WO2019044668A1

WO2019044668A1 - Active light-sensitive or radiation-sensitive resin composition, active light-sensitive or radiation-sensitive resin film, pattern-forming method, and electronic device production method

Info

Publication number: WO2019044668A1
Application number: PCT/JP2018/031231
Authority: WO
Inventors: 高桑　英希; 文博吉野
Original assignee: 富士フイルム株式会社
Priority date: 2017-08-31
Filing date: 2018-08-23
Publication date: 2019-03-07
Also published as: JPWO2019044668A1; JP6865290B2; TW201912664A

Abstract

Provided is an active light-sensitive or radiation-sensitive resin composition comprising: (A) a resin containing a repeating unit expressed by a specific general formula, a repeating unit expressed by a specific general formula, and a repeating unit expressed by a specific general formula, the content amount of the repeating unit expressed by general formula (1) being a range of 25-50 mol% with respect to all of the repeating units in the resin (A); (B) a compound that produces an acid through irradiation with an active light ray or radiation; and (C) a solvent. Also provided are: an active light-sensitive or radiation-sensitive resin film that uses the active light-sensitive or radiation-sensitive resin composition; a pattern-forming method; and a method for producing an electronic device.

Description

Actinic light sensitive or radiation sensitive resin composition, active light sensitive or radiation sensitive resin film, pattern forming method, and method of manufacturing electronic device

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in semiconductor manufacturing processes such as IC, manufacturing of circuit substrates such as liquid crystals and thermal heads, and other lithography processes of photofabrication. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin film, a method of forming a pattern, and a method of manufacturing an electronic device. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used for exposure with a KrF exposure device, an actinic ray-sensitive or radiation-sensitive resin film, a method of forming a pattern, and a method of manufacturing an electronic device. About.

From the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification is used as an image forming method of a resist in order to compensate for the decrease in sensitivity due to light absorption. The image forming method of positive type chemical amplification will be described by way of example. The acid generator in the exposed area is decomposed to generate an acid by exposure with an excimer laser, electron beam, extreme ultraviolet light or the like, and baking after exposure (PEB In Post Exposure Bake, the generated acid is used as a reaction catalyst to convert an alkali-insoluble group into an alkali-soluble group, and an exposed part is removed by an alkali developer.
At the request of microfabrication technology, development of micropattern formation by negative image as well as positive type of mainstream at present has been carried out.

For example, Patent Document 1 discloses a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition containing a resin having a specific structure, a step of exposing the resist film, and an organic compound containing an antioxidant. A pattern forming method is disclosed that includes a step of developing with a system processing solution. Here, in the embodiment of Patent Document 1, a 4-inch silicon wafer, a 6-inch silicon wafer, and 8-inch silicon are used as silicon wafers on which a resist film is formed.

International Publication 2016/104565

By the way, the resist composition is applied to substrates of various sizes depending on the application, and a mode in which the resist composition is applied on a substrate with a wide diameter (for example, 12 inches or more in diameter) may also be mentioned. However, in particular, a film provided on such a wide-diameter substrate is difficult to obtain high film thickness uniformity, and further improvement of film thickness uniformity has been desired.
In view of the above problems, it is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin excellent in film thickness uniformity even when provided on a substrate of the above wide diameter (for example, 12 inches or more in diameter). An actinic ray-sensitive or radiation-sensitive resin composition capable of forming a film, and an actinic ray-sensitive or radiation-sensitive resin film using the same, a method of forming a pattern, and a method of manufacturing an electronic device . In particular, an actinic ray-sensitive or radiation-sensitive resin composition suitable for KrF exposure and organic solvent development, an actinic ray-sensitive or radiation-sensitive resin film using the same, a method of forming a pattern, and a method of manufacturing an electronic device To provide.

The present invention has the following constitution, thereby achieving the above object of the present invention.

[1]
(A) A repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3),
A resin wherein the content of the repeating unit represented by the general formula (1) is in the range of 25 to 50 mol% with respect to all repeating units in the resin (A)
An actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a solvent.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R ₂ and R ₃ may be bonded to each other to form a ring having 3 to 8 carbon atoms. R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R ₅ is a hydrogen atom or a methyl group. R ₆ , R ₇ and R ₈ each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

[2]
The actinic ray-sensitive or radiation-sensitive resin composition as described in [1], wherein in the repeating unit represented by the general formula (2), R ₄ is an adamantyl group, a norbornyl group or a bicyclooctyl group.
[3]
The actinic ray according to [1] or [2], wherein the content of the repeating unit represented by the general formula (2) is 25 to 50 mol% with respect to all the repeating units in the resin (A). Or radiation sensitive resin composition.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], which is for KrF exposure.
[5]
An actinic ray obtained by applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4] onto a substrate by spin coating at a maximum number of revolutions of 2500 rpm or less Or radiation sensitive resin film.

[6]
(A) forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], (b) exposing the film, and (c) A pattern forming method comprising a step of developing the exposed film with a developer containing an organic solvent to form a negative pattern.
[7]
The pattern forming method according to [6], wherein the developer is butyl acetate.
[8]
[6] or [7] the manufacturing method of the electronic device which includes the pattern formation method of statement

According to the present invention, an actinic ray capable of forming an actinic ray-sensitive or radiation-sensitive resin film excellent in film thickness uniformity even when provided on a substrate with a wide diameter (for example, a diameter of 12 inches or more) A radiation or radiation sensitive resin composition, an actinic ray sensitive or radiation sensitive resin film using the same, a method of forming a pattern, and a method of producing an electronic device can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term "actinic ray" or "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB) and the like. Do. In the present invention, light means actinic rays or radiation.
Further, unless otherwise specified, the "exposure" in the present specification means not only exposure by far ultraviolet rays represented by a mercury lamp or excimer laser, extreme ultraviolet rays, X rays, EUV light, etc., but also electron beams, ion beams, etc. Particle beam drawing is also included in the exposure.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises (A) a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and Contains a repeating unit represented by 3),
Resin in which the content of the repeating unit represented by the above general formula (1) is in the range of 25 to 50 mol% with respect to all repeating units in the resin (A) (hereinafter referred to simply as “resin (A)” Say),
It is an actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a solvent.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R ₂ and R ₃ may be bonded to each other to form a ring having 3 to 9 carbon atoms. R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R ₅ is a hydrogen atom or a methyl group. R ₆ , R ₇ and R ₈ each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

