Compound, polymeric compound, resist composition, and method of forming resist pattern

Abstract

To provide means of improving the sensitivity and resolution of a resist composition.SOLUTION: Provided are compounds represented by the general formula 1 in the figure, polymeric compounds having a structural unit derived from the compounds, resist compositions containing the polymeric compounds, and methods of forming resist patterns by using the resist compositions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, a polymeric compound, a resist composition, and a method of forming a resist pattern. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid advances in the miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display devices. A common method for achieving this miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.

[0003] Resist materials are required to have lithography properties such as sensitivity to these exposure light sources, resolution capable of reproducing fine-sized patterns, etc. To satisfy these requirements, a chemically amplified resist composition containing a base component whose solubility in a developer changes with the action of acid and an acid generator component that generates acid upon exposure has been used.

[0004] Chemically amplified resist compositions generally use resins having multiple structural units in order to improve lithography properties, etc. Furthermore, in the formation of a resist pattern, the behavior of the acid generated from an acid generator component upon exposure is considered to be a factor that has a significant impact on the lithography properties.

[0005] As such chemically amplified resist compositions, for example, the resist compositions disclosed in Patent Documents 1 to 3 have been proposed. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2016 / 147357 [Patent Document 2] Special Publication No. 2017-500275 [Patent Document 3] Patent Publication No. 2021-076636 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the techniques described in the above patent documents have the problem of being insufficient in terms of sensitivity and resolution.

[0008] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a means for further improving the sensitivity and resolution of a resist composition. [Means for solving the problem]

[0009] The above-mentioned problems of the present invention can be solved by the following means: That is, the present invention is a compound represented by the following general formula 1.

[0010] [ka]

[0011] In the above general formula 1, X is a hydrogen atom or a methyl group; Y is a linear alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, an unsubstituted cycloalkylalkyl group having from 4 to 21 carbon atoms, a cycloalkylalkyl group having from 4 to 21 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, or an aryl group having from 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

[0012] Another embodiment of the present invention is a polymer compound having a structural unit derived from the compound represented by general formula 1 above.

[0013] Yet another embodiment of the present invention is a resist composition containing at least the above polymer compound and an organic solvent.

[0014] Yet another embodiment of the present invention is a method for forming a resist pattern, comprising the steps of forming a resist film on a substrate using the resist composition; exposing the resist film to light; and developing the exposed resist film to form a resist pattern. [Effects of the Invention]

[0015] According to the present invention, a means for further improving the sensitivity and resolution of a resist composition is provided. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the claims. The embodiments described in this specification can be combined in any way to form other embodiments. Unless otherwise specified, in this specification, operations and measurements of physical properties, etc. are performed under conditions of room temperature (20°C or higher and 25°C or lower) and a relative humidity of 40% RH or higher and 50% RH or lower.

[0017] In this specification, unless otherwise specified, the term "alkyl group" includes linear and branched monovalent saturated hydrocarbon groups. The term "cycloalkyl group" includes cyclic monovalent saturated hydrocarbon groups (alicyclic groups). The term "cycloalkylalkyl group" includes groups in which a hydrogen atom in an alkyl group is substituted with a cycloalkyl group. The term "aryl group" includes monovalent aromatic hydrocarbon groups.

[0018] In this specification, "(meth)acrylic" is a general term including acrylic and methacrylic, and means "at least one of acrylic and methacrylic." Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid."

[0019] In this specification, the term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer).

[0020] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, electron beams (EB), etc. As used herein, "light" refers to actinic rays or radiation.

[0021] Unless otherwise specified, "exposure" in this specification includes not only exposure to the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser (such as an ArF excimer laser), extreme ultraviolet light, X-rays, etc., but also drawing with particle beams such as electron beams and ion beams.

[0022] In this specification, some structures represented by chemical formulas may have asymmetric carbon atoms, and may exist as enantiomers or diastereomers. In such cases, a single chemical formula represents all isomers. These isomers may be used alone or as a mixture of two or more isomers.

[0023] [Compound] A first embodiment of the present invention is a compound represented by the following general formula 1.

[0024] [ka]

[0025] In the above general formula 1, X is a hydrogen atom or a methyl group; Y is a linear alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, an unsubstituted cycloalkylalkyl group having from 4 to 21 carbon atoms, a cycloalkylalkyl group having from 4 to 21 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, or an aryl group having from 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

[0026] The compound according to one embodiment of the present invention having such a structure can further improve the sensitivity and resolution of the resist composition.

[0027] The mechanism by which the compound according to this embodiment provides the above-described effects is believed to be as follows: However, the following mechanism is merely speculation, and the scope of the present invention is not limited thereto.

[0028] In conventional resist compositions containing a photoacid generator, the photoacid generator tends to partially aggregate, resulting in a decrease in the number of photosensitive sites (photosensitive points) and a tendency for these sites to become non-uniform. In contrast, the compound of the present invention represented by the above general formula 1 has a photoacid generating group in its molecule, and in the polymer compound obtained by polymerizing this compound, the photoacid generating groups that serve as photosensitive sites are dispersed almost uniformly. Therefore, the apparent number of photosensitive sites increases, the rate at which the solubility of the polymer compound contained in the exposed areas changes in the developer solution increases, and sensitivity is improved.

[0029] Furthermore, in conventional resist compositions (especially positive-tone) containing a photoacid generator, the photoacid generator contained in the unexposed portion has a low molecular weight, which increases the dissolution rate of the unexposed portion in a developer, making it difficult to differentiate it from the dissolution rate of the exposed portion in a developer. On the other hand, by using a polymer compound obtained by polymerizing a compound represented by the above general formula 1, the content of low-molecular-weight components in the resist composition can be reduced, thereby reducing the dissolution rate of the unexposed portion. Therefore, the difference between the dissolution rate of the exposed portion and the dissolution rate of the unexposed portion in a developer becomes larger (dissolution contrast increases), and resolution improves.

[0030] Examples of the linear alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom and the branched alkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, which are used for Y in the above general formula 1, include the following groups. That is, examples of such groups include a trifluoromethyl group (perfluoromethyl group), a difluoromethyl group, a pentafluoroethyl group (perfluoroethyl group), a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoropropyl group, an n-heptafluoropropyl group (perfluoropropyl group), a 2H-perfluoropropyl group, a 3,3,3-trifluoropropyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group (perfluoroisopropyl group), a nonafluoroisobutyl group (perfluoroisobutyl group), an n-nonafluorobutyl group (n-perfluorobutyl group), a 4H-n-perfluorobutyl group, a 2H-perfluoroisobutyl group, a tert-nonafluorobutyl group, an n-perfluoropentyl group, a 1H,1H,2H,2H-perfluoropentyl group, a perfluoroisopentyl group, an n-perfluorohexyl group, and a 1H,1H,2H,2H-perfluorohexyl group.

[0031] The unsubstituted cycloalkyl group having 3 to 20 carbon atoms used for Y in the above general formula 1 may be monocyclic or polycyclic. Specific examples of the unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a bicyclo[1.1.0]butyl group, a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.0]pentyl group, a bicyclo[3.1.0]hexyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.0]hexyl group, a bicyclo[2.2.1]heptyl group (norbornyl group), a bicyclo[3.1.1]heptyl group, a bicyclo[3.2.0 ... chloro[4.1.0]heptyl, bicyclo[2.2.2]octyl, bicyclo[3.2.1]octyl, bicyclo[3.3.0]octyl, bicyclo[4.1.1]octyl, bicyclo[4.2.0]octyl, bicyclo[5.1.0]octyl, bicyclo[3.2.2]nonyl, bicyclo[3.3.1]nonyl, bicyclo[4.2.1]nonyl, bicyclo[4.3.0]nonyl, bicyclo[5.1.1]nonyl, bicyclo[5.2.0]nonyl, bicyclo[6.1.0]nonyl, bicyclo[4.3.1]decyl, tricyclo[5.2.1.0]nonyl 2,6 ]decyl group, isobornyl group, adamantyl group, and androstanyl group.

[0032] The cycloalkyl group having 3 to 20 carbon atoms and at least one hydrogen atom of which is substituted with a fluorine atom and used for Y in the above general formula 1 may be monocyclic or polycyclic. Specific examples of such groups include a 1-fluorocyclopropyl group, a 2-fluorocyclopropyl group, a 2,2-difluorocyclopropyl group, a 2,3-difluorocyclopropyl group, a 2,2-difluorocyclobutyl group, a 3,3-difluorocyclobutyl group, a 2,2-difluorocyclopentyl group, a 3,3-difluorocyclopentyl group, a 3,3-difluorocyclohexyl group, a 4,4-difluorocyclohexyl group, a 4,4-difluorocycloheptyl group, and a 4,4-difluorocyclooctyl group.

[0033] The cycloalkyl group having 3 to 20 carbon atoms and at least one hydrogen atom of which is substituted with an oxygen atom, used for Y in the above general formula 1, may be monocyclic or polycyclic. Specific examples of such a group include a 1,4-epoxycyclohexyl group (7-oxabicyclo[2.2.1]heptan-2-yl group) and a 3,4-epoxycyclohexyl group.

[0034] The cycloalkyl group contained in the unsubstituted cycloalkylalkyl group having 4 to 21 carbon atoms and used for Y in the above general formula 1 may be monocyclic or polycyclic. Specific examples of such groups include a cyclopropylmethyl group, a 2-cyclopropylethyl group, a 1-cyclopropylethyl group, a 3-cyclopropylpropyl group, a 4-cyclopropylbutyl group, a 5-cyclopropylpentyl group, a 6-cyclopropylhexyl group, a 2-cyclopropyl-1-methylethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, a cyclodecylmethyl group, a norbornan-1-ylmethyl group, a norbornan-2-ylmethyl group, an adamantan-1-ylmethyl group, and an adamantan-2-ylmethyl group.

