

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a cerium carboxylate salt. Examples of the cerium carboxylate salt include the cerium carboxylate salt described in [0605] to [0606] of U.S. Patent Application Publication No. 2008/0187860.

The cerium carboxylate salt can be synthesized by reacting cerium hydroxide, cerium hydroxide, ammonium hydroxide, and a carboxylic acid with silver oxide in a suitable solvent.

When the sensitizing ray-sensitive or radiation-sensitive resin composition contains a cerium carboxylate salt, the content thereof is generally 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass based on the total solid content of the composition. More preferably, it is 1% by mass to 7% by mass.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbing agent, an alkali-soluble resin, a dissolution inhibitor, and is used for accelerating dissolution in a developer, if necessary. A compound (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound having a carboxyl group) and the like.

A phenolic compound having a molecular weight of 1,000 or less can be easily referred to by those skilled in the art by, for example, Japanese Patent Application Laid-Open No. H4-122938, Japanese Patent Application Laid-Open No. H2-28531, No. 4,916,210 Synthesis by the method described in European Patent No. 219294 and the like.

Specific examples of the alicyclic or aliphatic compound having a carboxylic acid include a carboxylic acid derivative having a steroid structure (such as cholic acid, deoxycholic acid, and lithocholic acid), adamantane The carboxylic acid derivative, adamantane dicarboxylic acid, cyclohexanecarboxylic acid, cyclohexane dicarboxylic acid, and the like are, but not limited to, the examples.

From the viewpoint of improving the resolution, the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 30 nm to 250 nm and more preferably in a film of 30 nm to 200 nm. Thickness is used. The film thickness can be achieved by setting the solid concentration of the composition to a sufficient range to have an appropriate viscosity, thereby improving coatability and film formation characteristics.

The solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is usually from 1.0% by mass to 10% by mass, preferably from 2.0% by mass to 5.7% by mass, and more preferably from 2.0% by mass to 5.3% by mass. quality%. When the solid content concentration is set within the above range, the resist solution can be uniformly coated on the substrate, and a resist pattern excellent in line width roughness can be formed. Although the reason is not clear, it is considered that the substance in the resist solution can be suppressed by setting the solid content concentration to 10% by mass or less, preferably 5.7 mass% or less, or 5.7% by mass. The photoacid generator is aggregated, and thus a uniform resist film can be formed.

The solid content concentration is a weight percentage based on the total weight of the photosensitive ray-sensitive or radiation-sensitive resin composition, based on the weight of the other resist components other than the solvent.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is prepared by dissolving the above components in a predetermined organic solvent, preferably in a mixed solvent, filtering the solution through a filter, and then coating the filtered solution. Used on a predetermined support (substrate). The filter for filtration is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore diameter of 0.1 μm or less, more preferably 0.05 μm or less and more preferably 0.03. Micron or less than 0.03 microns. The filtration may be performed as described in, for example, Japanese Patent Application Laid-Open No. 2002-62667, or may be performed by connecting a plurality of filters in series or in parallel. In addition, the composition can be filtered multiple times. In addition, a degassing treatment or the like may be applied to the composition before or after filtration.

[9] Pattern forming method

The pattern forming method (negative pattern forming method) of the present invention comprises at least: (a) forming a film (resist film) from the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, (b) exposing the film, and (c) Development using a developer.

The exposure in step (b) can be an immersion exposure.

It is preferable that the pattern forming method of the present invention has the heating step (d) after the exposure step (b).

The pattern forming method of the present invention may further have (e) a step of developing using an alkali developer.

The pattern forming method of the present invention may have a multiple exposure step (b).

The pattern forming method of the present invention may have a plurality of heating steps (e).

The resist film of the present invention is formed of the above-described sensitized ray-sensitive or radiation-sensitive resin composition of the present invention, and more specifically, by applying a sensitizing ray-sensitive or radiation-sensitive resin composition to a film formed on the substrate. In the pattern forming method of the present invention, the step of forming a film on the substrate by the sensitizing ray-sensitive or radiation-sensitive resin composition, the step of exposing the film, and the step of performing development can be carried out by a generally known method.

It is also preferred that the method is packaged after the film formation and before the exposure step Contains a pre-baking step (PB).

Furthermore, it is also preferred that the method comprises a post-exposure bake step (PEB) after the exposure step but before the development step.