When such an actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied to a wide-diameter substrate, an actinic ray-sensitive or radiation-sensitive resin film excellent in film thickness uniformity is formed The reason why it can be done is not clear, but it is estimated as follows.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the resin (A) is a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and The repeating unit represented by the above general formula (3) is contained, and the content of the repeating unit represented by the above general formula (1) is 25 to 50% by mole based on all the repeating units in the resin (A) It has become. In particular, the content of the repeating unit represented by the general formula (1) to all the repeating units is considered to contribute to the improvement of the film thickness uniformity.
When the content of the repeating unit represented by the general formula (1) is 25 mol% or more based on all repeating units in the resin (A), the interaction between the resins can be sufficiently obtained. An actinic ray-sensitive or radiation-sensitive resin obtained by suppressing the occurrence of unevenness on the film surface which is likely to be generated as the interaction between the resins is too weak when dried in forming the actinic ray-sensitive or radiation-sensitive resin film It is estimated that the film thickness uniformity of the film is excellent.
On the other hand, when the content of the repeating unit represented by the above general formula (1) is 50 mol% or less with respect to all repeating units in the resin (A), the interaction between the resins does not become too high. . Here, for example, when an actinic ray-sensitive or radiation-sensitive resin composition is applied by a spin coating method to a wafer having a large aperture such as a 12-inch wafer, as compared with the case where a wafer having a small aperture is used. The coating film provided on the outer periphery of the wafer is susceptible to the wind accompanying the rotation of the wafer. Specifically, in the peripheral portion of the actinic ray-sensitive or radiation-sensitive resin film to be obtained in particular, unevenness due to the above-mentioned wind occurs, and the film thickness uniformity tends to be lowered. However, in the actinic ray-sensitive or radiation-sensitive resin film according to the present invention, since the interaction between the resins is not too high as described above, the unevenness of the outer peripheral portion derived from the above-mentioned wind hardly occurs, It is estimated that the film thickness uniformity of the actinic ray-sensitive or radiation-sensitive resin film is excellent.
By the above, the content of the repeating unit represented by the above general formula (1) is 25 to 50 mol% with respect to all the repeating units in the resin (A), the actinic ray sensitivity or sensitivity obtained It is estimated that the film thickness uniformity of the radioactive resin film is excellent.

Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention will be described.
In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, negative development (if exposed, the solubility in the developer decreases, the exposed portions remain as a pattern, and the unexposed portions are removed. Is preferably used in the development). That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for developing an organic solvent used for development using a developer containing an organic solvent. be able to. Here, the use for organic solvent development means the use provided to the process developed using the developing solution which contains an organic solvent at least.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and is preferably a negative resist composition (that is, a resist composition for developing an organic solvent). The composition according to the present invention is typically a chemically amplified resist composition.

[1] Resin (A)
The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a repeating unit represented by the above general formula (1), and is represented by the above general formula (1) The content of the repeating unit is 25 to 50% by mole, preferably 30 to 45% by mole, more preferably 35 to 40% by mole, based on all repeating units in the resin (A).

In the general formula (1), the hydroxyl group is preferably bonded to the benzene ring in the para position relative to the main chain. Specifically, general formula (1) is preferably a parahydroxystyrene skeleton.

In the general formula (2), R ₁ represents a hydrogen atom or a methyl group.
R ₂ and R ₃ each independently represent a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Or tert-butyl group.

The ring having 3 to 8 carbon atoms which may be formed by bonding of R ₂ and R ₃ to each other is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group and a cyclopentyl group, Cyclohexyl group, cyclooctyl group and the like can be mentioned.

R ₄ represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms. The polycyclic hydrocarbon group having 6 to 20 carbon atoms is preferably a polycyclic cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, a camphanyl group, a dicyclopentyl group and a bicyclooctyl group. And α-pinel group, tricyclodecanyl group, tetracyclododecyl group, androstanyl group and the like can be mentioned. In addition, at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.
The R _4, adamantyl group, norbornyl group, or a bicyclooctyl group (bicyclo [2.2.2] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl group) preferable.

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

The content of the repeating unit represented by the above general formula (2) is preferably 25 to 50 mol%, more preferably 30 to 47.5, with respect to all repeating units in the resin (A). The mole% is more preferably 35 to 45 mole%.
The content of the repeating unit represented by the general formula (2) is preferably 25 to 50 mol% with respect to all the repeating units in the resin (A), and is represented by the general formula (2) It is considered that the interaction between the repeating unit and the repeating unit represented by the general formula (1) can be weakened, and the film thickness uniformity of the actinic ray-sensitive or radiation-sensitive resin film becomes good.

The repeating unit represented by the above general formula (2) of the resin (A) may be of one type or two or more types in combination.

Although the preferable specific example of the repeating unit represented by the said General formula (2) is shown below, this invention is not limited to this.
In specific examples, Rx represents a hydrogen atom or a methyl group. Each of Rxa and Rxb independently represents a hydrocarbon group having 1 to 4 carbon atoms. Z represents a substituent, and when there are two or more, a plurality of Z may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as R ₁ to R ₄ may have.

In the general formula (3), R ₅ is a hydrogen atom or a methyl group.
R ₆ , R ₇ and R ₈ each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms. As the linear or branched hydrocarbon group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group And isopropyl, n-butyl, isobutyl or tert-butyl.

The content of the repeating unit represented by the above general formula (3) is preferably 10 to 35 mol%, more preferably 15 to 30 mol%, based on all repeating units in the resin (A). More preferably, it is 20 to 25 mol%.

The repeating unit represented by the above general formula (3) of the resin (A) may be of one type or two or more types in combination.

Although the preferable specific example of the repeating unit represented by the said General formula (3) is shown below, this invention is not limited to this.

The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a repeating unit represented by the above general formula (1), a repeating unit represented by the above general formula (2), And when it contains only the repeating unit represented by the said General formula (3), content (mol%) with respect to all the repeating units in resin (A) of the repeating unit represented by the said General formula (1) Content (mol%) of all the repeating units in the resin (A) of the repeating unit represented by the general formula (2) and all the repetition in the resin (A) of the repeating unit represented by the general formula (3) The sum of the content (mol%) with respect to the unit is 100.

[Other repeat unit]
The resin (A) may further have a repeating unit having a lactone structure. As a repeating unit which has a lactone structure, the repeating unit represented by the following general formula (AII) is more preferable.

In the general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having a carbon number of 1 to 4) which may have a substituent.
Preferred examples of the substituent which the alkyl group of Rb ₀ may have 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 hydroxymethyl group or a trifluoromethyl group, with a hydrogen atom or a methyl group being particularly preferred.

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 combining these. Ab is preferably a single bond or a divalent linking group represented by -Ab ₁ -CO _2- .
Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group having a lactone structure.

As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a 5- to 7-membered lactone structure is preferably a bicyclo structure or a spiro structure. Those in which another ring structure is condensed in the form to be formed are preferable. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Also, the lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13) and (LC1-14).

The lactone structure 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 monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. And a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid decomposable group and the like. More preferably, it is an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-degradable group. n ₂ represents an integer of 0 to 4; When n ₂ is 2 or more, plural substituents (Rb ₂ ) may be the same or different, and plural substituents (Rb ₂ ) may be combined to form a ring .

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one type of optical isomer is mainly used, one having an optical purity (ee) of 90% or more is preferable, and more preferably 95% or more.