[0035] The cycloalkyl group contained in the cycloalkylalkyl group having 4 to 21 carbon atoms and at least one hydrogen atom substituted with an oxygen atom, which is used for Y in the above general formula 1, may be monocyclic or polycyclic. Specific examples of such groups include a 1,4-epoxycyclohexylmethyl group (7-oxabicyclo[2.2.1]heptan-2-ylmethyl group), a 3,4-epoxycyclohexylmethyl group, a 3,4-epoxycyclohexylethyl group, and a camphanyl group.

[0036] The aryl group having 6 to 18 carbon atoms and at least one hydrogen atom of which is substituted with a fluorine atom and used for Y in the above general formula 1 may be monocyclic or polycyclic. Specific examples of such groups include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,3-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a 2,3,4,5,6-pentafluorophenyl group, a 2-fluoronaphthyl group, a 3-fluoronaphthyl group, a 4-fluoronaphthyl group, a 2,3,4,5,6,7-hexafluoronaphthyl group, a 2,3,4,5,6,7,8-heptafluoronaphthyl group, a 1,3,4,5,6,7,8-heptafluoronaphthyl group, and a 4,4'-difluorobiphenyl group.

[0037] Preferred groups for Y in the above general formula 1 are a linear alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or an aryl group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Groups having a structure substituted with a fluorine atom are preferred from the viewpoints that the strength of the generated acid is increased, the rate of change in the solubility of the polymer compound in the developer is accelerated, and the sensitivity is further improved, and the solubility in organic solvents can be improved. In addition, cyclic groups are preferred from the viewpoints that the sterically bulky nature of the cyclic group suppresses the diffusibility of the generated acid and improves resolution. Considering the above points, more preferred groups as Y in the above general formula 1 are a linear alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a cycloalkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or an aryl group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

[0038] More specific examples of the compound represented by the above general formula 1 include compounds 1 to 26 shown below.

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] Among the compounds listed above, preferred are Compound 1, Compound 2, Compound 10, Compound 14, Compound 21, and Compound 26. Among these compounds, Compound 1, Compound 2, Compound 10, or Compound 14 is more preferred.

[0043] The synthesis method of the compound represented by the general formula 1 is not particularly limited. One example is a method in which N-hydroxynaphthalimide is reacted with a sulfonic acid halide to obtain a sulfonic acid ester derivative of the N-hydroxyimide compound, and then a (meth)acryloyloxy group is introduced into the naphthalene ring. A more specific synthesis method of the compound represented by the general formula 1 can be easily understood by those skilled in the art by referring to the examples described below.

[0044] [High molecular compound] A second embodiment of the present invention is a polymeric compound (A) (hereinafter also referred to simply as component (A)) that contains a structural unit derived from a compound represented by the above general formula 1. The structural unit derived from the compound represented by the above general formula 1 (hereinafter also referred to simply as structural unit (O)) has a photoacid-generating group, and therefore can further improve the sensitivity and resolution of the resist composition. The structural unit (O) in component (A) can be used either alone or in combination of two or more types.

[0045] The structural unit (O) is a divalent structural unit generated by cleavage of an ethylenically unsaturated double bond in the compound represented by the above general formula 1. In the structural unit (O), the structure other than the structure in which the ethylenically unsaturated double bond is cleaved is the same as the structure in the above general formula 1, and therefore a description thereof will be omitted here. The component (A) may have structural units other than the structural unit (O). Such other structural units will be described below.

[0046] <Structural Unit Having an Acid-Decomposable Group> The component (A) preferably has a structural unit (hereinafter simply referred to as structural unit (L)) containing an acid-decomposable group whose polarity increases under the action of an acid. The "acid-decomposable group" is a group having acid decomposability such that at least some of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.

[0047] Examples of acid-decomposable groups whose polarity increases under the action of an acid include groups that dissociate under the action of an acid to generate polar groups, such as carboxyl, hydroxyl, amino, and sulfo groups (-SO3H).

[0048] More specific examples of the acid-decomposable group include groups in which the above polar groups are protected with acid-dissociable groups (for example, groups in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).

[0049] The term "acid-dissociable group" refers to either (1) a group having acid dissociability such that the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group can be cleaved by the action of an acid, or (ii) a group in which a portion of the bond is cleaved by the action of an acid, and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group.

[0050] The acid-dissociable group constituting the acid-decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid-dissociable group. Therefore, when the acid-dissociable group dissociates due to the action of an acid, a polar group with higher polarity than the acid-dissociable group is generated, increasing the polarity. As a result, the polarity of the entire component (A) increases. The increase in polarity results in a relative change in solubility in the developer. When the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.

[0051] Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups for base resins used in chemically amplified resist compositions.

[0052] Specific examples of acid-dissociable groups that have been proposed for use in base resins for chemically amplified resist compositions include the following "acetal-type acid-dissociable groups," "tertiary alkyl ester-type acid-dissociable groups," and "tertiary alkyloxycarbonyl acid-dissociable groups."

[0053] (acetal type acid dissociable group) Among polar groups, examples of the acid-dissociable group that protects a carboxy group or a hydroxyl group include acid-dissociable groups represented by the following general formula (Lr-1) (hereinafter also referred to as "acetal-type acid-dissociable groups").

[0054] [ka]

[0055] In the above formula (Lr-1), Ra' 1 and Ra' 2 are each independently a hydrogen atom or an alkyl group, and Ra' 3 is a hydrocarbon group, and Ra' 3 Ra' 1 , Ra' 2 may be bonded to any one of the following to form a ring.

[0056] In the above formula (Lr-1), Ra' 1 and Ra' 2 At least one of these is preferably a hydrogen atom, and both are more preferably hydrogen atoms.

[0057] Ra' 1 or Ra' 2 When is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples thereof include linear and branched alkyl groups. More specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl groups.

[0058] In the above formula (Lr-1), Ra' 3 Examples of the hydrocarbon group include a linear or branched alkyl group, and a cyclic hydrocarbon group.

[0059] The linear alkyl group preferably has a carbon atom number of 1 to 5. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group.

[0060] The branched alkyl group preferably has 3 to 10 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.

[0061] Ra' 3 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0062] The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.

[0063] The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane is preferably one having from 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0064] Ra' 3 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0065] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0066] Ra' 3 Specific examples of the aromatic hydrocarbon group in include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring or aromatic heterocycle (aryl groups or heteroaryl groups); groups in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups in which one hydrogen atom of an aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl). The number of carbon atoms in the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 or more and 4 or less.

[0067] Ra' 3 The cyclic hydrocarbon group in may have a substituent. Examples of the substituent include -R P1 , -R P2 -OR P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN, or -R P2 -COOH (hereinafter these substituents are collectively referred to as "Ra x5 ") are also examples.

[0068] where RP1 is a chain saturated hydrocarbon group having 1 to 10 carbon atoms, an aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. P2 is a single bond, a chain saturated hydrocarbon group having 1 to 10 carbon atoms, an aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms. P1 and R P2 Some or all of the hydrogen atoms in the chain saturated hydrocarbon group, the alicyclic saturated hydrocarbon group, and the aromatic hydrocarbon group may be substituted with fluorine atoms. The alicyclic hydrocarbon group may have one or more of the above-mentioned substituents, or may have one or more of each of multiple types of the above-mentioned substituents.

[0069] Ra' 3 But Ra' 1 , Ra' 2 When the cyclic group is bonded to any one of the above to form a ring, the cyclic group is preferably a 4-, 5-, 6-, or 7-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

[0070] (Tertiary alkyl ester type acid-dissociable group) Among the polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (Lr-2).

[0071] Among the acid-dissociable groups represented by the following formula (Lr-2), those constituted by an alkyl group are hereinafter also referred to as "tertiary alkyl ester-type acid-dissociable groups" for convenience.

[0072] [ka]

[0073] In the above formula (Lr-2), Ra' 4 ~Ra' 6 are each independently a hydrocarbon group, and Ra'5 and Ra' 6 may be bonded to each other to form a ring.

[0074] Ra' 4 Examples of the hydrocarbon group include a linear or branched alkyl group, a linear or cyclic alkenyl group, and a cyclic hydrocarbon group.

[0075] Ra' 4 The linear or branched alkyl group and the cyclic hydrocarbon group (the monocyclic aliphatic hydrocarbon group, the polycyclic aliphatic hydrocarbon group, and the aromatic hydrocarbon group) in 3 The same can be mentioned.

[0076] Ra' 4 The chain or cyclic alkenyl group in the formula (I) is preferably an alkenyl group having from 2 to 10 carbon atoms.

[0077] Ra' 5 and Ra' 6 The hydrocarbon group of Ra' is 3 The same can be mentioned.

[0078] Ra' 5 and Ra' 6 When these are bonded to each other to form a ring, suitable examples thereof include a group represented by the following general formula (L-r2-1), a group represented by the following general formula (L-r2-2), and a group represented by the following general formula (L-r2-3).

[0079] On the other hand, Ra' 4 ~Ra' 6 When are not bonded to each other and are independent hydrocarbon groups, preferred examples include groups represented by the following general formula (L-r2-4).

[0080] [ka]

[0081] In the above general formula (L-r2-1), Ra' 10represents a linear or branched alkyl group having 1 to 12 carbon atoms, at least a portion of which may be substituted with a halogen atom or a heteroatom-containing group. 11 Ra' 10 represents a group that forms an aliphatic cyclic group together with the carbon atom to which it is bonded. In the above general formula (L-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted. Ra 101 ~Ra 103 are each independently a hydrogen atom, a saturated chain hydrocarbon group having 1 to 10 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in the saturated chain hydrocarbon group and the alicyclic hydrocarbon group may be substituted. 101 ~Ra 103 Two or more of these may be bonded to each other to form a cyclic structure. In the above general formula (L-r2-3), Yaa is a carbon atom. Xaa is a group that forms an alicyclic group together with Yaa. Ra 104 In the general formula (L-r2-4), Ra' is an aromatic hydrocarbon group which may have a substituent. 12 and Ra' 13 are each independently a chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted. 14 is a hydrocarbon group which may have a substituent. In addition, * represents a bond.

[0082] In the above general formula (L-r2-1), Ra' 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group.