As for the heating temperature, both PB and PEB are preferably carried out at from 70 ° C to 130 ° C, and more preferably from 80 ° C to 120 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and still more preferably from 30 seconds to 90 seconds.

Heating may be performed using a member equipped with a typical exposure/developer or may be performed using a hot plate or the like.

By baking, the reaction in the exposed portion can be accelerated, and thus the sensitivity or pattern profile can be improved.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, but examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, and the like, but preferably have a good wavelength. It is 250 nm or less, more preferably 220 nm or less and particularly preferably 1 nm to 200 nm. Specific examples thereof include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam And analogs, and KrF excimer laser, ArF excimer laser, EUV or electron beam are preferred, and ArF excimer laser is better.

Further, in the step of performing exposure in the present invention, an immersion exposure method can be applied.

The immersion exposure method as a technique for improving the resolution is a technique of performing exposure by filling a high refractive index liquid (hereinafter also referred to as "immersion liquid") between a projection lens and a sample.

As described above, for "effect of immersion", it is assumed that λ ₀ is the wavelength of the exposed light in the air, n is the refractive index of the immersion liquid to the air, and θ is the half convergence angle of the light beam (convergence half- Angle) and NA _o = sin θ, the resolution and depth of focus in the immersion can be expressed by the following equation. Here, k ₁ and k ₂ are coefficients related to the steps.

(resolution) = k ₁ (λ ₀ /n) / NA ₀

(focus depth) = ± k ₂ . (λ ₀ /n)/NA ₀ ²

That is, the impregnation is equal to the use of an exposure wavelength of 1/n. In other words, in the case of a projection optical system having the same NA, the depth of focus can be n times by dipping. This is effective for all pattern shapes and can be combined with super-resolution techniques currently being investigated, such as phase-shift methods and modified illumination methods.

In the case of immersion exposure, (1) may be performed after the film is formed on the substrate but before the step of performing the exposure and/or (2) after the step of exposing the film through the immersion liquid, but before the step of heating the film. The step of washing the surface of the film with an aqueous chemical solution.

The immersion liquid is preferably a liquid which is transparent to the light of the exposure wavelength and whose temperature coefficient of the refractive index is as small as possible to minimize the deformation of the optical image projected on the film, but in particular, when the exposure light source is an ArF excimer laser ( In the case of the wavelength: 193 nm, in addition to the above viewpoints, water is preferably used from the viewpoint of ease of use and ease of handling.

When water is used, a small ratio of an additive (liquid) capable of lowering the surface tension of water and increasing the interfacial activity may be added. The additive preferably does not dissolve the resist layer on the wafer and has only negligible effects on the optical coating on the lower surface of the lens component.

The additive is preferably an aliphatic alcohol having a refractive index almost equal to, for example, water, and specific examples thereof include methanol, ethanol, isopropanol, and the like. By adding refraction An alcohol having a ratio almost equal to that of water, even when the alcohol component in the water evaporates and the concentration of its contents changes, it is possible to obtain an advantage due to the extremely small change in the refractive index of the liquid as a whole.

On the other hand, when incorporated into a substance that is opaque to 193 nm of light, or an impurity having a large difference in refractive index from water, the incorporation causes deformation of the optical image projected on the resist, and thus, The water is preferably distilled water. Further, pure water filtered through an ion exchange filter or the like can also be used.

The electric resistance of the water used as the immersion liquid is preferably 18.3 megaohms (MQcm) or more than 18.3 mega ohms, and the organic concentration (TOC) is preferably 20 ppb or less and preferably water. Degassing treatment.

In addition, the lithographic efficacy can be enhanced by increasing the refractive index of the immersion liquid. From this point of view, an additive for increasing the refractive index may be added to the water, or heavy water (D ₂ O) may be used instead of water.

In the case of exposure through an immersion medium, water has a receding contact angle at a temperature of 23 ° C ± 3 ° C and a resist film formed on the resist film formed by using the sensitized ray-sensitive or radiation-sensitive resin composition of the present invention. 70 degrees or more than 70 degrees of humidity at % ± 5% is suitable, and is preferably 75 degrees or more, and more preferably 75 degrees to 85 degrees.

When the receding contact angle is very small, the receding contact angle may not be suitable for exposure through the impregnating medium, and may not sufficiently exhibit the effect of reducing watermark defects.

The resin (D) is substantially free of fluorine atoms and ruthenium atoms, and therefore water can be modified on the surface of the resist film by containing the resin (D) in the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention. Then retreat the contact angle.

