DESCRIPTION

Title of Invention: METHOD FOR FORMING NEGATIVE PATTERN, METHOD FOR PRODUCING ELECTRONIC DEVICE, ELECTRONIC DEVICE AND ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a method for forming a negative pattern which is applicable to semiconductor production processes for ICs and the like, production of circuit boards such as a liquid crystal circuit board and a thermal head circuit board, and further, other lithography processes for photopublication, a method for producing an electronic device including the pattern forming method, an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition. In particular, the present invention relates to a method for forming a negative pattern which is suitable for exposure by means of an ArF exposure apparatus that uses far-ultraviolet light having a wavelength of 300 nm or less as a light source, an ArF liquid immersion type projection exposure apparatus, and an EUV exposure apparatus, a method for producing an electronic device including the pattern forming method, an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition.

[0003] 2. Description of the Related Art

[0004] After resists for KrF excimer lasers (248 nm) were developed, an image forming method called chemical amplification has been used as an image forming method of the resists in order to compensate for a decrease in sensitivity due to light absorption. To explain the mechanism by taking an example of the image forming method based on positive type chemical amplification, it is an image forming method in which an acid generator at an exposed area is decomposed by exposure using excimer laser light, an electron beam, extreme ultraviolet light or the like to produce an acid, an alkali- insoluble group is converted to an alkali-soluble group through a process of post exposure bake (PEB) by using the generated acid as a reaction catalyst, and the exposed area is removed by alkali development.

[0005] As the alkali developer used in the above-described method, various alkali developers have been proposed but an aqueous alkali developer of 2.38% by mass TMAH (an aqueous tetramethylammonium hydroxide solution) is used for general purposes.

[0006] Along with the miniaturization of semiconductor elements, shortening of the wavelength of exposure light sources and an enhancement of the numerical aperture (high NA) of projection lenses are in progress. Therefore, recently, an exposure apparatus that uses ArF excimer laser light having a wavelength of 193 nm as a light source has been developed. In addition, as a technique which is intended to further increase the resolving power, a so-called liquid immersion method which involves filling of the space between the projection lens and a sample with a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") has been proposed in the related art. Furthermore, EUV lithography, which performs the exposure using ultraviolet light having a short wavelength (13.5 nm), or the like has been proposed.

[0007] However, in the current circumstances, it is very difficult to find an appropriate combination of a resist composition, a developer, and a rinsing liquid, and the like, necessary for forming a pattern that has an excellent performance overall. Therefore, further improvement of the performance is required. Particularly, as the resolution line width of a resist is miniaturized, improvements of line edge roughness performance of a line pattern and uniformity of local pattern dimensions become necessary.

[0008] On the other hand, in addition to developing a positive type resist composition that has recently become mainstream, a chemically amplified negative type resist composition in a pattern forming method by alkali development has been developed (see, for example, JP2006-317803A, JP2006-259582A, JP2006- 195050 A, and JP2000-206694A). This is because, while there is a demand for forming a pattern having various shapes such as lines, trenches, and holes when producing a semiconductor device or the like, there are patterns that are difficult to be formed by the present positive type resist.

[0009] Recently, a pattern forming method using a developer containing an organic solvent has been developed (see, for example, JP2008-292975A and JP2011-141494A). For example, in consideration of demands for further improving line width roughness (LWR), depth of focus (DOF), and other various performances, which may be influenced by swelling as a main cause during development, in forming a pattern by alkali development using a negative type resist composition of the related art, in JP2011-141494A, a chemically amplified negative type resist composition to which a specific compound containing at least one of a fluorine atom and a silicon atom is added is used in a method for forming a negative pattern using a developer containing an organic solvent.

SUMMARY OF THE INVENTION [0010] In consideration of a demand for forming a pattern having various shapes such as lines, trenches, and holes when producing a semiconductor device or the like, an object of the present invention is to provide a method for forming a negative pattern which is capable of forming a pattern with excellent depth of focus (DOF), uniformity of local pattern dimensions and resolution even in forming a pattern having various shapes including a contact hole pattern, a method for producing an electronic device including the pattern forming method, an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition.