[0083] Ra' 10 The linear alkyl group in Ra' has 1 to 12 carbon atoms. 10 In the formula (I), the branched alkyl group is the above-mentioned Ra' 3 The same can be mentioned.

[0084] Ra' 10 The alkyl group in may be partially substituted with a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Furthermore, some of the carbon atoms (e.g., methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group.

[0085] Examples of heteroatoms include oxygen, sulfur, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0086] In the above formula (L-r2-1), Ra' 11 (Ra' 10 The alicyclic group formed together with the carbon atom to which Ra' is bonded is 3 Among these, a monocyclic alicyclic hydrocarbon group is preferred, and specifically, a cyclopentyl group or a cyclohexyl group is more preferred, with a cyclopentyl group being even more preferred.

[0087] In the above formula (L-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya includes Ra' in the above formula (Lr-1). 3 Examples of such groups include groups in which one or more hydrogen atoms have been further removed from the monovalent alicyclic hydrocarbon group shown above.

[0088] The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. The substituent may be any of the above-mentioned Ra' 3 Examples of the substituents include the same as those that the cyclic hydrocarbon group in the above may have.

[0089] In the above formula (L-r2-2), Ra 101 ~Ra 103In the formula (I), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group.

[0090] Ra 101 ~Ra 103 In the formula, examples of the aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic alicyclic hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group. 101 ~Ra 103 Among these, from the viewpoint of ease of synthesis, a hydrogen atom or a chain saturated hydrocarbon group having 1 to 10 carbon atoms is preferred.

[0091] The above Ra 101 ~Ra 103 Examples of the substituents that the chain saturated hydrocarbon group or alicyclic hydrocarbon group represented by the formula: x5 The same groups as those shown below can be mentioned.

[0092] Ra 101 ~Ra 103 Examples of the group containing a carbon-carbon double bond formed by two or more of the above being bonded to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc. Among these, from the viewpoint of ease of synthesis, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.

[0093] In the above general formula (L-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is the same as Ra' in formula (Lr-1).3 The groups mentioned above as the aliphatic hydrocarbon group are preferably monocyclic or polycyclic groups.

[0094] In the above general formula (L-r2-3), Ra 104 The aromatic hydrocarbon group in the formula (I) may be a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. 104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene.

[0095] Ra in the above general formula (L-r2-3) 104 Examples of the substituent that may be possessed by include a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), and an alkyloxycarbonyl group.

[0096] In the above general formula (L-r2-4), Ra' 12 and Ra' 13 are each independently a chain saturated hydrocarbon group having 1 to 10 carbon atoms. 12 and Ra' 13 In the formula, the chain saturated hydrocarbon group having 1 to 10 carbon atoms includes the above-mentioned Ra 101 ~Ra 103 Examples include the same chain saturated hydrocarbon groups having 1 to 10 carbon atoms as those in the chain saturated hydrocarbon group. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted.

[0097] Ra' 12 and Ra' 13 Among these, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0098] The above Ra' 12 and Ra' 13When the chain saturated hydrocarbon group represented by the formula: is substituted, examples of the substituent include the above-mentioned Ra x5 The same groups as those shown below can be mentioned.

[0099] In the above general formula (L-r2-4), Ra' 14 Ra' is a hydrocarbon group which may have a substituent. 14 The hydrocarbon group in the formula (I) includes a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0100] Ra' 14 The linear alkyl group in the formula (I) preferably has a carbon atom number of 1 to 5. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group.

[0101] Ra' 14 The branched alkyl group in the formula (I) preferably has 3 to 10 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.

[0102] Ra' 14 When is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.

[0103] The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.

[0104] The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has from 7 to 12 carbon atoms. Specific examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0105] Ra' 14 As the aromatic hydrocarbon group in 104 Among them, the aromatic hydrocarbon groups Ra' are the same as those in 14 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene.

[0106] Ra' 14 Examples of the substituent that may be possessed by Ra include 104 Examples of the substituents include the same as those that may be possessed by the group.

[0107] Ra' in the above general formula (L-r2-4) 14 When is a naphthyl group, the position at which it is bonded to the tertiary carbon atom in the above formula (L-r2-4) may be either the 1st or 2nd position of the naphthyl group.

[0108] Ra' in the above general formula (L-r2-4) 14 When is an anthryl group, the position at which it is bonded to the tertiary carbon atom in the above formula (L-r2-4) may be any one of the 1st, 2nd, or 9th position of the anthryl group.

[0109] Specific examples of the group represented by the above general formula (L-r2-1) are listed below.

[0110] [ka]

[0111] [ka]

[0112] Specific examples of the group represented by the above general formula (L-r2-2) are listed below.

[0113] [ka]

[0114] [ka]

[0115] Specific examples of the group represented by the above general formula (L-r2-3) are listed below.

[0116] [ka]

[0117] Specific examples of the group represented by the above general formula (L-r2-4) are listed below.

[0118] [ka]

[0119] (Tertiary alkyloxycarbonyl acid dissociating group) Among the polar groups, examples of the acid-dissociable group that protects the hydroxyl group include acid-dissociable groups represented by the following general formula (Lr-3) (hereinafter, for convenience, also referred to as "tertiary alkyloxycarbonyl acid-dissociable group").

[0120] [ka]

[0121] In the above general formula (Lr-3), Ra' 7 ~Ra' 9 are each independently an alkyl group.

[0122] In the above general formula (Lr-3), Ra' 7 ~Ra' 9 are each independently preferably an alkyl group having 1 to 5 carbon atoms. The total number of carbon atoms in the alkyl groups is preferably 3 to 7.

[0123] Examples of the structural unit (L) include a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent; a structural unit derived from an acrylamide; a structural unit derived from hydroxystyrene or a hydroxystyrene derivative in which at least a portion of the hydrogen atoms in the hydroxyl groups are protected with a substituent containing the above-mentioned acid-decomposable group; and a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative in which at least a portion of the hydrogen atoms in -C(═O)-OH are protected with a substituent containing the above-mentioned acid-decomposable group.

[0124] Of the above, the structural unit (L) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent.

[0125] Preferred specific examples of such structural units (L) include structural units represented by the following general formula (L1-1) or (L1-2).

[0126] [ka]

[0127] In the above general formulas (L1-1) and (L1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. 1 is a hydrocarbon group which may have an ether bond. a1 is 0, 1, or 2. Ra 1 is an acid-dissociable group represented by the above general formula (Lr-1) or (Lr-2). 1 is n a2 + monovalent hydrocarbon group, n a2 is 1, 2, or 3, and Ra 2 is an acid-dissociable group represented by the above general formula (Lr-1) or (Lr-3).

[0128] In the above general formula (L1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferred.

[0129] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.

[0130] In the above general formula (L1-1), Va 1 The hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0131] Va 1 The aliphatic hydrocarbon group as the hydrocarbon group in may be saturated or unsaturated, and is usually preferably saturated.

[0132] More specifically, the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0133] As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, and specific examples include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], and a pentamethylene group [-(CH2)5-].

[0134] The branched aliphatic hydrocarbon group preferably has 3 or more and 10 or less carbon atoms, and more preferably has 3 or more and 6 or less carbon atoms.

[0135] The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include alkyl alkylene groups such as alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0136] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same as the straight-chain aliphatic hydrocarbon group or the branched-chain aliphatic hydrocarbon group.

[0137] The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specific examples of which include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0138] Va 1 The aromatic hydrocarbon group as the divalent hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring.

[0139] The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, but does not include the number of carbon atoms in the substituents.

[0140] Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0141] Specific examples of the aromatic hydrocarbon group include an arylene group (a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring); an aryl group (a group in which one hydrogen atom has been removed from an aromatic hydrocarbon ring) in which one hydrogen atom has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, or another group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.

[0142] In the above formula (L1-1), Ra 1 is an acid-dissociable group represented by the above formula (Lr-1) or (Lr-2).

[0143] In the above general formula (L1-2), Wa 1 n in a2 The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity and may be saturated or unsaturated, but is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in their structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in their structure.

[0144] Above n a2 The +1 valence is preferably from 2 to 4, more preferably 2 or 3.

[0145] In the above formula (L1-2), Ra 2 is an acid-dissociable group represented by the above general formula (Lr-1) or (Lr-3).

[0146] Specific examples of the structural unit represented by the general formula (L1-1) are shown below. αeach independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] The structural unit (L) contained in the component (A) may be used alone or in combination of two or more different types.

[0152] As the structural unit (L), a structural unit represented by the above formula (L1-1) is more preferred because it is more likely to further improve lithography properties (sensitivity, shape, etc.).

[0153] Among these, the structural unit (L) is particularly preferably one containing a structural unit represented by the following general formula (L1-1-1).

[0154] [ka]

[0155] In the above formula (L1-1-1), Ra 1” is an acid-dissociable group represented by the above general formula (L1-r2-1), (L1-r2-3) or (L1-r2-4).

[0156] In the above formula (L1-1-1), R and Va 1 , and n a1represents R, Va in the above general formula (L-1). 1 , and n a1 is the same as:

[0157] The acid-dissociable group represented by general formula (L1-r2-1), (L1-r2-3), or (L1-r2-4) has been described above. Among these, it is preferable to select an acid-dissociable group that is a cyclic group, since this is suitable for enhancing reactivity.

[0158] In the above general formula (L1-1-1), Ra 1” Among the above, is preferably an acid-dissociable group represented by general formula (L1-r2-1).

[0159] Component (A) may further contain a structural unit derived from a polymerizable compound having an ether bond. Examples of polymerizable compounds having an ether bond include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond. Specific examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. These polymerizable compounds having an ether bond may be used alone or in combination of two or more.

[0160] Furthermore, the polymer compound (A) may contain structural units derived from other polymerizable compounds in order to appropriately control the physical and chemical properties, including (1) solubility in a coating solvent, (2) film-forming property (glass transition temperature), (3) alkaline developability, (4) film loss (hydrophilicity / hydrophobicity, alkali-soluble group selection), (5) adhesion of unexposed areas to the substrate, and (6) etching resistance.