From the viewpoint of improving the receding contact angle, the resin (D) preferably has at least one repeating unit represented by the formula (II) or the formula (III) as described above. Further, from the viewpoint of improving the receding contact angle, the CLogP value of the resin (D) is preferably 1.5 or more as described above. Further, from the viewpoint of improving the receding contact angle, in the resin (D), the mass content ratio of the CH ₃ partial structure of the side chain portion in the resin (D) is preferably 12.0% or more as described above. %.

In the immersion exposure step, the immersion liquid is moved over the wafer as the exposure head moves, wherein the exposure head scans the wafer at a high speed and forms an exposure pattern, and thus, immersion in a dynamic state The contact angle of the resist film is important, and it is possible to obtain an effect from the resist that allows the immersion liquid to follow the high speed scanning of the exposure head without remaining droplets.

In the present invention, the substrate on which the film is formed is not particularly limited, and it is possible to use an inorganic substrate such as germanium, SiN, SiO ₂ or SiN; a coated inorganic substrate such as SOG; or generally in the manufacture of a semiconductor such as an IC Or a substrate used in the fabrication of a liquid crystal cell or circuit board (such as a thermal head) or in a lithography process of other photolithographic processes. Further, an organic anti-reflection film may be formed between the film and the substrate as necessary.

When the pattern forming method of the present invention further comprises development using an alkali developer, it is possible to use an alkaline aqueous solution of each of the following as an alkali developer: an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate , sodium metasilicate and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines, Such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; cyclic amines such as pyrrole and piperidine; and the like.

In addition, each of the appropriate amount of alcohol and surfactant can be added to the alkaline water. A mixture can be used in the solution.

The alkali concentration of the alkali developer is usually from 0.1% by mass to 20% by mass.

The pH of the alkaline developer is usually from 10.0 to 15.0.

In particular, an aqueous solution of 2.38 mass% tetramethylammonium hydroxide is preferred.

As for the rinsing solution in the rinsing treatment performed after the alkali development, pure water is used, and an appropriate amount of the surfactant may be added thereto to use the mixture.

Further, after the development treatment or the rinsing treatment, a treatment of removing the developer or the rinsing solution adhered to the pattern by the supercritical fluid may be performed.

As the developer in the step of developing using a developer containing an organic solvent in the pattern forming method of the present invention (hereinafter also referred to as "organic-based developer"), a polar solvent such as a ketone may be used. Solvents, ester solvents, alcohol solvents, guanamine solvents and ether solvents, and hydrocarbon solvents.

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, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetonyl acetone, ketone ketone (ionone), diacetone alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acid ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3 acetate - methoxybutyl ester, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.

Examples of the alcohol solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol and N-decyl alcohol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; and the like.

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

As the guanamine-based solvent, it is possible to use, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, trimethylamine hexamethylphosphate , 1,3-dimethyl-2-imidazolidinone and the like.

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.

The above various solvents may be mixed, or the solvent may be used by mixing with a solvent other than the above or with water. However, in order to sufficiently exhibit the effect of the present invention, the water content ratio of the entire developer is preferably less than 10% by mass, and more preferably, the developer is substantially free of moisture.

That is, the amount of the organic solvent used in the organic developer is preferably from 90% by mass to 100% by mass, and more preferably from 95% by mass to 100% by mass based on the total amount of the developer.

More specifically, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The organic developer has a vapor pressure of preferably 5 kPa or less at 20 ° C. Preferably, the Pa, more preferably 3 kPa or less, and particularly preferably 2 kPa or less than 2 kPa. By adjusting the vapor pressure of the organic developer to 5 kPa or less, it is possible to suppress evaporation of the developer on the substrate or in the developing cup, thereby improving temperature uniformity in the wafer plane, and thus improving the wafer. Dimensional uniformity in the plane.

Specific examples of the solvent having a vapor pressure of 5 kPa or less include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl pentyl) Ketone), 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methyl isobutyl ketone; ester solvents such as butyl acetate, pentyl acetate Ester, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3 -ethyl ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and lactate Ester; alcohol solvent such as n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol and n-nonanol; diol Solvents such as ethylene glycol, diethylene glycol and triethylene glycol; glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol Alcohol monomethyl ether, triethylene glycol monoethyl ether Methoxymethylbutanol; ether solvent such as tetrahydrofuran; guanamine solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethyl Formamide; aromatic hydrocarbon solvents such as toluene and xylene; and aliphatic hydrocarbon solvents such as octane and decane.