The resin (A) may or may not contain a repeating unit having a lactone structure, but in the case of containing a repeating unit having a lactone structure, the content of the repeating unit in the resin (A) is all The preferred range is 0.5 to 50 mol%, more preferably 1 to 40 mol%, and still more preferably 3 to 30 mol%, with respect to the repeating unit. The repeating unit may be of one type, or two or more types may be used in combination. By using a specific lactone structure, the resolution of the pattern is improved and the rectangular profile is improved.
Although the specific example of the repeating unit which has a lactone structure in resin (A) below is shown, this invention is not limited to this. Wherein, Rx _{is, H,} represents a CH 3, _CH 2 OH, or CF _3.

The resin (A) may have a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (e.g., hexafluoroisopropanol group) in which the alpha position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit. By containing a repeating unit having an acid group, the resolution in contact hole applications and the like is increased. As a repeating unit having an acid group, a repeating unit in which an acid group is directly bonded to the resin main chain such as a repeating unit of acrylic acid or methacrylic acid, or an acid group is attached to the resin main chain via a linking group A polymerization initiator having an attached repeating unit, or an acid group, or a chain transfer agent is preferably used at the end of the polymer chain at the time of polymerization, and the linking group is preferably a monocyclic or polycyclic hydrocarbon ring structure. May be included. Particularly preferred are repeating units of acrylic acid and methacrylic acid.
Although the specific example of the repeating unit which has an acidic radical is shown below, this invention is not limited to this.
In the specific examples, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (A) may or may not contain a repeating unit having an acid group, but when the resin (A) contains a repeating unit having an acid group, the content of the repeating unit is the resin (A) 1 to 25 mol% is preferable, more preferably 1 to 20 mol%, still more preferably 3 to 15 mol%, based on all the repeating units in the above).

The resin (A) may further have a repeating unit having a hydroxyl group or a cyano group, which is a repeating unit other than the above-described repeating units. Thereby, the substrate adhesion and the developer affinity can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid decomposable group. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, an adamantyl group, a diamantyl group, and a norbornane group are preferable, and an adamantyl group is more preferable. Moreover, it is preferable that it is substituted by the hydroxyl group, and it is more preferable to contain the repeating unit which has the adamantyl group substituted by at least 1 hydroxyl group.
In particular, the resin (A) most preferably contains a repeating unit having a hydroxyadamantyl group or a dihydroxyadamantyl group from the viewpoint of suppressing the diffusion of the generated acid. As the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable, and partial structures represented by the following general formula (VIIa) are more preferable. .

In the general formulas (VIIa) to (VIIc),
Each of R ₂ c to R ₄ c independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remainder is a hydrogen atom. In the general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remainder is a hydrogen atom.

As repeating units having a partial structure represented by general formulas (VIIa) to (VIId), repeating units represented by the following general formulas (AIIa) to (AIId) can be mentioned.

In general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
_R ₂ c ~ R ₄ c is in the general formula (VIIa) ~ _(VIIc), the same meanings as _R 2 c ~ R ₄ c.
Although the specific example of the repeating unit which has a hydroxyl group or a cyano group is given to the following, this invention is not limited to these.

The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but when the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the above-mentioned repetition is repeated The content of the unit is preferably 1 to 40 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 30 mol%, based on all repeating units in the resin (A).

The resin (A) in the present invention may further have an alicyclic hydrocarbon structure which does not have a polar group (for example, the above-mentioned acid group, hydroxyl group, cyano group) and may have a repeating unit which does not exhibit acid decomposability. Thereby, the solubility of resin can be appropriately adjusted at the time of the image development using the developing solution containing the organic solvent. As such a repeating unit, the repeating unit represented by general formula (IV) is mentioned.

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

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. The monocyclic hydrocarbon group is, for example, a cycloalkyl group having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group or cyclooctyl group, cycloalkenyl group having 3 to 12 carbon atoms such as cyclohexenyl group Groups are mentioned. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having a carbon number of 3 to 7, and more preferably a cyclopentyl group or a cyclohexyl group.

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

As preferred crosslinked-ring hydrocarbon rings, a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6] decanyl group, and the like. A norbornyl group and an adamantyl group are mentioned as a more preferable bridged cyclic hydrocarbon ring.

These alicyclic hydrocarbon groups may have a substituent, and preferable substituents include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amino group substituted with a hydrogen atom, and the like. Be Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The above alkyl group may further have a substituent, and as the substituent which may further have, a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amino substituted with a hydrogen atom Groups can be mentioned.

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 aralkyloxycarbonyl group. The preferred alkyl group is an alkyl group having 1 to 4 carbon atoms, the preferred substituted methyl group is methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, and the preferred substituted ethyl group is 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups are aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyls Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit not showing acid decomposability, but the resin (A) is an oil having no polar group. In the case of containing a repeating unit having a cyclic hydrocarbon structure and not showing acid decomposability, the content of the repeating unit is preferably 1 to 40% by mole, relative to all repeating units in the resin (A). Preferably, it is 1 to 20 mol%.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not showing acid decomposability are listed below, but the present invention is not limited thereto. In the formulas, _{Ra, H,} represents a CH 3, _CH 2 OH, or CF _3.

The resin (A) used in the composition of the present invention is, besides the above-mentioned repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, actinic ray sensitive or radiation sensitive resin composition It may have various repeating structural units for the purpose of adjusting the resolution, heat resistance, sensitivity and the like which are generally necessary characteristics of the above.

As such repeating structural units, repeating structural units corresponding to the following monomers can be mentioned, however, it is not limited thereto.
Thereby, the performance required for the resin used in the composition of the present invention, in particular
(1) Solubility in coating solvents,
(2) Film forming property (glass transition point),
(3) Alkali developability,
(4) Membrane-like (hydrophilic, alkali-soluble group selection),
(5) Adhesion of the unexposed area to the substrate,
(6) Fine adjustment such as dry etching resistance is possible.

As such a monomer, for example, addition polymerization is selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates and the like The compound etc. which have one unsaturated bond can be mentioned.
In addition, as long as it is an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to the above-mentioned various repeating structural units, it may be copolymerized.

In the resin (A) used in the composition of the present invention, the content molar ratio of each repeating structural unit is the dry etching resistance of the actinic ray sensitive or radiation sensitive resin composition, the standard developing solution suitability, the substrate adhesion, the resist The profile is set appropriately to adjust the resolution, heat resistance, sensitivity and the like which are generally necessary performance of the resist.
The form of the resin (A) in the present invention may be any form of random type, block type, comb type, and star type. The resin (A) can be synthesized, for example, by radical, cation or anionic polymerization of unsaturated monomers corresponding to each structure. It is also possible to obtain a target resin by polymer reaction after polymerization using unsaturated monomers corresponding to precursors of each structure.

The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a batch polymerization method in which monomer species and an initiator are dissolved in a solvent and polymerization is carried out by heating, a solution of monomer species and an initiator is dropped over a heating solvent over 1 to 10 hours. The dropping polymerization method etc. are mentioned, and the drop polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, and amide solvents such as dimethylformamide and dimethylacetamide. Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, a propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, polymerization is performed using the same solvent as the solvent used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. This makes it possible to suppress the generation of particles during storage.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.) as the polymerization initiator. As a radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methyl propionate) and the like. If desired, an initiator is added additionally or in portions, and after completion of the reaction, it is poured into a solvent and the desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.