[0161] Such other polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds.

[0162] Specific examples of the other polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acrylic acid hydroxy esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Examples of suitable polymerizable compounds include alkyl esters, aryl (meth)acrylate esters such as phenyl (meth)acrylate and benzyl (meth)acrylate, dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate, vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene, vinyl group-containing aliphatic compounds such as vinyl acetate, conjugated diolefins such as butadiene and isoprene, nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile, chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride, and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide. These other polymerizable compounds may be used alone or in combination of two or more.

[0163] Component (A) may contain a structural unit (P) that contains an acid-non-dissociable alicyclic group. The presence of the structural unit (P) in component (A) improves the etching resistance of the formed resist pattern. It also enhances the hydrophobicity of component (A). The improved hydrophobicity contributes to improvements in resolution, resist pattern shape, and the like, particularly in solvent development processes.

[0164] The “acid-non-dissociable alicyclic group” in the structural unit (P) is an alicyclic group that, when acid is generated in the resist composition upon exposure (for example, when acid is generated from a structural unit that generates acid upon exposure or from the component (B)), does not dissociate even when acted upon by the acid, and remains as is in the structural unit.

[0165] The structural unit (P) is preferably a structural unit derived from an acrylate ester containing an acid-non-dissociable alicyclic group, and the alicyclic group may be any of a number of groups conventionally known to be used in resin components of resist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers), etc.

[0166] The alicyclic group is preferably at least one selected from the group consisting of a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group, in view of industrial availability, etc. These polycyclic groups may have a linear or branched alkyl group having from 1 to 5 carbon atoms as a substituent.

[0167] The structural unit (P) contained in the component (A) may be used either individually or in combination of two or more different types.

[0168] The content of the structural unit (O) in component (A) is not particularly limited, but is preferably 0.1 mol % to 30 mol % (based on 100 mol % of the total of all structural units in component (A)), more preferably 0.5 mol % to 20 mol % (based on 100 mol %), and even more preferably 1 mol % to 10 mol % (based on 100 mol %). When the content of the structural unit (O) falls within this range, the amount of catalytic acid generated is sufficient, further improving sensitivity. Furthermore, sufficient light transmission for exposure is achieved, resulting in excellent resolution and pattern formability.

[0169] Furthermore, the content of the structural unit (L) (structural unit having an acid-decomposable group) in the component (A) is more preferably from 20 mol % to 80 mol % inclusive, even more preferably from 25 mol % to 75 mol % inclusive, and even more preferably from 30 mol % to 70 mol % inclusive, with the total of all structural units in the component (A) being 100 mol %.

[0170] The content (molar ratio) of each structural unit contained in component (A) is, for example, 13 It can be calculated by analysis using C-NMR.

[0171] The weight-average molecular weight (Mw) of component (A) is not particularly limited, but is preferably from 1,000 to 500,000, and more preferably from 3,000 to 100,000. Within this range, etching resistance is improved, and the difference in dissolution rate before and after exposure can be ensured, ensuring resolution. The dispersity (weight-average molecular weight / number-average molecular weight, Mw / Mn) of component (A) is not particularly limited, but is preferably from 1.0 to 5.0, and more preferably from 1.0 to 3.0. The weight-average molecular weight and dispersity can be measured by gel permeation chromatography (GPC) in polystyrene equivalent, more specifically, by the method described in the Examples.

[0172] The component (A) of the present invention can be produced by copolymerizing the compound represented by the above general formula (1) with, as needed, a polymerizable compound into which the structural unit (L) can be introduced or another polymerizable compound. Various examples of the copolymerization reaction include radical polymerization, anionic polymerization, and coordination polymerization.

[0173] The reaction conditions for the radical polymerization reaction are, for example, as follows: (A) Using a hydrocarbon such as benzene, an ether such as tetrahydrofuran, an alcohol such as ethanol, or a ketone such as methyl ethyl ketone as a solvent, (a) Using an azo compound such as 2,2'-azobisisobutyronitrile or dimethyl-2,2'-azobis(2-methylpropionate), or a peroxide such as benzoyl peroxide or lauroyl peroxide as a polymerization initiator, (c) Keep the reaction temperature between 0°C and 100°C. (D) The reaction time is set to approximately 0.5 hours or more and 48 hours or less. However, cases outside these ranges are not excluded.

[0174] The reaction conditions for the anionic polymerization reaction are, for example, as follows: (A) Using hydrocarbons such as benzene, ethers such as tetrahydrofuran, or liquid ammonia as a solvent, (a) A metal such as sodium or potassium, an alkyl metal such as n-butyllithium or sec-butyllithium, a ketyl, or a Grignard reaction agent is used as a polymerization initiator. (c) Keep the reaction temperature between -78°C and 0°C. (D) The reaction time is set to approximately 0.5 hours or more and 48 hours or less. (E) Use proton-donating compounds such as methanol, halides such as methyl iodide, or other electrophilic substances as terminating agents. However, cases outside these ranges are not excluded.

[0175] The reaction conditions for coordination polymerization are, for example, (A) Use hydrocarbons such as n-heptane and toluene as solvents. (a) As a catalyst, a Ziegler-Natta catalyst consisting of a transition metal such as titanium and alkylaluminum, a Phillips catalyst in which chromium and nickel compounds are supported on a metal oxide, or an olefin metathesis mixed catalyst represented by a tungsten and rhenium mixed catalyst is used. (c) Keep the reaction temperature between 0°C and 100°C. (D) The reaction time is set to approximately 0.5 hours or more and 48 hours or less. However, cases outside these ranges are not excluded.

[0176] Furthermore, a polymeric compound in which some or all of the acid-dissociable groups of the component (A) produced by the above polymerization method have been deprotected can also be used in a negative resist composition. Furthermore, acid-dissociable groups can be reintroduced into a polymeric compound in which the acid-dissociable groups have been deprotected, thereby introducing substituents different from the acid-dissociable groups introduced during polymerization.

[0177] [Resist composition] A third embodiment of the present invention is a resist composition containing at least the polymeric compound (A) of the second embodiment and an organic solvent (E) (hereinafter, also referred to simply as "component (E)"). As described above, the polymeric compound (A) has a structural unit derived from the compound represented by general formula 1 above, and has a structural unit having a photoacid-generating group that generates acid upon irradiation with actinic rays or radiation. The resist composition of this embodiment, which contains such a polymeric compound (A), exhibits improved sensitivity and resolution.

[0178] When a resist film is formed using the resist composition of this embodiment and then subjected to selective exposure, acid is generated in the exposed areas of the resist film, and the solubility of component (A) in a developer changes due to the action of the acid, whereas the solubility of component (A) in a developer does not change in the unexposed areas of the resist film, resulting in a difference in solubility in a developer between the exposed and unexposed areas of the resist film. Therefore, when the resist film is developed, if the resist composition is positive, the exposed areas of the resist film are dissolved and removed, forming a positive resist pattern, whereas if the resist composition is negative, the unexposed areas of the resist film are dissolved and removed, forming a negative resist pattern.

[0179] In this specification, a resist composition that dissolves and removes exposed portions of a resist film to form a positive resist pattern is also referred to as a positive resist composition, and a resist composition that dissolves and removes unexposed portions of a resist film to form a negative resist pattern is also referred to as a negative resist composition. The resist composition of this embodiment may be a positive resist composition or a negative resist composition. Furthermore, the resist composition of this embodiment may be for use in an alkaline development process in which an alkaline developer is used for the development treatment during resist pattern formation, or may be for use in a solvent development process in which a developer containing an organic solvent (organic developer) is used for the development treatment.

[0180] When the resist composition of this embodiment is a positive resist composition, the composition comprises: High molecular compound (A), organic solvent (E), and, if necessary, Acid generator (photosensitizer) (B), Acid diffusion inhibitor (C), Adhesion improver (D), Preferably, it contains:

[0181] When the resist composition of this embodiment is a negative resist composition, the composition comprises: High molecular compound (A), organic solvent (E), and, if necessary, Acid generator (photosensitizer) (B), Acid diffusion inhibitor (C), Adhesion improver (D) Crosslinker (F) Preferably, it contains:

[0182] Components (B) to (F) and other additives will be described below.

[0183] <Organic solvent (E)> The resist composition of this embodiment contains an organic solvent (E) (also referred to simply as component (E) in this specification).

[0184] The component (E) used in the present invention may be any organic solvent capable of dissolving the component (A) and other additives. Examples of such organic solvents include ketones such as cyclohexanone and methyl 2-n-amyl ketone, alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether, esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate, and lactones such as γ-butyrolactone. These components (E) can be used singly or in combination of two or more. Among these components (E), at least one selected from the group consisting of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is preferred.

[0185] The amount of the component (E) used is preferably from 70 to 3,000 parts by mass, and more preferably from 100 to 2,500 parts by mass, per 100 parts by mass of the component (A). When the resist composition contains two or more types of component (E), the above content of the component (E) refers to the combined amount of all of these.

[0186] <Acid generator (photosensitizer) (B)> The component (A) included in the resist composition of this embodiment has a photoacid-generating group in the molecule. In addition to this component (A), the resist composition of this embodiment may further include an acid generator (photosensitizer) (B) (hereinafter also simply referred to as component (B)). There are no particular restrictions on the acid generator, as long as it is a compound that generates acid upon irradiation with light (such as actinic rays). The component (B) can be used alone or in combination of two or more types.

[0187] Examples of component (B) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, etc. From the viewpoint of availability, component (B) preferably contains at least one selected from the group consisting of onium salt compounds and sulfonimide compounds.

[0188] Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Examples of onium salt compounds include diaryliodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tris(pentafluoroethyl)trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, and diphenyliodonium tris[(trifluoromethyl)sulfonyl]methanide; and triarylsulfonium salts. As the onium salt compound, sulfonium salts are preferred from the viewpoint of further improving sensitivity and thermal stability. As the sulfonium salt, triarylsulfonium salts are preferred from the viewpoint of further improving thermal stability.