Specific examples of the solvent having a vapor pressure of 2 kPa or less (in a particularly preferred range) include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone and phenylacetone; ester solvents such as butyl acetate, amyl acetate, propylene glycol monomethyl ether Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate Ester, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate; alcohol solvents such as n-butanol, second butanol, tert-butanol, isobutanol , n-hexanol, n-heptanol, n-octanol and n-nonanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; glycol ether solvents, such as ethylene glycol monomethyl ether, Propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol; guanamine solvents such as N-methyl-2 Pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide; aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane and decane ; and the like.

An appropriate amount of the surfactant may be added to the organic developer as necessary.

The surfactant is not particularly limited, but for example, an ionic or nonionic fluorine-based and/or quinone-based surfactant and the like can be used. Examples of the fluorine-based and/or hydrazine-based surfactants include Japanese Patent Application Laid-Open No. S62-36663, No. S61-226746, No. S61-226745, No. S62-170950, No. S63-34540, No. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, The surfactants described in Nos. 5,294,511 and 5,824,451, and nonionic surfactants are preferred. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.

As for the developing method, it is possible to apply, for example, a method of immersing the substrate in a bath filled with a developer for a fixed period of time (dipping method); by the action of surface tension, the developer is sufficiently lifted on the surface of the substrate and the substrate is allowed to stand for a while. a method of performing development for a fixed period of time (puddle method); a method of spraying a developer on a surface of a substrate (spraying method); continuously ejecting a developer on a substrate rotating at a constant speed while scanning at a constant rate A developer nozzle method (dynamic dispense method); and the like.

When the above various developing methods include developing the nozzle of the developing device to eject the developer to the resist film, the ejection pressure of the ejected developer (the flow rate of the developer ejected per unit area) is preferably 2 ml/sec/mm 2 . Or less than 2 ml/sec/mm 2 , more preferably 1.5 ml/sec/mm 2 or less than 1.5 ml/sec/mm 2 , and more preferably 1 ml/sec/mm 2 or less than 1 ml/sec/mm 2 . There is no specific lower limit for the flow rate, but in view of the treatment amount, it is preferably 0.2 ml/sec/mm 2 or more than 0.2 ml/sec/mm 2 .

By setting the ejection pressure of the ejected developer to the above range, pattern defects caused by the resist scum after development can be remarkably reduced. Although the details of the mechanism are not clear, it is considered that by setting the ejection pressure within the above range, the pressure applied to the resist film by the developer can be reduced, and the resist film or the resist pattern can be suppressed. Inadvertently cut or ruptured.

Further, the ejection pressure of the developer (ml/sec/mm 2 ) is the value at the exit of the developing nozzle in the developing device.

Examples of the method of adjusting the developer ejection pressure include a method of adjusting the ejection pressure by a pump or the like, a method of supplying the developer from the pressurized canister and adjusting the pressure to change the ejection pressure, and the like.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping development when the solvent is replaced with another solvent may be performed.

Preferably, the step of rinsing the film with the rinsing solution is carried out after the step of developing using a developer containing an organic solvent.

The rinsing solution used in the rinsing step after the step of developing using the developer containing the organic solvent is not particularly limited as long as the rinsing solution does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described above for the developer containing the organic solvent.

After the step of developing using a developer containing an organic solvent, it is more preferably carried out using a rinsing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. a washing step; a step of washing with a washing solution containing an alcohol solvent or an ester solvent; more preferably, a step of washing with a washing solution containing a monohydric alcohol; and the best use contains 5 or A washing step of a rinsing solution of one of more than 5 carbon atoms.

Here, examples of the monohydric alcohol used in the rinsing step include a linear, branched or cyclic monohydric alcohol, and it is especially possible to use 1-butanol, 2-butanol, 3-methyl-1-butanol, Tributanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like, and as a particularly preferred monohydric alcohol having 5 or more than 5 carbon atoms, it is possible to use 1-hexanol, 2-hexanol, 4-methyl- 2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of components may be mixed, or the solvent may be used by being mixed with an organic solvent other than the above solvent.

The water content ratio in the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Good development characteristics can be obtained by setting the water content ratio to 10% by mass or less.