After completion of the reaction, the reaction solution is allowed to cool to room temperature and purified. Purification is carried out by washing with water, liquid-liquid extraction which removes residual monomers and oligomer components by combining appropriate solvents, and purification method in solution such as ultrafiltration which extracts and removes only those having a specific molecular weight or less. The resin solution is dropped into a poor solvent to coagulate the resin in the poor solvent to remove residual monomers and the like Reprecipitation method or purification of the filtered resin slurry with a poor solvent in a solid state such as washing with a poor solvent The usual method such as the method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is poorly soluble or insoluble in a volume of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be any poor solvent for the polymer, and depending on the type of the polymer, hydrocarbon, halogenated hydrocarbon, nitro It can be used by appropriately selecting from compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like.

The amount of precipitation or reprecipitation solvent used can be appropriately selected in consideration of the efficiency, yield, etc. Generally, 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution More preferably, it is 300 to 1000 parts by mass.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but it is usually about 0 to 50 ° C., preferably around room temperature (eg, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch system or a continuous system using a conventional mixing vessel such as a stirring tank.
The precipitated or reprecipitated polymer is usually subjected to conventional solid-liquid separation such as filtration, centrifugation and the like, dried and used. The filtration is carried out using a solvent resistant filter medium, preferably under pressure. Drying is carried out at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C., under normal pressure or reduced pressure (preferably under reduced pressure).
Alternatively, the resin may be once precipitated and separated, and then dissolved again in a solvent and brought into contact with a solvent in which the resin is poorly soluble or insoluble. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is poorly soluble or insoluble is brought into contact to precipitate the resin (step a), separate the resin from the solution (step b), and dissolve again in the solvent. Is prepared (step c), and then the resin solution A is brought into contact with a solvent in which the resin is sparingly soluble or insoluble in a volume less than 10 times (preferably 5 times or less the volume of) the resin solution A Thus, the method may include a method of precipitating a resin solid (step d) and separating the precipitated resin (step e).

Further, in order to suppress aggregation of the resin after preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution, and the solution is A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.
The weight average molecular weight of the resin (A) used in the composition of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, in terms of polystyrene as determined by GPC method. More preferably, it is 3,000 to 70,000, and particularly preferably 5,000 to 50,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated or viscosity is increased to deteriorate film forming property. You can prevent that.

The degree of dispersion (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.2 to 2.4, particularly preferably 1.4 to 2.2. Those in the range of When the molecular weight distribution satisfies the above range, the resolution and the resist shape are excellent, and the side wall of the resist pattern is smooth and the roughness is excellent.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, based on the total solid content. It is.
In the present invention, the resin (A) may be used alone or in combination of two or more.

[3] Compounds that generate an acid upon irradiation with actinic rays or radiation (B)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter, also referred to as "acid generator (B)").
The acid generator (B) is not particularly limited, but is preferably a compound capable of generating an organic acid upon irradiation with an actinic ray or radiation.
The compound (B) capable of generating an acid upon irradiation with an actinic ray or radiation may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. Further, the form of the low molecular weight compound and the form incorporated into a part of the polymer may be used in combination.
When the compound (B) capable of generating an acid upon irradiation with an actinic ray or radiation is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less Is more preferred.
When the compound (B) capable of generating an acid upon irradiation with an actinic ray or radiation is in a form incorporated into a part of a polymer, the compound (B) may be incorporated into a part of the resin (A) described above. ) May be incorporated into a different resin.

Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyl sulfonates, and the acid generator (B) contains sulfonium salts or iodonium salts Is preferred.

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

Furthermore, compounds capable of generating an acid by the action of light described in U.S. Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with an actinic ray or radiation to generate an acid as the acid generator (B), compounds represented by the following general formulas (ZI), (ZII) and (ZIII) Can be mentioned.

In the above general formula (ZI), each of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ independently represents an organic group.
Z ^- represents a non-nucleophilic anion, preferably a sulfonate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide _{^{_{^{anion, BF 4 -, PF 6 -}}}} , SbF 6 - are exemplified, etc., preferably Is an organic anion containing a carbon atom. Preferred organic anions include organic anions represented by the following formulas AN1 to AN3.

In formulas AN1 to AN3, Rc ₁ to Rc ₃ each independently represent an organic group. The organic group in Rc ₁ to Rc ₃ includes one having 1 to 30 carbon atoms, preferably an alkyl group which may be substituted, a monocyclic or polycyclic cycloalkyl group, a hetero atom-containing cyclic group, an aryl group Or a plurality of these are linked via a linking group such as a single bond, -O-, -CO _2- , -S-, -SO _3- , -SO _2- , -SO ₂ N (Rd ₁ )-or the like Groups can be mentioned. Furthermore, it may form a ring structure with another linked alkyl group or aryl group.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with a bonded alkyl group or aryl group.
The organic group of Rc ₁ to Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R ₂₀₁ to R ₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.
Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, a butylene group and a pentylene group).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. be able to.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula _R 201 _{~ R 203} of a compound represented by (ZI) at least one is, the structures attached to at least one of the general formulas (ZI) of another compound represented by _R 201 _{~ R 203} It may be a compound which it has.

Further preferable examples of the component (Z1) include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remaining may be an alkyl group.
Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, and aryldialkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group, a naphthyl group or a fluorene group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group which the arylsulfonium compound optionally has is preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -Butyl, t-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.
The aryl group and the alkyl group as _R201 to _R203 are an alkyl group (for example, 1 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, It may have a hydroxyl group or a phenylthio group as a substituent. Preferred substituents are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferred are alkyl groups having 1 to 4 carbon atoms, It is an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted on any one of three R ₂₀₁ to R ₂₀₃ or may be substituted on all three. When R ₂₀₁ to R ₂₀₃ are aryl groups, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound where R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represents an aromatic ring-free organic group. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The aromatic ring-free organic group as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Each of _R201 to _R203 independently is preferably an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group, and more preferably a straight chain. It is a chain or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, and most preferably a linear or branched 2-oxoalkyl group.
The alkyl group and cycloalkyl group as R ₂₀₁ to R ₂₀₃ are preferably linear or branched alkyl groups having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), Mention may be made of cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be either linear or branched, and preferably includes a group having> C = O at the 2-position of the above alkyl group.
Preferred _examples of the 2-oxocycloalkyl group as R ₂₀₁ to R ₂₀₃ include a group having> C = O at the 2-position of the above-mentioned cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R ₂₀₃ is preferably an alkoxy group having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.
Two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, a butylene group and a pentylene group).

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

In the general formula (ZI-3),
Each of R _1c to R _5c independently represents 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 or 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.
Each of R _x and R _y independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y respectively combine to form a ring structure The ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic fused ring in which two or more of these rings are combined. The ring structure may be a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.