[0189] Examples of triarylsulfonium salts include sulfonium salts having at least one cation selected from the group consisting of cations represented by the following general formula (b1), cations represented by the following general formula (b2), cations represented by the following general formula (b3), and cations represented by the following general formula (b4), and an anion having at least one skeleton selected from the group consisting of a tetraphenylborate skeleton, an alkylsulfonate skeleton having from 1 to 20 carbon atoms, a phenylsulfonate skeleton, a 10-camphorsulfonate skeleton, a trisalkylsulfonylmethanide skeleton having from 1 to 20 carbon atoms, a tetrafluoroborate skeleton, a hexafluoroantimonate skeleton, and a hexafluorophosphate skeleton.

[0190] [ka]

[0191] The hydrogen atoms of the phenyl groups in the above general formulae (b1), (b2), (b3), and (b4) may be substituted with a hydroxy group, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an alkylcarbonyl group having from 2 to 12 carbon atoms, or an alkoxycarbonyl group having from 2 to 12 carbon atoms. When there are multiple substituents, they may be the same or different.

[0192] The hydrogen atoms of the phenyl groups in the tetraphenylborate skeleton may be substituted with fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups having from 1 to 12 carbon atoms, alkoxy groups having from 1 to 12 carbon atoms, alkylcarbonyl groups having from 2 to 12 carbon atoms, or alkoxycarbonyl groups having from 2 to 12 carbon atoms. When there are multiple substituents, they may be the same or different.

[0193] The hydrogen atoms of the alkylsulfonate skeleton may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, or an alkoxycarbonyl group. When there are multiple substituents, they may be the same or different.

[0194] The hydrogen atoms of the phenyl group of the phenylsulfonate skeleton may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an alkylcarbonyl group having from 2 to 12 carbon atoms, or an alkoxycarbonyl group having from 2 to 12 carbon atoms. When there are multiple substituents, they may be the same or different.

[0195] The hydrogen atoms of the trisalkylsulfonylmethane skeleton may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, or an alkoxycarbonyl group. When there are multiple substituents, they may be the same or different.

[0196] The fluorine atoms in the hexafluorophosphate skeleton may be substituted with hydrogen atoms, alkyl groups having from 1 to 12 carbon atoms, or perfluoroalkyl groups having from 1 to 12 carbon atoms. When there are multiple substituents, they may be the same or different.

[0197] The sulfonium salt used as component (B) is preferably a compound having at least one cation selected from the group consisting of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, (2-methyl)phenyl[4-(4-biphenylylthio)phenyl]4-biphenylylsulfonium, [4-(4-biphenylylthio)-3-methylphenyl]4-biphenylylphenylsulfonium, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium, and tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium.

[0198] The sulfonium salt used as component (B) is preferably a compound having, as an anion, at least one anion selected from the group consisting of trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris[(trifluoromethyl)sulfonyl]methanide, 10-camphorsulfonate, tris(pentafluoroethyl)trifluorophosphate, and tetrakis(pentafluorophenyl)borate.

[0199] Specific examples of sulfonium salts include [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium trifluoromethanesulfonate, (2-ethoxy)phenyl[4-(4-biphenylylthio)-3-ethoxyphenyl]4-biphenylylsulfonium nonafluorobutanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0200] Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(p-toluenesulfonyloxy)-1,8-naphthalimide, and N-(10-camphorsulfonyloxy)-1,8-naphthalimide.

[0201] The amount of component (B) is not particularly limited, but is preferably from 0.1 to 15 parts by mass, more preferably from 0.3 to 10 parts by mass, and even more preferably from 0.5 to 5 parts by mass, per 100 parts by mass of component (A). When the resist composition contains two or more types of component (B), the above-mentioned amount of component (B) refers to the combined total amount of these.

[0202] <Acid diffusion inhibitor (C)> The resist composition of the present invention preferably contains an acid diffusion inhibitor (quencher) (C) (hereinafter simply referred to as component (C)). The term "acid diffusion inhibitor" is a term commonly used in this technical field and refers to a compound that can suppress the diffusion rate of acids generated in the system when they diffuse into the resist film. The incorporation of the acid diffusion inhibitor (C) not only facilitates adjustment of resist sensitivity, but also suppresses the diffusion rate of acids in the resist film, thereby improving resolution. Furthermore, the acid diffusion inhibitor (C) can play a role in improving exposure margins, pattern profiles, etc. by suppressing changes in sensitivity after exposure and reducing substrate and environmental dependencies.

[0203] Examples of such component (C) include primary, secondary, or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, ammonium salts, etc. Component (C) can be used either alone or in combination of two or more.

[0204] Aliphatic amines are amines having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms. Examples of aliphatic amines include amines in which at least one hydrogen atom of ammonia (NH3) has been substituted with an alkyl group or hydroxyalkyl group having 1 to 12 carbon atoms (alkylamines or alkyl alcohol amines), and alicyclic amines.

[0205] Specific examples of alkylamines and alkyl alcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines having an alkyl group having from 2 to 10 carbon atoms are more preferred, and triethylamine is particularly preferred.

[0206] Examples of alicyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. The heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines).

[0207] Examples of the aliphatic monocyclic amine include piperidine and piperazine.

[0208] The aliphatic polycyclic amine is preferably one having 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0209] Examples of other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, and triethanolamine triacetate.

[0210] Examples of aromatic amines include triphenylamine.

[0211] Examples of heterocyclic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, and the like.

[0212] Furthermore, the compounds described in paragraphs

[0146] to

[0163] of JP-A No. 2008-111103 can also be used as the component (C).

[0213] When the resist composition contains component (C), there are no particular restrictions on the amount of component (C) in the resist composition, but it is preferably from 0.01 to 5 parts by mass per 100 parts by mass of component (A). By ensuring that the amount of component (C) falls within the above range, the resist pattern shape, deposition stability, and other properties are improved. When the resist composition contains two or more types of component (C), the above content refers to the combined amount of all of these.

[0214] <Adhesion improver (D)> The resist composition of the present invention preferably contains an adhesion improver (D) (hereinafter also referred to simply as component (D)).

[0215] The adhesion improver (D) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to metals, etc. used in substrates or wiring, etc. By preventing metal corrosion, it exhibits a rust-preventing effect. In addition to these effects, it can also improve adhesion between the substrate or metal, etc. and the resist composition.

[0216] Examples of component (D) include sulfur-containing compounds, aromatic hydroxy compounds, benzotriazole-based compounds, triazine-based compounds, and silicon-containing compounds. Component (D) can be used singly or in combination of two or more.

[0217] The sulfur-containing compound may be, for example, a compound having a sulfide bond and / or a mercapto group. The sulfur-containing compound may be a chain compound or a compound having a cyclic structure.

[0218] Examples of chain compounds include dithiodiglycerol [S(CH2CH(OH)CH2(OH))2], bis(2,3-dihydroxypropylthio)ethylene [CH2CH2(SCH2CH(OH)CH2(OH))2], sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], sodium 3-mercapto-1-propanesulfonate [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioglycolic acid [HSCH2CO2H], and 3-mercapto-1-propanol [HSCH2CH2CH2].

[0219] The sulfur-containing compound is preferably a compound having a sulfide bond and a mercapto group, and more preferably a heterocyclic compound having a sulfide bond and a mercapto group. The number of sulfide bonds and mercapto groups in the sulfur-containing compound is not particularly limited, as long as each is 1 or more.

[0220] The heterocycle may be either a monocycle or a polycycle, and may be either a saturated or unsaturated ring. The heterocycle preferably further contains a heteroatom other than a sulfur atom. Examples of the heteroatom include an oxygen atom and a nitrogen atom, and preferably a nitrogen atom.

[0221] The heterocycle is preferably a heterocycle having 2 to 12 carbon atoms, more preferably a heterocycle having 2 to 6 carbon atoms. The heterocycle is preferably a monocycle. The heterocycle is preferably an unsaturated ring. The heterocycle is more preferably an unsaturated monocycle.

[0222] Examples of the heterocycle include the heterocycles shown below.

[0223] [ka]

[0224] The sulfur-containing compound may be a polymer. The polymer preferably contains a structural unit having a sulfide bond and a mercapto group in a side chain. The structure having the sulfide bond and the mercapto group is preferably bonded to the main chain via a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond.

[0225] The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, it may contain the above-mentioned structural units having an acid-dissociable group and structural units not having an acid-dissociable group.

[0226] The weight-average molecular weight of the polymer is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50,000 or less. When the sulfur-containing compound is a polymer, the content of structural units having a sulfide bond and a mercapto group is usually 0.1 mol % or more and 50 mol % or less, preferably 0.5 mol % or more and 30 mol % or less, based on the total structural units of the polymer of the sulfur-containing compound.

[0227] Specific examples of the sulfur-containing compound include the compounds shown below.

[0228] [ka]

[0229] The sulfur-containing compound may be synthesized by a known method (for example, the method described in JP-A-2010-79081) or may be a commercially available product. The polymer containing the sulfur-containing compound may be synthesized by a known method (for example, the method described in JP-A-2001-75277) or may be a commercially available product.

[0230] Examples of the aromatic hydroxy compound include phenol, cresol, xylenol, pyrocatechol (=1,2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and gallic acid.

[0231] Examples of the benzotriazole-based compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-methylbenzotriazole, 5-benzotriazolecarboxylic acid, 1-methoxybenzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 1-methyl ... Examples thereof include azoles, or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethane, and 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane, which are commercially available from BASF as the "Irgamet (registered trademark)" series.

[0232] Examples of the triazine compounds include 1,3,5-triazine-2,4,6-trithiol.