The vapor pressure of the rinsing solution used after the step of developing using the developer containing the organic solvent at 20 ° C is preferably from 0.05 kPa to 5 kPa, more preferably from 0.1 kPa to 5 kPa, and most preferably from 0.12 thousand. Pa to 3 kPa. By setting the vapor pressure of the rinsing solution to 0.05 kPa to 5 kPa, the temperature uniformity in the plane of the wafer can be improved, and in addition, the expansion caused by the penetration of the rinsing solution can be suppressed, and thus the wafer plane is improved. Size uniformity.

The rinsing solution can also be used by adding an appropriate amount of a surfactant thereto.

In the rinsing step, the wafer developed using the developer containing the organic solvent is washed by using the above-described rinsing solution containing an organic solvent. Although the method of the rinsing treatment is not particularly limited, it is possible to apply, for example, a method of continuously spraying a rinsing solution on a substrate rotating at a constant speed (spin coating method), immersing the substrate in a bath filled with a rinsing solution for a fixed period of time. Method (dipping method), a method of spraying a rinsing solution on a surface of a substrate (spraying method), and the like, and wherein, preferably, rinsing treatment is performed by spin coating, and 2,000 rpm to 4,000 after rinsing Transfer / minute The clock rotates the substrate to remove the rinse solution from the substrate. It is also preferred to include a heating step (post-baking) after the rinsing step. The developer and the rinsing solution remaining between the patterns and inside the pattern can be removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, and preferably at 70 ° C to 95 ° C, usually for 10 seconds to 3 minutes, and preferably 30 seconds to 90 seconds.

Further, the present invention relates to a method for manufacturing an electronic component comprising the above-described pattern forming method of the present invention; and an electronic component manufactured by the manufacturing method.

The electronic component of the present invention is adapted to be mounted on electrical and electronic components such as household appliances, OA media related components, optical components, and communication components.

Instance

Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the invention is not limited to the examples.

<Synthesis Example (Synthetic Resin A-1)>

102.3 parts by mass of cyclohexanone was heated at 80 ° C under a nitrogen stream. While stirring the liquid, 22.2 parts by mass of the monomer represented by the following structural formula M-1, 22.8 parts by mass of the monomer represented by the following structural formula M-2, and 6.6 parts by mass of the following structural formula were added dropwise thereto over 5 hours. M-3 represents a monomer, 189.9 parts by mass of cyclohexanone, and 2.40 parts by mass of 2,2'-dimethyl ester of azobisisobutyric acid [V-601, manufactured by Wako Pure Chemical Industries, Ltd. Ltd.) Manufacturing] mixed solution. After the dropwise addition was completed, the solution was further stirred at 80 ° C for 2 hours. The reaction solution was cooled, and then reprecipitated with a large amount of hexane/ethyl acetate (mass ratio: 9:1), and filtered to give a solid, and the solid was dried in vacuo to give 41.1 parts by mass of the resin (A-1).

The weight average molecular weight (Mw: according to polystyrene) of the obtained resin was determined by GPC (carrier: tetrahydrofuran (THF)) to be Mw = 9,500, and the polydispersity Mw / Mn = 1.60. The composition ratio by ¹³ C-NMR measurement was 40/50/10.

<Acid decomposable resin>

Hereinafter, Resin A-2 to Resin A-9 were synthesized in the same manner. The structure of the synthesized polymer will be described below.

In addition, the composition ratio of each repeating unit (Mohr ratio; corresponding to the opening from the left side The starting order), weight average molecular weight and polydispersity are shown in the table below.

<Synthesis Example (Synthetic Resin D-1)>

68.3 parts by mass of cyclohexanone was heated at 80 ° C under a nitrogen stream. While stirring the liquid, 12.0 parts by mass of the monomer represented by the following structural formula M-4, 22.4 parts by mass of the monomer represented by the following structural formula M-5, and 126.9 parts by mass of cyclohexanone were added dropwise thereto over 6 hours. 2.40 parts by mass of a mixed solution of 2,2'-dimethyl ester of azobisisobutyric acid [V-601, manufactured by Wako Pure Chemical Industries, Ltd.]. After the dropwise addition was completed, the solution was further stirred at 80 ° C for 2 hours. The reaction solution was cooled, followed by reprecipitation with a large amount of hexane/ethyl acetate (mass ratio: 9:1), and filtered to give a solid, and the solid was dried in vacuo to give 16.9 parts by mass of the resin (D-1).

The weight average molecular weight (Mw: according to polystyrene) of the obtained resin was determined by GPC (carrier: tetrahydrofuran (THF)) to be Mw = 11,700, and the polydispersity Mw / Mn = 1.66. The composition ratio by ¹³ C-NMR measurement was 30/70.