[0011] The present invention is, for example, as follows.

[0012] [1] A method for forming a negative pattern including (i) forming a film from an actinic ray-sensitive or radiation-sensitive resin composition, (ii) exposing the film, and (iii) developing the exposed film by using a developer containing an organic solvent, in which the actinic ray-sensitive or radiation-sensitive resin composition includes a non-polymer compound (compound (G)) having a molecular weight of 500 or more which contains a nitrogen atom, and any of a fluorine atom and a silicon atom.

[0013] [2] The method for forming a negative pattern according to [1], in which the nitrogen atom contained in the compound (G) is substituted with a group which is capable of being desorbed by the action of an acid.

[0014] [3] The method for forming a negative pattern according to [2], in which the group which is capable of being desorbed by the action of an acid is represented by the following General Formula (1).

[Chem. 1]

In the formula,

Rbi, Rb ₂ , and Rb ₃ each independently represent an alkyl group or a cycloalkyl group, any two of Rbi, Rb ₂ , and Rb ₃ may be bonded with each other to form a ring, and

* represents a bonding site with a nitrogen atom.

[0015] [4] The method for forming a negative pattern according to any one of [1] to [3], in which the compound (G) is a compound represented by the following General Formula (2).

[Chem. 2]

In General Formula (2),

Rb _t , Rb ₂ , and Rb ₃ each independently represent an alkyl group or a cycloalkyl group and any two of Rbi, Rb ₂ , and Rb ₃ may be bonded with each other to form a ring,

Ra represents a group including a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or an amino group which is substituted with the group represented by the following General Formula (1),

Rci represents a single bond or an n+1 valent linking group and the linking group may include an amino group which is substituted with the group represented by the following General Formula (1),

Ra and Rci may be bonded with each other to form a ring structure,

Rfi represents a monovalent group containing a fluorine atom,

x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x, y, and z satisfy x+y+z=3, and

n represents an integer of 1 or more,

[Chem. 3]

In General Formula (1), Rbi, Rb ₂ , and Rb ₃ are synonymous with Rbi, Rb ₂ , and Rb ₃ in General Formula (2), and

* represents a bonding site with a nitrogen atom.

[0016] [5] The method for forming a negative pattern according to [4], in which the compound represented by General Formula (2) has two or more groups represented by Rfi.

[0017] [6] The method for forming a negative pattern according to any one of [1] to [5], in which the compound (G) is a compound which has two or more perfluoroalkyl groups having 2 to 4 carbon atoms.

[0018] [7] The method for forming a negative pattern according to any one of [1] to [6], in which the content ratio of fluorine atoms in the compound (G) is 30% by mass or more. [0019] [8] The method for forming a negative pattern according to any one of [1] to [7], in which the actinic ray-sensitive or radiation-sensitive resin composition includes (A) a resin which is capable of being decomposed by the action of an acid so that the solubility in a developer containing an organic solvent decreases, (B) a compound capable of generating an acid by irradiation of actinic rays or radiation, and (C) a solvent, in addition to the compound (G).

[0020] [9] The method for forming a negative pattern according to any one of [1] to [8], in which the exposure is an immersion exposure.

[0021] [10] A method for producing an electronic device including the method for forming a negative pattern according to any one of [1] to [9].

[0022] [11] An electronic device produced by the method for producing an electronic device according to [10].

[0023] [12] An actinic ray-sensitive or radiation-sensitive resin composition used in the method for forming a negative pattern according to any one of [2] to [7].

[0024] [13] An actinic ray-sensitive or radiation-sensitive resin composition used in the method for forming a negative pattern according to [8].

[0025] According to the present invention, it is possible to provide a method for forming a negative pattern which is capable of forming a pattern with excellent depth of focus (DOF), uniformity of local pattern dimensions and resolution even in forming a pattern having various shapes including a contact hole pattern, a method for producing an electronic device including the pattern forming method, an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Hereinafter, the embodiments of the present invention will be described in detail.