[0233] Examples of the silicon-containing compound include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

[0234] When the resist composition contains component (D), there are no particular limitations on the amount of component (D) in the resist composition, but it is preferably at least 0.001 part by weight, more preferably at least 0.002 part by weight, and even more preferably at least 0.005 part by weight, per 100 parts by weight of component (A). Furthermore, the amount of component (D) in the resist composition is preferably no more than 10 parts by weight, more preferably no more than 3 parts by weight, and even more preferably no more than 1 part by weight, per 100 parts by weight of component (A). That is, the amount of component (D) in the resist composition is preferably at least 0.001 part by weight and no more than 10 parts by weight, more preferably at least 0.002 parts by weight and no more than 3 parts by weight, and even more preferably at least 0.005 parts by weight and no more than 1 part by weight, per 100 parts by weight of component (A). By ensuring the amount of component (D) in this range, a resist composition can be obtained that is capable of forming a highly accurate resist pattern and also ensures good adhesion between the resist pattern and the substrate. When the resist composition contains two or more types of component (D), the above content refers to the combined amount of all of these components.

[0235] <Crosslinking agent (F)> When the resist composition of this embodiment is a negative resist, the inclusion of a crosslinking agent (F) (hereinafter simply referred to as component (F)) reduces the dissolution rate of the exposed area, enabling a negative pattern to be obtained. Examples of such crosslinking agents include epoxy compounds, melamine compounds, guanamine compounds, glycoluril compounds, or urea compounds substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups, as well as compounds containing double bonds such as isocyanate compounds, azide compounds, and alkenyloxy groups. Hydroxy-containing compounds can also be used as crosslinking agents. The component (F) can be used alone or in combination.

[0236] Examples of the epoxy compound include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.

[0237] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound of hexamethylol melamine in which one to six methylol groups are methoxymethylated, or a mixture thereof; hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound of hexamethylol melamine in which one to six methylol groups are acyloxymethylated, or a mixture thereof.

[0238] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound of tetramethylolguanamine in which one to four methylol groups are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound of tetramethylolguanamine in which one to four methylol groups are acyloxymethylated, or a mixture thereof; and the like.

[0239] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril have been methoxymethylated, or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluril have been acyloxymethylated, or mixtures thereof, etc. Examples of urea compounds include tetramethylol urea, tetramethoxymethyl urea, compounds in which one to four methylol groups of tetramethylol urea have been methoxymethylated, or mixtures thereof, tetramethoxyethyl urea, etc.

[0240] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0241] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0242] Examples of compounds containing an alkenyloxy group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0243] When the resist composition of this embodiment is negative and contains the component (F), there are no particular restrictions on the amount of the component (F), but it is preferably from 0.1 to 50 parts by mass, and more preferably from 1 to 40 parts by mass, per 100 parts by mass of the component (A). Note that when the resist composition contains two or more types of component (F), the above content refers to the combined amount of all of these.

[0244] <Other additives> In addition to the components described above, the resist composition of this embodiment may contain other additives, such as surfactants, dissolution inhibitors, acidic compounds, stabilizers, photosensitizers, dyes, etc. The amounts of these other additives added may be normal amounts as long as they do not impair the effects of the present invention.

[0245] <Method for preparing resist composition> The resist composition according to this embodiment is prepared by mixing and stirring the above components by a conventional method. When mixing and stirring the above components, a device such as a dissolver, homogenizer, or triple-roll mill may be used. After the above components are mixed uniformly, the resulting mixture may be further filtered using a mesh, membrane filter, or the like.

[0246] [Method for forming resist pattern] Known lithography techniques can be applied to the method for forming a resist pattern according to the fourth embodiment of the present invention. For example, the method for forming a resist pattern may include the steps of forming a resist film on a substrate using the resist composition according to the third embodiment of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.

[0247] First, the resist composition according to the present invention is applied onto a substrate. Examples of the substrate include substrates for manufacturing integrated circuits (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, and substrates made of metals such as copper, chromium, iron, and aluminum), and substrates on which a predetermined wiring pattern has been formed. Examples of materials that can be used for the wiring pattern include copper, aluminum, nickel, and gold.

[0248] Examples of coating methods include spin coating, roll coating, flow coating, dip coating, spray coating, and doctor coating. The coating thickness is, for example, in the range of 0.01 μm to 2 μm. This is then pre-baked (post-applied bake (PAB)) on a hot plate, preferably at a temperature of 60° C. to 150° C. for a time of preferably 10 seconds to 30 minutes, more preferably at a temperature of 80° C. to 120° C. for a time of preferably 30 seconds to 20 minutes, to form a resist film.

[0249] Next, the resist film is exposed to light. Examples of light used for exposure include high-energy rays such as ultraviolet rays, far ultraviolet rays, electron beams (EB), extreme ultraviolet rays (EUV) with a wavelength of 3 nm to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation are used as high-energy rays, the exposure dose is preferably 1 mJ / cm, either directly or using a mask for forming a desired pattern. 2 More than 700mJ / cm 2 less than about 10 mJ / cm 2 More than 600mJ / cm 2 When EB is used as the high energy beam, the exposure dose is preferably 0.1 μC / cm 2 More than 300μC / cm 2 less than about 0.5 μC / cm 2 More than 200μC / cm 2 The pattern is written directly or using a mask to form the desired pattern.

[0250] In this embodiment, the exposure method for the resist film may be immersion exposure. Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure apparatus is filled in advance with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in this state. The immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of the immersion medium include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent. Water is preferably used as the immersion medium.

[0251] After exposure, the film may or may not be baked (post-exposure bake (PEB)) on a hot plate or in an oven, preferably at a temperature of 30°C or higher and 150°C or lower, for a time of preferably 10 seconds or higher and 30 minutes or lower, more preferably at a temperature of 50°C or higher and 120°C or lower, more preferably for a time of 30 seconds or higher and 20 minutes.

[0252] After exposure or PEB, the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.

[0253] Examples of the alkaline developer include aqueous alkaline solutions of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc., preferably having a concentration of 0.1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 5% by mass or less.

[0254] The organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any solvent capable of dissolving component (A) (component (A) before exposure), and may be appropriately selected from known organic solvents. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more.

[0255] Ketone-based solvents are organic solvents that contain CC(=O)-C in their structure. Ester-based solvents are organic solvents that contain CC(=O)-OC in their structure. Alcohol-based solvents are organic solvents that contain an alcoholic hydroxyl group in their structure. "Alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile-based solvents are organic solvents that contain a nitrile group in their structure. Amide-based solvents are organic solvents that contain an amide group in their structure. Ether-based solvents are organic solvents that contain COC in their structure.

[0256] Some organic solvents contain multiple types of functional groups that characterize the above-mentioned solvents in their structure, and in such cases, the term "organic solvent" refers to any solvent type containing the functional groups possessed by the organic solvent. For example, diethylene glycol monomethyl ether is considered to be both an alcohol-based solvent and an ether-based solvent in the above classification.

[0257] The hydrocarbon solvent is a hydrocarbon solvent that is composed of a hydrocarbon that may be halogenated and has no substituents other than halogen atoms, and the halogen atoms are preferably fluorine atoms.

[0258] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methyl amyl ketone (2-heptanone).

[0259] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl ether ...2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl ether acetate, 2-ethoxybutyl butyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate propyl, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like.

[0260] Examples of nitrile solvents include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

[0261] Known additives can be blended into the organic developer as needed. Examples of such additives include surfactants. The surfactant is not particularly limited, but examples include ionic and nonionic fluorine-based and / or silicon-based surfactants. When a surfactant is blended, the blending amount is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.005% by mass or more and 2% by mass or less, based on the total amount of the organic developer.

[0262] The development process can be carried out by a known development method, such as a method of immersing a substrate in a developer for a certain period of time (dip method), a method of piling up developer on the surface of the substrate by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying developer onto the surface of the substrate (spray method), or a method of continuously applying developer while scanning a developer application nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).

[0263] In the case of a positive resist material, the irradiated portion dissolves in the developer, while the unexposed portion remains insoluble, forming the desired positive pattern on the substrate. In the case of a negative resist material, the opposite is true: the irradiated portion becomes insoluble in the developer, while the unexposed portion dissolves. The development time is not particularly limited, but is, for example, between 3 seconds and 3 minutes.

[0264] After the development process, a rinse process is preferably carried out. In the case of an alkaline development process, the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse solution containing an organic solvent is preferably used.

[0265] In the case of a solvent development process, after the development treatment or rinsing treatment, a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed using a supercritical fluid.

[0266] The organic solvent contained in the rinse solution used in the rinsing treatment after development in the solvent development process can be selected appropriately from the organic solvents listed as organic solvents used in organic developers, so long as the resist pattern is not easily dissolved in the organic solvent. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used.

[0267] After the development is completed, rinsing is performed. A solvent that is miscible with the developer but does not dissolve the resist film is preferred as the rinsing solution. Preferred examples of such solvents include alcohol compounds having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents having 6 to 12 carbon atoms.

[0268] Examples of alcohols having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, and 3-hexanol. alcohol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.

[0269] Examples of ether compounds having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, and di-n-hexyl ether.

[0270] Examples of alkanes having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Examples of alkenes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Examples of alkynes having 6 to 12 carbon atoms include hexyne, heptine, and octyne.

[0271] Examples of aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0272] These organic solvents may be used alone or in combination of two or more. They may also be used in combination with other organic solvents or water. However, taking into consideration the development characteristics, the amount of water in the rinse solution is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the rinse solution.

[0273] If necessary, known additives can be added to the rinse solution. Examples of such additives include surfactants. When a surfactant is added, the amount of the surfactant added is preferably 0.001% by mass or more and 5% by mass or less, and more preferably 0.005% by mass or more and 2% by mass or less, based on the total amount of the rinse solution.

[0274] The rinse treatment (cleaning treatment) using a rinse solution can be carried out by a known rinse method. Examples of the rinse treatment method include a method in which the rinse solution is continuously applied onto a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the substrate surface (spray method). Rinsing can reduce the collapse of the resist pattern and the occurrence of defects. Furthermore, rinsing is not necessarily required, and the amount of solvent used can be reduced by not performing rinsing.

[0275] Although the embodiments of the present invention have been described in detail, it is clear that this is by way of illustration and example only and not of limitation, and that the scope of the present invention should be interpreted by the appended claims.