<Hydrophilic resin>

Hereinafter, Resin D-2 to Resin D-19 were synthesized in the same manner. The structure of the synthesized polymer will be described below.

Further, the composition ratio of each repeating unit in each resin (mole ratio; corresponding to the order from the left), weight average molecular weight and polydispersity, CLogP value of each resin, and CH ₃ partial structure in the side chain portion of each resin The mass content ratios are shown in the table below.

Further, the CLogP value of each resin is calculated as the total number of the molar fraction of the repeating unit in the resin multiplied by the CLoP value of the monomer corresponding to each repeating unit constituting the resin.

Here, the CLogP value corresponding to the monomer constituting each repeating unit of the resin was calculated by using a chemical drawing software (version 8.0) manufactured by Cambridgesoft Corp.

<acid generator>

The following compounds were used as the acid generator.

<Basic compound with reduced alkalinity after irradiation with actinic rays or radiation (N) and basic compound (N')>

The following compounds are used as a basic compound having a reduced alkalinity after irradiation with actinic rays or radiation or as a basic compound.

<Combined hydrophobic resin (E)>

The resin is appropriately selected from the resin (HR-1) to the resin (HR-80) previously exemplified as the combination of the hydrophobic resin (E), and then used.

<Surfactant>

The following was prepared as a surfactant.

W-1: Meg Vanes F176 (manufactured by DIC Corporation; fluorine)

W-2: Meg Vanes R08 (manufactured by DIC Corporation; fluorine and anthraquinones)

W-3: polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; anthraquinone)

W-4: Troiso S-366 (manufactured by Troy Chemical Corp.)

W-5: KH-20 (manufactured by Asahi Glass Co., Ltd.)

W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine)

<solvent>

The following was prepared as a solvent.

(ethnic group a)

SL-1: propylene glycol monomethyl ether acetate (PGMEA), boiling point: 146 ° C

SL-2: propylene glycol monomethyl ether propionate, boiling point: 160 ° C

SL-3: 2-heptanone, boiling point: 151 ° C

(ethnic group b)

SL-4: ethyl lactate, boiling point: 154 ° C

SL-5: propylene glycol monomethyl ether (PGME), boiling point: 120 ° C

SL-6: cyclohexanone, boiling point: 156 ° C

(ethnic group c)

SL-7: γ-butyrolactone, boiling point: 204 ° C

SL-8: propyl carbonate, boiling point: 242 ° C

<developer>

The following was prepared as a developer.

SG-1: butyl acetate

SG-2: methyl amyl ketone

SG-3: ethyl 3-ethoxypropionate

SG-4: Amyl acetate

SG-5: isoamyl acetate

SG-6: Propylene glycol monomethyl ether acetate (PGMEA)

SG-7: cyclohexanone

<flushing solution>

Use the following as a rinse solution.

SR-1: 4-methyl-2-pentanol

SR-2: 1-hexanol

SR-3: butyl acetate

SR-4: methyl amyl ketone

SR-5: 3-ethoxypropionate ethyl ester

Example 1 to Example 34 and Comparative Example 1 to Comparative Example 4

<ArF impregnated exposure>

(preparation of resist)

The components shown in the following Table 5 were dissolved in a solvent shown in the same table to have a solid content of 3.5% by mass, and each was filtered through a polyethylene filter having a pore diameter of 0.03 μm to prepare sensitizing ray or A radiation sensitive resin composition (resist composition). An organic anti-reflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was coated on a tantalum wafer and baked at 205 ° C for 60 seconds to form an anti-reflection film having a thickness of 95 nm. A sensitizing ray-sensitive or radiation-sensitive resin composition was applied thereon and baked at 100 ° C for 60 seconds (PB: prebaking) to form a resist film having a thickness of 90 nm.

By using an ArF excimer laser immersion scanner (manufactured by ASML Co., Ltd.; XT1700i, NA: 1.20, C-Quad, external σ: 0.900, internal σ: 0.812, XY deflection) via A halftone mask with a pitch of 100 nm and a mask width of 40 nm is used to pattern the resulting wafer. Light. Ultrapure water was used as the immersion liquid. Thereafter, heating (PEB: post-exposure baking) was carried out at 105 ° C for 60 seconds. Subsequently, the wafer was developed by coating with a developer shown in the following table for 30 seconds, and then rinsed by laminating with the rinsing solution shown in the following table for 30 seconds while at 1,000 rpm. The wafer was rotated at the number of revolutions (however, the rinsing step was not performed in Example 17 and Comparative Example 4). Subsequently, a line pitch pattern having a line width of 55 nm was obtained by rotating the wafer at a rotation speed of 2,000 rpm for 30 seconds.