[0027] In the notation of a group (an atomic group) in the present specification, a notation in which substituted and unsubstituted are not specified includes not only a group (an atomic group) having no substituents, but also a group (an atomic group) having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (an unsubstituted alkyl group), but also an alkyl group having a substituent (a substituted alkyl group).

[0028] The term "actinic rays" or "radiation" as used in the present specification means, for example, far-ultraviolet radiation represented by the bright line spectrum of a mercury lamp or excimer laser light, extreme ultraviolet (EUV) rays, X-rays, soft X-rays, an electron beam (EB) or the like. In addition, in the present invention, light means actinic rays or radiation.

[0029] The term "exposure" as used in the present specification includes, unless particularly stated otherwise, exposure to far-ultraviolet radiation represented by mercury lamp light or excimer laser light, X-rays, EUV light or the like, as well as image drawing by means of a particle beam such as an electron beam or an ion beam.

[0030] <Actinic ray-sensitive or radiation-sensitive resin composition>

[0031] First, an actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (hereinafter, also referred to as a "composition of the present invention") will be described. Typically, the composition of the present invention is preferably used in a method for forming a negative pattern which includes a development step using the developer containing an organic solvent.

[0032] The composition of the present invention includes a non-polymer compound (G) (hereinafter, also referred to as a "compound (G)") having a molecular weight of 500 or more which contains a nitrogen atom, and, any of a fluorine atom and a silicon atom.

[0033] Furthermore, in an aspect, the composition of the present invention may include (A) a resin which is capable of being decomposed by the action of an acid so that the solubility in a developer containing an organic solvent decreases, (B) a compound capable of generating an acid by irradiation of actinic rays or radiation, and (D) a solvent, in addition to the compound (G).

[0034] Moreover, in another aspect, the composition of the present invention may further include at least one of a hydrophobic resin, a basic compound, an ammonium salt compound, a surfactant, and other additives.

[0035] Hereinafter, these respective components will be described.

[0036] [1] Compound (G)

[0037] Generally, when exposure is performed on a resist film formed by using a chemically amplified type resist composition which includes a compound (photoacid generator) capable of generating an acid by light, a surface layer portion of the resist film tends to have a higher degree of exposure and a higher concentration of acid to be generated than the inside portion of the resist film and thus the reaction is likely to further proceed. Moreover, when negative type development is performed to this exposed film, defects in that the cross section of the obtained pattern becomes a T-top shape or bridge defects are generated easily occur. [0038] The composition of the present invention includes the non-polymer compound (G) having a molecular weight of 500 or more which contains at least one of a fluorine atom, and a silicon atom.

[0039] When the compound (G) contains at least one of a fluorine atom, and a silicon atom, compared with a case of the compound (G) not containing these atoms, the compound (G) has low surface free energy and is likely to be unevenly distributed in a surface layer portion of a resist film.

[0040] Accordingly, when exposure is performed on the resist film containing this compound (G), nitrogen-containing compounds are present at high concentration in the surface layer portion of the resist film. Therefore, acid excessively generated in the surface layer of the exposed area can be captured. In other words, it is possible to make acid concentration distribution in a thickness direction of the exposed area of the resist film uniform. According to this, since it is possible to more uniformly perform insoluble or sparingly soluble reactions with the developer containing an organic solvent of the resist film by using acid as a catalyst in the thickness direction of the resist film, defects such as a T-top shape and bridge defects as described above can be suppressed.

[0041] When the compound (G) is a non-polymer compound having a molecular weight of 500 or more, for example, volatilization thereof at the time of baking after exposure is suppressed and a sufficient uneven distribution at the surface is secured by appropriate fluctuation (diffusivity). The molecular weight of the compound (G) is preferably 500 to 1,000, more preferably 550 to 950, and still more preferably 600 to 950.