[0276] The present invention encompasses the following aspects and configurations: 1. A compound represented by the following general formula 1:

[0277] [ka]

[0278] In the general formula 1, X is a hydrogen atom or a methyl group; Y is a linear alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, an unsubstituted cycloalkylalkyl group having from 4 to 21 carbon atoms, a cycloalkylalkyl group having from 4 to 21 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, or an aryl group having from 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom: 2. The compound according to 1 above, wherein Y in the general formula 1 is a linear alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or an aryl group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom: 3. A polymeric compound having a structural unit derived from the compound described in 1. or 2. above: 4. The polymer compound according to 3 above, further having a structural unit having an acid-decomposable group: 5. The polymer compound according to 3. or 4. above, wherein the content of the structural unit derived from the compound represented by General Formula 1 in the polymer compound is 0.1 mol % or more and 30 mol % or less, with the total of all structural units in the polymer compound being 100 mol %: 6. A resist composition comprising at least the polymer compound according to any one of 3. to 5. above and an organic solvent: 7. The resist composition according to 6 above, further comprising an acid diffusion inhibitor: 8. A method for forming a resist pattern, comprising the steps of forming a resist film on a substrate using the resist composition according to 6. or 7. above, exposing the resist film to light, and developing the exposed resist film to form a resist pattern. [Example]

[0279] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited to the following examples. The weight average molecular weight and dispersity of the polymer compound were measured by the following methods: <Measurement of weight average molecular weight and dispersity> Measurement was carried out using gel permeation chromatography (GPC) under the following measurement conditions, and values ​​calculated in terms of polystyrene were calculated: Measuring device: Tosoh Corporation, HLC-8320GPC Column: TSK-GEL SuperAW2500 (3 columns connected) Detector: RI Mobile phase: tetrahydrofuran Column temperature: 40℃ The weight average molecular weight (Mw) and dispersity (Mw / Mn) are values ​​converted into standard polystyrene (manufactured by Sigma-Aldrich).

[0280] (Example 1-1: Synthesis of Compound 1)

[0281] [ka]

[0282] <Synthesis of Intermediate 1-1> 20.0 g of N-hydroxynaphthalimide was added to a flask and dissolved in 100 g of dichloromethane. Then, 14.2 g of triethylamine was added, cooled to 0°C, and 19.0 g of trifluoromethanesulfonic acid chloride was added dropwise. After the dropwise addition, the mixture was reacted at room temperature for 2 hours and then washed with pure water. After washing with pure water, the reaction solution was concentrated and added to methanol to precipitate crystals. The crystals were collected by filtration and dried under reduced pressure at 40°C, yielding 30.8 g of Intermediate 1-1 (yield: 95%).

[0283] <Synthesis of Intermediate 1-2> 25.0 g of intermediate 1-1 was added to a flask and dissolved in 200 g of dichloromethane. Then, 16.5 g of trifluoroacetic acid and 65.2 g of N-iodosuccinimide (NIS) were added, and the reaction was carried out at room temperature for 2 hours. 243 g of a 5% by mass aqueous solution of sodium bicarbonate was added dropwise to the reaction solution to terminate the reaction, and the organic layer was washed with pure water. The organic layer was concentrated and purified by silica gel column chromatography (developing solvent: dichloromethane / methanol), yielding 24.6 g of intermediate 1-2 (yield: 72%).

[0284] <Synthesis of intermediate 1-3> 20.0 g of intermediate 1-2 was added to a flask and dissolved in 160 g of N,N-dimethylformamide (DMF), followed by the addition of 3.6 g of potassium hydroxide and 1.5 g of tetrakistriphenylphosphine palladium. These were mixed uniformly and reacted at 120°C for 2 hours. After the reaction solution was cooled to room temperature (25°C), 120 g of dichloromethane was added to extract the target product, and the organic layer was washed with 310 g of 1% by mass hydrochloric acid and purified water. The washed organic layer was concentrated and purified by silica gel column chromatography (developing solvent: dichloromethane / methanol), yielding 13.3 g of intermediate 1-3 (yield: 87%).

[0285] <Synthesis of Compound 1> 15.0 g of intermediate 1-3, 120 g of dichloromethane, and 10.5 g of triethylamine were added to a flask, and 8.7 g of methacrylic acid chloride was added dropwise to the system at 5°C or below. After stirring for an additional hour under ice cooling, 150 g of pure water was added dropwise to the reaction solution, and the mixture was stirred and the aqueous layer was removed. The organic layer was concentrated and purified by silica gel column chromatography (developing solvent: dichloromethane / methanol) to obtain 14.6 g of compound 1 (yield: 82%). The obtained compound 1 was 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.61(d, Ar-H, 1H), 8.54(d, Ar-H, 1H), 8.26(s, Ar-H, 1H), 8.09(s, Ar-H, 1H), 7.79(t, Ar-H, 1H), 5.88(d, =CH2, 1H), 5.70(d, =CH2, 1H), 1.90(s, -CH3, 3H).

[0286] (Example 1-2: Synthesis of Compound 2) In the synthesis of compound 1 in Example 1-1, except that methacrylic acid chloride was replaced with acrylic acid chloride, 12.5 g of compound 2 (see the following chemical formula) was obtained in the same manner as in Example 1-1 (yield: 78%). 1H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.58(d, Ar-H, 1H), 8.52(d, Ar-H, 1H), 8.25(s, Ar-H, 1H), 8.10(s, Ar-H, 1H), 7.78(t, Ar-H, 1H), 6.40(d, =CH2, 1H), 6.13(t, =CH-, 1H), 5.82(d, =CH2, 1H).

[0287] [ka]

[0288] (Example 1-3: Synthesis of Compound 10) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was replaced with n-nonafluorobutanesulfonic acid chloride, 10.9 g of compound 10 (see the following chemical formula) was obtained (yield: 72%) in the same manner as in Example 1-1. 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.61(d, Ar-H, 1H), 8.54(d, Ar-H, 1H), 8.26(s, Ar-H, 1H), 8.09(s, Ar-H, 1H), 7.79(t, Ar-H, 1H), 5.88(d, =CH2, 1H), 5.70(d, =CH2, 1H), 1.90(s, -CH3, 3H).

[0289] [ka]

[0290] (Example 1-4: Synthesis of Compound 14) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was replaced with pentafluorobenzenesulfonic acid chloride, 11.7 g of compound 14 (see the following chemical formula) was obtained (yield: 77%) in the same manner as in Example 1-1. 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.63(d, Ar-H, 1H), 8.52(d, Ar-H, 1H), 8.28(s, Ar-H, 1H), 8.13(s, Ar-H, 1H), 7.80(t, Ar-H, 1H), 5.86(d, =CH2, 1H), 5.68(d, =CH2, 1H), 1.89(s, -CH3, 3H).

[0291] [ka]

[0292] (Example 1-5: Synthesis of Compound 21) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was replaced with norbornylsulfonic acid chloride, 10.5 g of compound 21 (see the following chemical formula) was obtained in the same manner as in Example 1-1 (yield: 75%). 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.60(d, Ar-H, 1H), 8.55(d, Ar-H, 1H), 8.24(s, Ar-H, 1H), 8.10(s, Ar-H, 1H), 7.78(t, Ar-H, 1H), 5.89(d, =CH2, 1H), 5.73(d, =CH2, 1H), 0.99-2.17(m, 13H).

[0293] [ka]

[0294] (Example 1-6: Synthesis of Compound 26) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was replaced with 10-camphorsulfonic acid chloride, the same method as in Example 1-1 was used to obtain 11.6 g of compound 26 (see the following chemical formula) (yield: 77%). 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR (DMSO-d6, 400MHz):δ(ppm)= 8.60(d, Ar-H, 1H), 8.52(d, Ar-H, 1H), 8.25(s, Ar-H, 1H), 8.12(s, Ar-H, 1H), 7.77(t, Ar-H, 1H), 5.87(d, =CH2, 1H), 5.72(d, =CH2, 1H), 0.72-3.04(m, 18H).

[0295] [ka]

[0296] (Comparative Example 1-1: Preparation of Comparative Compound 1) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was changed to methanesulfonyl chloride, 10.3 g of comparative compound 1 (see the following chemical formula) was obtained (yield: 75%) in the same manner as in Example 1-1. 1 H-NMR measurement was carried out and the structure was identified from the following data: 1H-NMR (DMSO-d6, 400MHz):δ(ppm)= 8.60(d, Ar-H, 1H), 8.54(d, Ar-H, 1H), 8.25(s, Ar-H, 1H), 8.09(s, Ar-H, 1H), 7.78(t, Ar-H, 1H), 5.88(d, =CH2, 1H), 5.71(d, =CH2, 1H), 3.41(s, -CH3, 3H), 1.99(s, -CH3, 3H).

[0297] [ka]

[0298] (Comparative Example 1-2: Preparation of Comparative Compound 2) In the synthesis of intermediate 1-1 in Example 1-1, except that trifluoromethanesulfonic acid chloride was replaced with p-toluenesulfonyl chloride, the same method as in Example 1-1 was used to obtain 12.0 g of comparative compound 2 (see the following chemical formula) (yield: 72%). 1 H-NMR measurement was carried out and the structure was identified from the following data: 1 H-NMR(DMSO-d6, 400MHz):δ(ppm)= 8.60(d, Ar-H, 1H), 8.54(d, Ar-H, 1H), 8.26(s, Ar-H, 1H), 8.10(s, Ar-H, 1H), 7.80-7.50(m, Ar-H, 5H), 5.88(d, =CH2, 1H), 5.70(d, =CH2, 1H), 2.43(s, -CH3, 3H), 1.91(s, -CH3, 3H).

[0299] [ka]

[0300] Example 2-1: Preparation of Polymer 1 4.0 g of Compound 1 obtained in Example 1-1 above, 4.0 g of methacrylic acid, 18.55 g of n-butyl methacrylate, 54.9 g of 1-ethylcyclohexyl methacrylate, and 1.9 g of V-601HP (dimethyl-2,2'-azobis(2-methylpropionate), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were dissolved in 165 g of methyl ethyl ketone and stirred at 80°C for 5 hours under a nitrogen atmosphere. The reaction solution was then cooled to room temperature and added to 330 g of heptane for reprecipitation. The resulting solid was filtered and dried under reduced pressure at room temperature overnight, yielding 65.1 g of the target polymer 1.