However, in Comparative Example 3, pattern exposure was performed via a halftone mask having a pitch of 100 nm and a mask width of 60 nm, and 2.38 mass% of hydroxide 4 was used in development processing (so-called alkali development). An aqueous solution of methylammonium for 30 seconds. Thereafter, the wafer was rinsed by using pure water and subjected to spin drying.

[Assessing water receding contact angle]

Each of the resist compositions prepared as shown in Table 5 below was spin-coated (coated under rotation) on a tantalum wafer, and then baked at 100 ° C for 60 seconds with a hot plate to form a film thickness of 90. Nano resist film. The water droplet receding contact angle (degrees) was measured by expansion and contraction using a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). Aspirate 35 microliters of initial water droplets at a rate of 6 μl/sec at room temperature of 23 °C ± 3 °C and a humidity of 45% ± 5% for 5 seconds, and the dynamic contact angle is stable during pumping. Defined as the receding contact angle.

[Film thickness uniformity]

For the obtained resist film, the film thickness was measured at 550 points in the plane of the wafer by VM-3110 (manufactured by Dainippon Screen Mfg. Co., Ltd.). To calculate the standard deviation (3σ). The smaller the value, the better the film thickness uniformity.

[Watermark Defect Performance]

In the case of observing the line spacing pattern resolved at the optimum exposure dose when analyzing the line pitch pattern having a line width of 55 nm, the crystal was measured by using 2360 manufactured by KLA TENCOR Corp. The number of watermarks (WM) defects on the circle, wherein the pixel size and the threshold value of the defect inspection device are set to 0.16 micrometers and 20, respectively, and the measurement is performed in a random manner, and the detection freedom overlaps the comparison image with the pixel unit. The developed defects were extracted, and then the development defects were observed by SEMVISION G3 (manufactured by APPLIED MATERIALS Inc.).

A, B, C, and D indicate that the number of WM defects observed on the wafer is 0, 1 to 4, 5 to 9, and 10 or more, respectively. The smaller the value, the better the WM defect reduction performance.

[Bridge defect performance]

In the case of observing the line spacing pattern resolved at the optimum exposure dose when analyzing the line pitch pattern having a line width of 55 nm, the crystal was measured by using 2360 manufactured by KLA TENCOR Corp. The number of bridge defects per unit area on the circle (number/square centimeter), where the pixel size and threshold of the defect inspection device are set to 0.16 micrometers and 20, respectively, and the measurement is performed in a random manner, and the detection freedom compares the image with The pixel units overlap to produce a difference in the developed defects, and then the development defects were observed by a Sammyson G3 (manufactured by APPLIED MATERIALS Inc.).

A, B, C, and D respectively indicate that the number of WM defects observed on the wafer is 0.1/cm 2 or less than 0.1/cm 2 , and is greater than 0.1/cm 2 and 1 /cm ^ 2 or less than 1 / square centimeter, greater than 1 / square And 10 / square centimeter or less than 10 / square centimeter, and 10 / square centimeter or more than 10 / square centimeter. The smaller the value, the better the performance of the bridge defect reduction.

The results of these assessments will be presented in the table below.

[Table 5] Continuation

As is apparent from the results shown in Table 5, it can be understood that Comparative Example 1 containing no resin (D) and resin mixed with Resin (A) (hereinafter, in some cases, simply referred to as "plus" Comparative film 2 having a fluorine atom and the film thickness uniformity deterioration of any of Comparative Example 4 in which the CLogP value of the addition resin is low and thus the receding contact angle does not satisfy the value of 70 degrees And therefore there are a large number of bridging defects as well as watermark defects.

It can be understood that in Comparative Example 3 in which positive development (alkali development) was carried out using a resin (D) having substantially no fluorine atom and germanium atom and having a back contact angle of 70 degrees or more, no image was formed and Not evaluated.

On the one hand, it is understood that in the examples 1 to 34 in which organic solvent development is carried out without substantially containing a fluorine atom and a ruthenium atom and using a resin (D) having a receding contact angle of 70 degrees or more, the film thickness is uniform. It is excellent in properties and has a small number of bridging defects and watermark defects during immersion exposure.