Examples of the group formed by bonding any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .
Zc ^- represents a non-nucleophilic anion, preferably Z ^- represents, in particular, as described above.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _{5c are the same} as the specific examples of the alkoxy group as R ₂₀₁ to R ₂₀₃ above.
Specific examples of the alkyl group in the alkylcarbonyloxy group and the alkylthio group as R _1c to R _{5c are the same} as the specific examples of the alkyl group as R ₂₀₁ to R ₂₀₃ above.
Specific examples of the cycloalkyl group in the cycloalkylcarbonyloxy group as R _1c to R _{5c are the same} as the specific examples of the cycloalkyl group as R ₂₀₁ to R ₂₀₃ described above.
Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _{5c are the same} as the specific examples of the aryl group as R ₂₀₁ to R ₂₀₃ described above.

As the cation in the compound (ZI-2) or (ZI-3) in the present invention, the cations described in paragraph [0036] or later of US Patent Application Publication No. 2012/0076996 can be mentioned.

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

In the general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 's} , each independently has a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represents These groups may have a substituent.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may bond to each other to form a ring. When two R ₁₅ bonds to each other to form a ring, the ring skeleton may contain a heteroatom such as oxygen atom or nitrogen atom. In one aspect, it is preferable that two R ₁₅ be an alkylene group and bond together to form a ring structure.
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
Zc ^- represents a non-nucleophilic anion, preferably Z ^- represents, in particular, as described above.

In the general formula (ZI-4), the alkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and is preferably an alkyl group having 1 to 10 carbon atoms, and a methyl group, an ethyl group, n -Butyl group, t-butyl group and the like are preferable.
As a cation of the compound represented by general formula (ZI-4) in the present invention, paragraphs [0121], [0123], [0124], and JP-A-2011-76056 of JP-A-2010-256842. The cation described in paragraphs [0127], [0129], [0130] and the like can be mentioned.

Next, general formulas (ZII) and (ZIII) will be described.
In formulas (ZII) and (ZIII), each of R ₂₀₄ to R ₂₀₇ independently has an aryl group which may have a substituent, an alkyl group which may have a substituent, or a substituent. Represents a cycloalkyl group which may be substituted.
Specific examples of the aryl group of R ₂₀₄ to R ₂₀₇ and preferable ones are the same as those described as the aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI-1).
Specific examples of the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ , preferably, those described as the linear, branched or cyclic alkyl group as R ₂₀₁ to R ₂₀₃ in the above compound (ZI-2) It is similar.
Z ^- is, in the general formula (ZI) Z ^- synonymous.

Among the compounds capable of generating an acid upon irradiation with an actinic ray or radiation as the acid generator (B), compounds represented by the following general formulas (ZIV), (ZV) and (ZVI) It can be mentioned.

In the general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.
R ₂₀₈ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted aryl group in general formulas (ZV) and (ZVI). From the viewpoint of enhancing the strength of the generated acid, R ₂₀₈ is preferably substituted by a fluorine atom.
Each of R ₂₀₉ and R ₂₁₀ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an alkylthio group or an electron-withdrawing group.
Further, R ₂₀₉ and R ₂₁₀ may be combined to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, an arylene group and the like.
Preferably R ₂₀₉ is a substituted or unsubstituted aryl group. R ₂₁₀ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkenylene group or a substituted or unsubstituted arylene group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ include the same as specific examples of the aryl group as R ₂₀₁ to R ₂₀₃ in the general formula (ZI-1). be able to.
Specific examples of the alkyl group and cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the alkyl group and cycloalkyl group as R ₂₀₁ to R ₂₀₃ in the general formula (ZI-2), respectively. Can be mentioned.
Examples of the alkyl moiety of the alkylthio group for R ₂₀₉ and R ₂₁₀ include the same as specific examples of the alkyl group as R ₂₀₁ to R ₂₀₃ in the general formula (ZI-2).
The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the cycloalkylene group of A is carbon number As a monocyclic or polycyclic cycloalkylene group (for example, cyclohexylene group, norbornylene group, adamantylene group etc.) of 3 to 12 and an alkenylene group for A, an alkenylene group having 2 to 12 carbon atoms (for example, ethenylene group) And the arylene group for A may be, for example, an arylene group having 6 to 10 carbon atoms (eg, a phenylene group, a tolylene group, a naphthylene group or the like).

In addition, the compound which has two or more structures represented by general formula (ZVI) is also preferable in this invention. For example, a one of _{R 209} or _{R 210} of the compound represented by the general formula (ZVI) is a structure bonded with either _{R 209} or _{R 210} of another compound represented by the general formula (ZVI) It may be a compound.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid as the acid generator (B), more preferably, the solubility in a developer containing an organic solvent in the unexposed area is good, and development defects From the viewpoint of being less likely to occur, compounds represented by the above general formulas (ZIII) to (ZVI), that is, so-called nonionic compounds are preferable. Among them, the compound represented by the above general formula (ZV) or (ZVI) is more preferable.
In addition, from the viewpoint of improving the acid generation efficiency and the acid strength, the acid generator (B) preferably has a structure that generates an acid containing a fluorine atom.
Although the specific example of an acid generator (B) is shown below, it does not limit to these.

An acid generator (B) can be used individually by 1 type or in combination of 2 or more types. When using in combination of 2 or more types, it is preferable to combine the compound which generate | occur | produces 2 types of organic acids from which the total number of atoms except a hydrogen atom differs 2 or more.
For example, from the viewpoint of improving acid generation efficiency and acid strength, an embodiment in which a compound having a structure that generates an acid containing a fluorine atom and a compound that does not have such a structure are used in combination is mentioned.
The content of the acid generator (B) in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The content is about 15% by mass, more preferably 1 to 10% by mass.

[4] Solvent (C)
Examples of the solvent that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition in the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, and alkoxy propion. Organic solvents such as alkyl acids, cyclic lactones (preferably having a carbon number of 4 to 10), monoketone compounds which may have a ring (preferably having a carbon number of 4 to 10), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like be able to.
Specific examples of these solvents may include those described in US Patent Application Publication 2008/0187860 [0441] to [0455].

In the present invention, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used as the organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, as the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among them, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the hydroxyl group-containing solvent to the hydroxyl group-free solvent is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferred in view of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably propylene glycol monomethyl ether acetate alone or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[5] Basic compound (E)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may contain a basic compound (E) in order to reduce the change in performance over time from exposure to heating.
As the basic compound, preferably, compounds having the structures represented by the following formulas (A) to (E) can be mentioned.