[0042] In an aspect of the present invention, it is preferable that a nitrogen atom in the molecule of the compound (G) be substituted with a group which is capable of being desorbed by the action of an acid (hereinafter, also referred to as an "acid-desorptionable group"). In this case, since more basic substances are generated in an area having a higher concentration of acid generated in the exposed area, acid-base neutralization is further promoted. As a result, it is possible to make the acid concentration distribution in the thickness direction of the exposed area of the resist film more uniform.

[0043] Therefore, it is important that a pKa of a compound obtained after the acid-desorptionable group is desorbed from the compound (G) (hereinafter, also referred to as a "compound (G')") is set to be within an appropriate range so as to express a performance of suppressing the diffusion of acid to be generated due to neutralization with the generated acid. The pKa of the compound (G') after deprotection of the compound (G) is preferably 5 to 12, more preferably 7 to 12, and still more preferably 8 to 12.

[0044] Herein, pKa indicates an acid dissociation index pKa in an aqueous solution. The acid dissociation index pKa is the logarithm of the reciprocal of the acid dissociation constant and can be measured, for example, by (a) a method described in The Journal of Physical Chemistry vol. 68, number 6, page 1560 (1964) or (b) a method of measuring by using an automatic potentiometric titrator manufactured by Kyoto Electronics Manufacturing Co., Ltd. (for example, AT-510 and the like). Moreover, (c) an acid dissociation constant described in Kagaku Binran Chemical Handbook II (4th revised edition, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.) can be used.

[0045] In Table 1, pKa values of various amine compounds are shown. In an aspect of the present invention, it is preferable that the compound (G) be a compound containing benzimidazole, imidazole, diethanolamine, benzylamine, ethylenediamine, 2-aminoethanol, 4-amino butyric acid or piperidine in which the pKa value is within a range of 5 to 12, as a partial structure of the compound (G').

[0046] Moreover, pKa values shown in Table 1 are values obtained by using a dissociation constant of an organic compound in an aqueous solution which is described in Kagaku Binran Chemical Handbook II (4th revised edition, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.) PII317 to II321.

[Table 1]

[0047] Furthermore, the meaning that a nitrogen atom in the compound (G) is substituted with an acid-desorptionable group has the above-described purpose. In addition, the meaning also has a purpose that, by protecting an amine group having a nucleophilic group, stability of the compound (G) itself in the actinic ray-sensitive or radiation- sensitive resin composition or an acid generator to be described later is secured and the storage stability of the composition is improved.

[0048] In an aspect of the present invention, the acid-desorptionable group which the compound (G) has is preferably a tertiary alkyl ester, from the viewpoint of being easily decomposed by acid so as to function as an amine and not having absorbance at 193 nm.

[0049] The acid-desorptionable group is represented by the following General Formula (1), for example.

[Chem. 4]

In the formula, Rbi, Rb ₂ , and Rb ₃ each independently represent an alkyl group or a cycloalkyl group, any two of Rbi, Rb ₂ , and Rb ₃ may be bonded with each other to form a ring.

* represents a bonding site with a nitrogen atom.

[0050] The alkyl group as Rbi, Rb ₂ and Rb ₃ is preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms and, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, an i-propyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-dodecyl group, or the like, may be included.

[0051] The cycloalkyl group as Rbi, Rb ₂ and Rb ₃ is preferably a cycloalkyl group having 3 to 20 carbon atoms and, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like may be included.

[0052] The ring which is formed by bonding two of Rbi to Rb ₃ to each other is preferably a (monocyclic or polycyclic) cycloalkyl group. More specifically, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group are preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

[0053] Rbi, Rb ₂ and Rb ₃ may further have substituents, and examples of these substituents may include a halogen atom (a fluorine atom or the like), a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably, having 3 to 10 carbon atoms), an aryl group (preferably, having 6 to 14 carbon atoms), an alkoxy group (preferably, having 1 to 10 carbon atoms), an acyl group (preferably, having 2 to 20 carbon atoms), an acyloxy group (preferably, having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably, having 2 to 20 carbon atoms), an aminoacyl group (preferably, having 2 to 10 carbon atoms), a group having a silicon atom, and the like. For a cyclic structure in a cycloalkyl group and the like, the substituent may further include an alkyl group (preferably, having 1 to 10 carbon atoms). For the aminoacyl group, the substituent may further include an alkyl group (preferably, having 1 to 10 carbon atoms).