Among them, it can be understood that in the case of using a mixed solvent containing two or more solvents and the two or more solvents containing at least one solvent having a boiling point of 200 ° C or more, examples 8, examples, examples 9. In Example 14 and Example 22 to Example 34, the number of bridging defects is particularly small.

Industrial utilization

According to the present invention, it is possible to provide a pattern forming method which is excellent in film thickness uniformity and suppresses bridging defects and occurrence of watermark defects when a fine pattern having a line width of 60 nm or less is formed by using an organic type developer by a dipping method. a photosensitive ray-sensitive or radiation-sensitive resin composition used therein; a resist film; a method of manufacturing an electronic component; and an electronic component.

The present application is based on a Japanese patent application filed on Feb. 17, 2012 (Japanese Patent Application No. 2012-033396), and Japanese Patent Application No. (S. The content of the application is incorporated herein by reference.

Claims (19)

A pattern forming method comprising: (a) forming a film by using a sensitizing ray-sensitive or radiation-sensitive resin composition containing: capable of increasing polarity under an action of an acid a resin (A) which is reduced in solubility in an organic solvent-containing developer; a compound (B) capable of generating an acid after irradiation with actinic rays or radiation; a solvent (C); and a fluorine-free atom and a germanium atom and a resin (D) different from the resin (A); (b) exposing the film; and (c) developing by using the organic solvent-containing developer to form a negative pattern in which water is (a) The receding contact angle on the film formed is 70 degrees or more. The pattern forming method according to claim 1, wherein the solvent (C) is a mixed solvent containing two or more solvents, and the two or more solvents contain at least one boiling point of 200 ° C. Or a solvent greater than 200 ° C. The pattern forming method according to claim 2, wherein the at least one solvent having a boiling point of 200 ° C or more is a solvent represented by one of the formulae (S1) to (S3): Wherein R ₁ to R ₄ and R ₆ to R ₈ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₇ and R ₈ may be bonded to each other to form a bond. ring. The pattern forming method according to claim 2, wherein the at least one solvent having a boiling point of 200 ° C or more is 1% by mass or more than 1% by mass based on the mixed solvent. The pattern forming method according to claim 1, wherein the resin (A) contains a repeating unit containing a group capable of decomposing to generate a polar group by an acid, and the repeating unit is composed of at least one (I) Representation of repeating unit composition: Wherein R ₀ represents a hydrogen atom or an alkyl group, R ₁ to R ₃ each independently represent an alkyl group or a cycloalkyl group, and two of R ₁ to R ₃ may be bonded to each other to form a monocyclic or polycyclic cycloalkyl group. . The pattern forming method according to claim 1, wherein the resin (D) has at least one repeating unit represented by the following formula (II) or formula (III): Wherein, in the formula (II), R ₂₁ to R ₂₃ each independently represent a hydrogen atom or an alkyl group, Ar ₂₁ represents an aromatic group, and R ₂₂ and Ar ₂₁ may form a ring, and in this case, R ₂₂ represents a stretching. An alkyl group, in the formula (III), R ₃₁ to R ₃₃ each independently represent a hydrogen atom or an alkyl group, X ₃₁ represents -O- or -NR ₃₅ -, R ₃₅ represents a hydrogen atom or an alkyl group, and R ₃₄ represents Alkyl or cycloalkyl. The pattern forming method according to claim 6, wherein the content of the repeating unit represented by the formula (II) or the formula (III) is 50 mol% based on all the repeating units in the resin (D) to 100% by mole. The pattern forming method according to claim 1, wherein the organic solvent-containing developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents and esters. A solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. The pattern forming method according to claim 1, further comprising: (d) washing by using a rinsing solution containing an organic solvent. The pattern forming method according to claim 1, wherein the exposure in (b) is immersion exposure. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method as described in claim 2 of the patent application. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method according to claim 3 of the patent application. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method according to item 4 of the patent application. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method as described in claim 5 of the patent application. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method according to claim 6 of the patent application. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method according to claim 7 of the patent application. A resist film formed of the sensitized ray-sensitive or radiation-sensitive resin composition according to any one of claims 11 to 16. A method of manufacturing an electronic component, comprising the pattern forming method according to any one of claims 1 to 10. An electronic component manufactured by the method of manufacturing an electronic component as described in claim 18.