In the general formulas (A) and (E)
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (carbon atoms) 6 to 20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ^{206, which} may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms.
As the alkyl group having a substituent, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
The alkyl group in these general formulas (A) and (E) is more preferably unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkyl morpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

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

Examples of preferable basic compounds further include amine compounds having a phenoxy group, ammonium salt compounds having a phenoxy group, amine compounds having a sulfonic acid ester group, and ammonium salt compounds having a sulfonic acid ester group.
The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group, and the ammonium salt compound having a sulfonic acid ester group have at least one alkyl group bonded to a nitrogen atom Is preferred. Moreover, it is preferable to have an oxygen atom in the said alkyl chain, and the oxyalkylene group is formed. The number of oxyalkylene groups in the molecule is one or more, preferably 3 to 9, and more preferably 4 to 6. _-CH 2 _CH 2 O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or _-CH 2 _CH 2 _CH 2 O- structure 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 sulfonic acid ester group, and the ammonium salt compound having a sulfonic acid ester group are disclosed in US Patent Application Publication No. 2007/0224539. Examples of the compound (C1-1) to (C3-3) exemplified in [0066] are not limited thereto.

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a basic compound, but when it is contained, the amount of the basic compound used is an actinic ray-sensitive or radiation-sensitive compound. The amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resin composition.

The ratio of the acid generator to the basic compound used in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppression of reduction in resolution due to thickening of the resist pattern over time after exposure and heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[6] Surfactant (F)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant, and when it contains a fluorine and / or silicon surfactant (a fluorine-based surfactant It is more preferable to contain one or more of a silicon-based surfactant, a surfactant having both a fluorine atom and a silicon atom, or two or more.

When the actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It is possible to provide a small resist pattern.
Examples of fluorine-based and / or silicon-based surfactants include the surfactants described in [0276] of US Patent Application Publication No. 2008/0248425, such as EF-TOP EF 301, EF 303, (Nihin Akita Kasei Made), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08, R41 (manufactured by DIC Corporation), Surflon S -382, SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toa Synthetic Chemical Co., Ltd.) (Manufactured by Co., Ltd.), Surfron S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF12 , EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G , 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

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

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

These surfactants may be used alone or in some combinations.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant. In this case, the amount of surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total amount (excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. %.

[7] Other additives (G)
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a carboxylic acid onium salt. As such a carboxylic acid onium salt, those described in US Patent Application Publication 2008/0187860 [0605] to [0606] can be mentioned.

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

When the actinic ray-sensitive or radiation-sensitive resin composition contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0 based on the total solid content of the composition. The content is preferably 5 to 10% by mass, more preferably 1 to 7% by mass.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further comprises, if necessary, solubility in a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor and a developer. A compound to be promoted (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic or aliphatic compound having a carboxyl group), and the like can be contained.

Such phenolic compounds having a molecular weight of 1000 or less are described in, for example, the methods described in JP-A-4-22938, JP-A-2-28531, US Pat. No. 4,916,210, EP 219 294, etc. Those skilled in the art can easily synthesize.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Although a dicarboxylic acid etc. are mentioned, it is not limited to these.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably 30 to 200 nm, from the viewpoint of improving resolution. preferable. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and the film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 15% by mass, preferably 2.5 to 13% by mass, more preferably 3.0 to 12%. It is mass%. By setting the solid content concentration in the above range, the resist solution can be uniformly applied on the substrate, and furthermore, a resist pattern having high resolution and a rectangular profile, and excellent etching resistance is formed. It becomes possible. Although the reason is not clear, probably, by setting the solid concentration to 10% by mass or less, preferably 5.7% by mass or less, aggregation of the material, particularly the photoacid generator in the resist solution is suppressed As a result, it is considered that a uniform resist film could be formed.
The solid content concentration is a weight percentage of the weight of the other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is prepared by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering it, and then applying it on a predetermined support (substrate). Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less, and made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, cyclic filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filter filtration.

[8] Pattern Forming Method The pattern forming method (negative pattern forming method) of the present invention is
(A) forming a film (an actinic ray-sensitive or radiation-sensitive resin composition film) with an actinic ray-sensitive or radiation-sensitive resin composition,
(A) exposing the film, and (c) developing the exposed film using a developer containing an organic solvent to form a negative pattern.
Have at least

The exposure in the step (i) may be immersion exposure.
The pattern formation method of the present invention preferably includes (d) a heating step after (a) exposure step.
The pattern formation method of the present invention may further include (e) developing with an alkaline developer.
The pattern formation method of the present invention can have (a) multiple exposure steps.
The pattern formation method of the present invention can have (e) multiple heating steps.

The actinic ray sensitive or radiation sensitive resin film is preferably a resist film.

The actinic ray-sensitive or radiation-sensitive resin film of the present invention is a film formed of the above actinic ray-sensitive or radiation-sensitive resin composition, and, for example, an actinic ray-sensitive or radiation-sensitive resin composition on a substrate It is a film formed by applying a substance.
Specifically, the actinic ray-sensitive or radiation-sensitive resin film of the present invention is obtained by applying the actinic ray-sensitive or radiation-sensitive resin composition onto a substrate by a spin coating method. Or a radiation sensitive resin film is preferable.
The maximum number of revolutions of the spin coating method is not particularly limited, but is preferably 2500 rpm or less, more preferably 2250 rpm or less, and still more preferably 2000 rpm or less.

The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention described above, and more specifically, it is preferable to be formed on a substrate. In the pattern formation method of the present invention, a step of forming a film of an actinic ray-sensitive or radiation-sensitive resin composition on a substrate, a step of exposing the film, and a development step are generally known methods. Can be done by

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 130 ° C. for both PB and PEB, and more preferably 80 to 120 ° C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
The heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The bake accelerates the reaction in the exposed area and improves the sensitivity and pattern profile.