[0054] The group having a silicon atom is not particularly limited as long as it is a group having at least one or more of silicon atoms, but examples thereof may include a silyl group, a silyloxy group, a group having a siloxane bond, and the like. In addition, the group having a silicon atom may be an alkylsilyl structure or a cyclic siloxane structure which a hydrophobic resin (D) to be described later may have (for example, groups represented by General Formulae (CS-1) to (CS-3) described later). These groups may further have a substituent and specific examples of the substituent are the same as the above specific examples of the substituent which Rbi, Rb ₂ and Rb ₃ may further have.

[0055] Specific examples of the group having a silicon atom may include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group and the like.

[0056] In an aspect of the present invention, it is preferable that the compound (G) include at least one group (Rf) containing a fluorine atom and include two or more groups (Rf) containing a fluorine atom.

[0057] Herein, it is preferable that the group (Rf) having a fluorine atom include a fluorinated alkyl site. When a fluorine atom is introduced to an alkyl group, as shown in Table 2 shown later, the surface tension is suppressed and the uneven distribution of the compound (G) at a surface is improved. Moreover, since a C-F bond has high bond energy, there are advantages that hydrogen fluoride or the like is not easily generated at the time of exposure and a fluorine atom can be stably introduced.

[0058] For example, it is preferable that the compound (G) include two or more groups (Rf) containing a perfluoroalkyl moiety having 2 to 4 carbon atoms. In addition, for example, the ratio of the fluorine atoms included in the molecule of the compound (G) (hereinafter, referred to as a "fluorination ratio") is preferably 30% by mass or more, and more preferably 35 to 50% by mass. [Table 2]

* "The latest trends in high- water-repellent techniques from ultra- water-repellent materials to latest applications thereof

Published by TORAY Research Center, Division of Investigative Research

[0059] The group (Rf) containing a fluorine atom which is included in the compound (G) is selected, for example, from the following groups. In an aspect, it is preferable that the compound (G) include two or more Rfs selected from the following groups.

[0060] In other words, Rf is selected, for example, from a fluorinated alkyl group, a fluorinated alkoxy group, a fluorinated alkylthio group, a fluorinated alkylamino group, a fluorinated alkoxycarbonyl group, a fluorinated alkylcarbonyloxy group, a fluorinated alkylcarbonylamide group, a fluorinated alkylaminocarbonyl group, a fluorinated alkylsulfonyl group, a fluorinated alkylsulfonylamide group, a fluorinated alkylsulfonylaminocarbonyl group, or a fluorinated alkylcarbonylaminosulfonyl group.

[0061] As a preferred embodiment, the compound (G) is represented by the following General Formula (2).

[0062] Since the compound represented by the following General Formula (2) has a fluorine atom in the moiety other than the group (a protective group constituting a carbamate group) represented by General Formula (1) described above, the compound (G') obtained by causing acid to act on the compound represented by General Formula (1) continuously has a fluorine atom. According to this, even in a heating step (PEB: Post Exposure Bake) after the exposure to be described later, the compound (G') does not readily diffuse in the direction inside the resist film and is present at a desired position. Therefore, acid excessively generated in the surface layer of the exposed area can be more reliably captured and it is possible to make acid concentration distribution in a thickness direction of the exposed area of the resist film uniform.

[Chem. 5]

In General Formula (2),

Rbi, Rb ₂ , and Rb ₃ each independently represent an alkyl group or a cycloalkyl group and any two of Rbi, Rb ₂ , and Rb ₃ may be bonded with each other to form a ring;

Ra represents a group including a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or an amino group which is substituted with the group represented by General Formula (1) described above;

Rci represents a single bond or an n+1 valent linking group and the linking group may include an amino group which is substituted with the group represented by General Formula (1) described above;

Ra and Rci may be bonded with each other to form a ring structure;

Rfi represents a monovalent group containing a fluorine atom;

x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x, y, and z satisfy x+y+z=3; and

n represents an integer of 1 or more.