[0301] The weight average molecular weight (Mw) of the obtained polymer 1, calculated in terms of standard polystyrene, determined by gel permeation chromatography (GPC) was 51,000, and the dispersity (Mw / Mn) was 2.5. 13 The copolymer composition ratio in polymer 1 (molar ratio of each structural unit in polymer 1; see the chemical formula below for the structure) determined by C-NMR was l / m / n / o = 60 / 10 / 28 / 2.

[0302] [ka]

[0303] (Examples 2-2 to 2-4: Production of Polymers 2 to 4) Polymers 2 to 4 were obtained by carrying out a polymerization reaction in the same manner as in Example 2-1, except that Compound 2, Compound 10, and Compound 14 obtained in Examples 1-2 to 1-4 were used instead of Compound 1. The weight average molecular weights, dispersities, and 13 The copolymer composition ratios in polymers 2 to 4 determined by C-NMR (molar ratios of each structural unit in polymers 2 to 4; see the chemical formulas below for structures) are shown in Table 1 below.

[0304] [ka]

[0305] [ka]

[0306] [ka]

[0307] (Example 2-5: Production of Polymer 5) Polymer 5 was obtained by carrying out a polymerization reaction in the same manner as in Example 2-1, except that 1-ethylcyclopentyl methacrylate was used instead of 1-ethylcyclohexyl methacrylate and Compound 21 obtained in Example 1-5 was used instead of Compound 1. The weight average molecular weight, dispersity, and 13 The copolymer composition ratio in Polymer 5 (molar ratio of each structural unit in Polymer 5, see the chemical formula below) determined by C-NMR is shown in Table 1 below.

[0308] [ka]

[0309] (Example 2-6: Production of Polymer 6) Polymer 6 was obtained by carrying out a polymerization reaction in the same manner as in Example 2-5, except that Compound 26 obtained in Example 1-6 was used instead of Compound 21. The weight average molecular weight, dispersity, and 13 The copolymer composition ratio in polymer 6 (molar ratio of each structural unit in polymer 6, see the chemical formula below) determined by C-NMR is shown in Table 1 below.

[0310] [ka]

[0311] (Example 2-7: Production of Polymer 7) Polymer 7 was obtained by carrying out a polymerization reaction in the same manner as in Example 2-5, except that Compound 1 obtained in Example 1-1 above was used instead of Compound 21. The weight average molecular weight, dispersity, and13 The copolymer composition ratio in polymer 7 determined by C-NMR (molar ratio of each structural unit in polymer 7; see the chemical formula below for the structure) is shown in Table 1 below.

[0312] [ka]

[0313] (Comparative Example 2-1: Production of Polymer 8) Polymer 8 was obtained by carrying out a polymerization reaction in the same manner as in Example 2-5, except that Comparative Compound 1 prepared in Comparative Example 1-1 above was used instead of Compound 5. The weight average molecular weight, dispersity, and 13 The copolymer composition ratio in polymer 8 (the molar ratio of each structural unit in polymer 8, see the chemical formula below for the structure) determined by C-NMR is shown in Table 1 below.

[0314] [ka]

[0315] (Comparative Example 2-2: Production of Polymer 9) Polymer 9 was obtained by carrying out a polymerization reaction in the same manner as in Example 2-5, except that Comparative Compound 2 prepared in Comparative Example 2-2 was used instead of Compound 5. The weight average molecular weight, dispersity, and 13 The copolymer composition ratio in polymer 9 determined by C-NMR (molar ratio of each structural unit in polymer 9; see the chemical formula below for the structure) is shown in Table 1 below.

[0316] [ka]

[0317] Comparative Example 2-3: Production of Polymer 10 4.0 g of methacrylic acid, 19.8 g of n-butyl methacrylate, 54.7 g of 1-ethylcyclohexyl methacrylate, and 1.9 g of V-601HP (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were dissolved in 165 g of methyl ethyl ketone and stirred at 80 °C for 5 hours under a nitrogen atmosphere. The reaction solution was then cooled to room temperature and added to 330 g of heptane for reprecipitation. The resulting solid was filtered and dried under reduced pressure at room temperature overnight to obtain 62.8 g of the target polymer 10.

[0318] The weight average molecular weight, dispersity, and 13 The copolymer composition ratio in polymer 10 determined by C-NMR (the molar ratio of each structural unit in polymer 10; see the chemical formula below for the structure) is shown in Table 1 below.

[0319] [ka]

[0320] [Table 1]

[0321] Example 3-1: Preparation of resist composition 1 To 100 parts by mass of the polymer 1 obtained in Example 2-1 above, 0.1 parts by mass of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., component C-1) as an acid diffusion inhibitor, 0.05 parts by mass of 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd., component D-1) as an adhesion improver, and 100 parts by mass of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGMEA) (PGMEA:PGME = 50:50 (mass ratio), component E-1) as a solvent were prepared. These components were mixed at 25°C for 15 minutes to prepare resist composition 1.

[0322] Examples 3-2 to 3-7: Preparation of Resist Compositions 2 to 7 Resist compositions 2 to 7 were prepared in the same manner as in Example 3-1, except that polymer 1 was replaced with polymers 2 to 7 obtained in the above examples 2-2 to 2-7.

[0323] (Examples 3-8) Resist composition 8 was prepared in the same manner as in Example 3-1, except that N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide (component B-1, manufactured by Tokyo Chemical Industry Co., Ltd., see the chemical formula below) was further added in an amount of 0.5 parts by mass per 100 parts by mass of polymer 1.

[0324] [ka]

[0325] Examples 3-9 Resist composition 9 was prepared in the same manner as in Example 3-1, except that [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium trifluoromethanesulfonate (component B-2, manufactured by San-Apro Co., Ltd., see the chemical formula below) was further added in an amount of 0.5 parts by mass per 100 parts by mass of polymer 1.

[0326] [ka]

[0327] (Comparative Examples 3-1 to 3-2) Comparative resist compositions 1 and 2 were prepared in the same manner as in Example 3-1, except that polymers 8 and 9 obtained in the above comparative examples 2-1 and 2-2 were used instead of polymer 1.

[0328] (Comparative Example 3-3) Comparative resist composition 3 was prepared in the same manner as in Example 3-8, except that polymer 10 obtained in Comparative Example 2-3 above was used instead of polymer 1, and the amount of component B-1 added was changed to 2 parts by mass per 100 parts by mass of polymer 10.

[0329] (Comparative Example 3-4) Comparative resist composition 4 was prepared in the same manner as in Example 3-9, except that polymer 10 obtained in Comparative Example 2-3 above was used instead of polymer 1, and the amount of component B-2 added was changed to 2 parts by mass per 100 parts by mass of polymer 10.

[0330] [evaluation] A Cu substrate (size: 8 inches) was prepared, with a 150 nm-thick Cu film formed on the silicon substrate surface by sputtering. The resist composition of each example and comparative example was spin-coated onto the Cu substrate and dried on a hot plate at 150°C for 10 minutes to form a 60 μm-thick resist film. Next, the resist film was pattern-exposed using an i-line stepper FPA-5520iV (Canon Inc., NA = 0.18) with i-line (wavelength: 365 nm) at a desired exposure dose through a photomask (hole diameter:hole spacing = 1:1) with holes ranging from 10 μm to 60 μm in 5 μm increments. The substrate was then placed on a hot plate and post-exposure baked (PEB) at 100°C for 5 minutes. This was followed by a puddle development process using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C for 60 seconds, repeating this process six times. Thereafter, the surface of the resist pattern was rinsed with pure water at 25° C. for 60 seconds, and then spin-dried to obtain a resist pattern.

[0331] The obtained resist pattern (hole pattern) was observed with a scanning electron microscope (SEM, Hitachi High-Tech Corporation, product number: S-9220), and the smallest hole diameter (unit: μm) that could be resolved was evaluated as "resolution." The obtained resist pattern (hole pattern) was also observed with a scanning electron microscope (SEM), and the smallest exposure dose (unit: mJ / cm) that could resolve a 40 μm hole pattern was evaluated as "resolution." 2 ) was evaluated as "sensitivity."

[0332] The evaluation results are shown in Table 2 below.

[0333] [Table 2]

[0334] As is clear from Table 2 above, the resist compositions of Examples 3-1 to 3-9 were found to be excellent in sensitivity and resolution. On the other hand, the resist compositions of Comparative Examples 3-1 to 3-4, which used polymer compounds that did not contain a structural unit derived from the compound represented by General Formula 1, were found to have reduced sensitivity and resolution.

Claims

1. A compound represented by the following general formula 1: 【Chemical 1】 In the general formula 1, X is a hydrogen atom or a methyl group; Y is a linear alkyl group having from 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having from 3 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a cycloalkyl group having from 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, an unsubstituted cycloalkylalkyl group having from 4 to 21 carbon atoms, a cycloalkylalkyl group having from 4 to 21 carbon atoms in which at least one hydrogen atom is substituted with an oxygen atom, or an aryl group having from 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

2. 2. The compound according to claim 1, wherein Y in General Formula 1 is a linear alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, a branched alkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or an aryl group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

3. A polymer compound having a structural unit derived from the compound according to claim 1.

4. The polymer compound according to claim 3 , further comprising a structural unit having an acid-decomposable group.

5. 4. The polymer compound according to claim 3, wherein the content of the structural unit derived from the compound represented by General Formula 1 in the polymer compound is 0.1 mol % or more and 30 mol % or less, where the total of all structural units in the polymer compound is 100 mol %.

6. The polymer compound according to claim 3; an organic solvent; A resist composition comprising at least

7. The resist composition according to claim 6, further comprising an acid diffusion inhibitor.

8. A step of forming a resist film on a substrate using the resist composition according to claim 6; exposing the resist film to light; and developing the resist film after the exposure to form a resist pattern; A method for forming a resist pattern, comprising:

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