As a light source wavelength used for the exposure apparatus in the present invention, a KrF excimer laser (248 nm), EUV (13 nm), an electron beam and the like can be mentioned, and a KrF excimer laser is preferable.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, an inorganic substrate such as SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG, a semiconductor manufacturing process such as IC, liquid crystal, thermal head Substrates generally used in circuit board manufacturing processes such as, and other lithography processes for photofabrication can be used.
In the pattern formation method of the present invention, for example, in microfabrication such as in ion implantation, a stepped substrate can be used as the substrate.
The stepped substrate is a substrate in which at least one stepped shape is formed on the substrate.
The film thickness of the laminated film formed on the above-described stepped substrate means the height from the bottom surface on the stepped substrate to the upper surface of the resist film formed.
The height from the bottom surface of the stepped substrate to the upper surface of the stepped shape is preferably smaller than the film thickness of the resist film, and may be, for example, less than 200 nm.
For example, in the case of microfabrication such as for ion implantation, a substrate in which fins and gates are patterned on a flat substrate can be used as a stepped substrate. The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition is applied on the stepped substrate on which the fins and the gate are patterned in this manner, and the film thickness of the resist film formed is formed from the upper surface of the fin and the gate. This means not the height to the upper surface of the resist film, but the height to the upper surface of the resist film formed from the bottom surface on the stepped substrate as described above.
For example, the sizes (width, length, height, etc.), intervals, structures, configurations, etc. of fins and gates can be found in, for example, Journal of the Institute of Electronics, Information and Communication Engineers Vol. 91, no. 1, 2008, pp. 25-29, "Advanced FinFET Process and Integration Technology", Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 4142-4146 Part 1, No. 6B, June 2003 “Fin-Type Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistors Fabricated by Orientation-Dependent Etching and Electron Beam Lithography” can be applied as appropriate.
The pattern forming method of the present invention does not require an antireflective film from the viewpoint of achieving the effects of the present invention, but an organic antireflective film may be formed between the film and the substrate as needed.
For example, an antireflective film may be provided below the resist. As the antireflective film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and amorphous silicon, and organic film types made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflective film, for example, a condensation product of a diphenylamine derivative described in Japanese Examined Patent Publication No. 7-69611 and a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. Reaction product of a combination and a diamine type light absorbing agent, one containing a resin binder described in JP-A-6-118631 and a methylolmelamine-based thermal crosslinking agent, a carboxylic acid group and an epoxy group and a light absorbing group described in JP-A-6-118656 An acrylic resin type antireflective film having in the same molecule, one comprising methylolmelamine described in JP-A-8-87115 and a benzophenone-based light absorber, and a low molecular weight absorber added to a polyvinyl alcohol resin described in JP-A-8-179509. And the like.
In addition, it is also possible to use commercially available organic antireflection films such as DUV30 series manufactured by Brewer Science, DUV-40 series, AR-2 manufactured by Shipley, AR-3, and AR-5 as organic antireflection films. it can.
In addition, an antireflective film can be used on the upper layer of the resist as needed.
Examples of the antireflective film include AQUATAR-II, AQUATAR-III, and AQUATAR-VII manufactured by AZ Electronic Materials Co., Ltd.

Examples of the developing solution (hereinafter, also referred to as an organic developing solution) in the step of developing using a developing solution containing an organic solvent according to the present invention include ketone solvents, ester solvents, alcohol solvents, Polar solvents such as amide solvents and ether solvents and hydrocarbon solvents can be used.
Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples thereof include cyclohexanone, methyl cyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.
As ester solvents, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, butyl formate, propyl lactate, ethyl lactate, butyl lactate, propyl lactate etc. Butyl acetate is particularly preferred.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, Alcohols such as n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvents include, in addition to the above glycol ether solvents, dioxane, tetrahydrofuran and the like.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. It can be used.
Examples of the hydrocarbon-based solvent include aromatic hydrocarbon-based solvents such as toluene and xylene, and aliphatic hydrocarbon-based solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water. However, in order to sufficiently achieve the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and it is more preferable to substantially not contain water.
That is, the use amount of the organic solvent with respect to the organic developer is preferably 90% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

At 20 ° C., the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimension uniformity in the wafer surface Sex improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formate Ester solvents such as propyl formate, ethyl lactate, butyl lactate and propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohol solvents such as n-heptyl alcohol, n-octyl alcohol and n-decanol glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy ether Glycol ether solvents such as rubanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic carbonization such as toluene and xylene Examples thereof include hydrogen based solvents, aliphatic hydrocarbon based solvents such as octane and decane.
Specific examples having a vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone and methylcyclohexanone Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, n-butyl alcohol, Alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol And 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, methoxymethyl butanol, N-methyl-2 Amide solvents of N-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aromatic hydrocarbon solvents such as cyclohexylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of surfactant can be added to the organic developer as needed.
The surfactant is not particularly limited, but for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As these fluorine and / or silicone surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, and the like The surfactants described in the specifications of 5360692, 5529881, 5296330, 5436098, 5576143, 5294511 and 5824451 can be mentioned. Preferably, they are nonionic surfactants. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
The amount of surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

As a developing method, for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of developing by standing up the developer on the substrate surface by surface tension and standing for a certain time (paddle Method), spraying the developer on the substrate surface (spraying method), and continuing to discharge the developer while scanning the developer discharging nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the above various developing methods include the step of discharging the developing solution toward the resist film from the developing nozzle of the developing device, the discharging pressure of the discharged developing solution (flow velocity per unit area of the discharged developing solution) is It is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and still more preferably 1 mL / sec / mm ² or less. The lower limit of the flow rate is not particularly limited, but in consideration of the throughput, 0.2 mL / sec / mm ² or more is preferable.
By setting the discharge pressure of the discharged developer to the above range, it is possible to significantly reduce the defects of the pattern derived from the resist residue after development.
The details of this mechanism are not clear, but perhaps the pressure applied by the developer to the resist film is reduced by setting the discharge pressure in the above range, and the resist film and resist pattern are carelessly broken or broken. Is considered to be suppressed.
The discharge pressure (mL / sec / mm ² ) of the developer is a value at the outlet of the developing nozzle in the developing device.

Examples of the method of adjusting the discharge pressure of the developing solution include a method of adjusting the discharge pressure by a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

In addition, after the step of developing using a developing solution containing an organic solvent, the step of stopping development while replacing with another solvent may be carried out.

It is preferable to include the process wash | cleaned using a rinse solution after the process developed using the developing solution containing an organic solvent.

The rinse solution used in the rinse process after the process of developing with the developer containing the organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. . As the rinse solution, a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Is preferred.
As specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, the same ones as described in the developer containing an organic solvent can be mentioned.
More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. The step of washing with a rinse liquid is carried out, more preferably, the step of washing with a rinse liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinse liquid containing a monohydric alcohol is used. The washing step is carried out, and the washing step is most preferably carried out using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched and cyclic monohydric alcohols, and more specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol , Tert-butyl alcohol, 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 can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

Each of the above components may be mixed, or may be mixed with an organic solvent other than the above.

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

At 20 ° C., the vapor pressure of the rinse solution used after the step of development using a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse solution to 0.05 kPa or more and 5 kPa or less, temperature uniformity within the wafer surface is improved, and further swelling due to penetration of the rinse solution is suppressed, and dimension uniformity within the wafer surface Improve.
An appropriate amount of surfactant may be added to the rinse solution.

In the rinse step, the wafer that has been developed using a developer containing an organic solvent is washed using the above-described rinse liquid containing an organic solvent. Although the method of the cleaning process is not particularly limited, for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a fixed time A method (dip method), a method of spraying a rinse solution on the substrate surface (spray method), etc. can be applied, among which the washing treatment is carried out by the spin coating method, and after washing, the substrate is rotated at a rotational speed of 2000 rpm to 4000 rpm. The substrate is preferably rotated to remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By the baking, the developer and the rinse solution remaining between the patterns and inside the patterns are removed. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually for 10 seconds to 3 minutes, preferably for 30 seconds to 90 seconds.

When the pattern formation method of the present invention further includes the step of developing using an alkaline developer, examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia Inorganic alkalis such as water, primary amines such as ethylamine and n-propylamine Secondary amines such as diethylamine and di-n-butylamine Tertiary amines such as triethylamine and methyl diethylamine, dimethylethanolamine, triamine It is possible to use an aqueous alkaline solution such as alcohol amines such as ethanolamine, quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide, and cyclic amines such as pyrrole and piheridine.
Furthermore, an appropriate amount of alcohol and surfactant can be added to the alkaline aqueous solution and used.
The alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
The pH of the alkaline developer is usually 10.0 to 15.0.
In particular, a 2.38% by mass aqueous solution of tetramethyl ammonium hydroxide is desirable.

Pure water can be used as a rinse solution in the rinse treatment performed after alkali development, and an appropriate amount of surfactant can be added and used.
Further, after the development process or the rinse process, a process of removing the developer or the rinse solution adhering on the pattern with a supercritical fluid can be performed.

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

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example 1 Synthesis of Resin (Pol-1) 600 g of cyclohexanone was placed in a 2 L flask, and nitrogen substitution was performed for 1 hour at a flow rate of 100 mL / min. Thereafter, 4.60 g (0.02 mol) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised until the internal temperature reached 80.degree. Next, the following monomers and 4.60 g (0.02 mol) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 200 g of cyclohexanone to prepare a monomer solution. The monomer solution was dropped into the flask heated to 80 ° C. over 6 hours. After completion of the dropwise addition, reaction was further carried out at 80 ° C. for 2 hours.
40.55 g (0.25 mol) of 4-acetoxystyrene
Monomer corresponding to Unit 2-1 104.96 g (0.40 mol)
49.77 g (0.35 mol) of a monomer corresponding to Unit 3-1
The reaction solution was cooled to room temperature and dropped into 3 liters of hexane to precipitate a polymer. The filtered solid is dissolved in 500 mL of acetone, dropped into 3 L of hexane again, and the filtered solid is dried under reduced pressure to obtain 4-acetoxystyrene / monomer corresponding to Unit 2-1 / copolymer of monomer corresponding to Unit 3-1 I got 172 g.

In a reaction vessel, 10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol and 1.5 mL of concentrated hydrochloric acid were added, and the mixture was heated to 80 ° C. and stirred for 5 hours. The reaction solution was allowed to cool to room temperature and dropped into 3 liters of distilled water. The filtered solid was dissolved in 200 mL of acetone, dropped again into 3 L of distilled water, and the filtered solid was dried under reduced pressure to obtain 8.1 parts by mass of resin (Pol-1). The weight average molecular weight of the obtained resin (Pol-1) is 13,000, the degree of dispersion (Mw / Mn) is 1.5, and the composition ratio measured by ¹³ C-NMR is 25/40/35. there were.

The same procedure as in Synthesis Example 1 was performed to synthesize resins (Pol-2) to (Pol-13) and resins (Pol-C1) to (Pol-C2).
Table 1 below shows repeating units (units), composition ratios (molar ratios), weight average molecular weights, and resin (Pol-2) to (Pol-13) and resins (Pol-C1) to (Pol-C2) Indicates the degree of dispersion.

The components and abbreviations in the above Table 1 are as follows.

[Examples 1 to 14 and Comparative Examples 1 to 2]
[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
The components shown in Table 2 below are dissolved in a solvent, a resist solution for each is prepared, and this is filtered with a nylon filter having a pore size of 0.03 μm, and an actinic ray sensitive material having a solid concentration of 3.5% A radiation sensitive resin composition (resist composition) was prepared.

The components and abbreviations in Table 2 above are as follows. [Acid generator]

[Basic compound]

[Surfactant]
W-1: Megafuck R41 (made by DIC Corporation)

[solvent]
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)

The prepared actinic ray sensitive or radiation sensitive resin composition was evaluated by the following method.
[Film thickness uniformity]
Spin-coater (CLEAN TRACK LITHIUS Pro manufactured by Tokyo Electron Ltd.) on the resist composition shown in the above table on a 12 inch silicon wafer (diameter: 300 mm thickness: 775 μm material: single crystal silicon 12 inch silicon wafer, manufactured by MEMC Electronic) The resist film was applied at a maximum rotation speed of 2000 rpm and baked at 100 ° C. for 60 seconds (Pre Bake; PB) to form a resist film having a film thickness of 400 nm.
The film thickness of the resist film was measured at 25 points using an F50 automatic mapping film thickness measurement system (manufactured by FILMETRICS), and the film thickness uniformity was evaluated as 3σ. The smaller the value, the better the film thickness uniformity. If it is 35 or less, there is no problem in practical use.
The results are shown in Table 3 below.

[Pattern formation]
An organic antireflective film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was coated on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflective film. The resist composition (Res-1) prepared thereon is coated using a spin coater (CLEAN TRACK LITHIUS Pro manufactured by Tokyo Electron Ltd.) at a maximum rotation speed of 2000 rpm, and baked at 100 ° C. for 60 seconds, A 400 nm resist film was formed. The obtained wafer was subjected to pattern exposure using a KrF excimer laser scanner (manufactured by ASML, PAS 5500/850) (NA 0.75). Thereafter, the film was heated at 100 ° C. for 60 seconds, developed with butyl acetate for 60 seconds, rinsed with pure water for 30 seconds, and a good hole pattern having a pitch of 400 nm and a hole diameter of 200 nm was obtained.

As apparent from Table 3, when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used, it is understood that the film thickness uniformity of the obtained resist film is excellent.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application (Application No. 2017-167851) filed on Aug. 31, 2017, the contents of which are incorporated herein by reference.

Claims

(A) A repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), and a repeating unit represented by the following general formula (3),
A resin wherein the content of the repeating unit represented by the general formula (1) is in the range of 25 to 50 mol% with respect to all repeating units in the resin (A)
An actinic ray-sensitive or radiation-sensitive resin composition containing (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a solvent.

In the general formula (2), R 1 represents a hydrogen atom or a methyl group. R 2 and R 3 each independently represent a hydrocarbon group having 1 to 4 carbon atoms. However, R 2 and R 3 may be bonded to each other to form a ring having 3 to 8 carbon atoms. R 4 represents a polycyclic hydrocarbon group having 6 to 20 carbon atoms.
In the general formula (3), R 5 is a hydrogen atom or a methyl group. R 6 , R 7 and R 8 each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein in the repeating unit represented by the general formula (2), R 4 is an adamantyl group, a norbornyl group, or a bicyclooctyl group.
The actinic ray sensitivity according to claim 1 or 2, wherein the content of the repeating unit represented by the general formula (2) is 25 to 50 mol% with respect to all the repeating units in the resin (A). Radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, which is for KrF exposure.
An actinic ray-sensitive or actinic ray-sensitive resin composition obtained by applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 onto a substrate by a spin coating method at a maximum rotation number of 2500 rpm or less. Radiation sensitive resin film.
(A) forming a film with the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, (A) exposing the film, and (C) the exposure Forming a negative pattern using a developer containing an organic solvent to form a negative pattern.
The pattern formation method according to claim 6, wherein the developer is butyl acetate.
The manufacturing method of an electronic device containing the pattern formation method of Claim 6 or 7.