[0063] When x=2, two of Ras may be the same as or different from each other.

[0064] When y=2, two of Rbi s, two of Rb ₂ s and two of Rb ₃ s may be the same as or different from each other, respectively.

[0065] When z=2, two of Rcis may be the same as or different from each other.

[0066] Moreover, when z=2 and/or n>2, plural Rfis may be the same as or different from each other.

[0067] General Formula (2) will be described in detail.

[0068] Rbi, Rb ₂ and Rb ₃ are synonymous with Rbi, Rb ₂ and Rb ₃ in General Formula (1) described above.

[0069] Specific examples of the alkyl group and the cycloalkyl group as Ra are the same as specific examples of Rbi, Rb ₂ , and Rb ₃ in General Formula (1) described above.

[0070] The aryl group as Ra is preferably an aryl group having 6 to 20 carbon atoms and examples thereof may include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, an anthryl group and the like.

[0071] The aralkyl group as Ra is preferably an aralkyl group having 6 to 12 carbon atoms and examples thereof may include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group and the like.

[0072] Examples of the alkenyl group as Ra may include a vinyl group, an allyl group, a methallyl group, an isocrotyl group, a 3-butenyl group, a sorbyl group and the like. [0073] Ra may be a group including an amino group substituted with a group represented by General Formula (1) described above. The amino group may be an alkylamino group, an anilino group, an imidazole group, a benzimidazole group and the like. When being present in a plural number, they may be identical with or different from each other.

[0074] Examples of the n+1 valent linking group represented by Rci, for example, as a divalent (n=l) linking group, may include an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an arylene group, -COO-, -OCO-, -CO-, -0-, -S-, -NHCO-, -NHCOO-, -NHCONH-, or a linking group combining plural groups of these. As a trivalent or higher (n>2) linking group, a trivalent or higher linking group corresponding to the above-described divalent linking group is exemplified.

[0075] The linking group represented by Rci may be further substituted with an amino group substituted with a group represented by General Formula (1) described above.

[0076] The monovalent group containing a fluorine atom represented by Rfi is synonymous with the above-described group (Rf) containing a fluorine atom.

[0077] In a preferred aspect, the compound (G) represented by General Formula (2) contains two or more groups represented by Rfi .

[0078] Ra, Rbi, Rb ₂ , Rb ₃ , Ret, and Rfi each may further have substituents and specific examples of these substituents are the same as the specific examples of the substituents which Rbi, Rb ₂ , and Rb ₃ in General Formula (1) described above may further have.

[0079] In addition, examples of the nitrogen-containing heterocyclic ring which is formed by bonding Ra and Rci to each other may include an aromatic or non-aromatic nitrogen-containing heterocyclic ring (preferably, having 3 to 20 carbon atoms). Examples of this nitrogen-containing heterocyclic ring may include rings corresponding to heterocyclic compounds such as pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, lH-l,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, imidazole, benzimidazole, imidazo[l,2-a]pyridine, (l S,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane, l,5,7-triazabicyclo[4.4.0]dec-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, and 1,5,9-triazacyclododecane. These rings may further have one or more kinds of substituents or may further have one or more substituents. Specific examples of these substituents are the same as the specific examples of the substituents which Rbi, Rb ₂ , and Rb ₃ in General Formula (1) described above may further have. [0080] The compound (G) can be synthesized, for example, from an amine through a method described in Protective Groups in Organic Synthesis 4th edition, or the like. For example, the compound represented by General Formula (2) described above is preferably obtained, as shown in the following scheme, by a method in which a dicarbonate ester or a halo formic acid ester is reacted with an amine. In the formula, X represents a halogen atom. Ra, Rbi, Rb ₂ , Rb ₃ , Rc _1; and Rfi each are synonymous with Ra, Rbi, Rb ₂ , Rb ₃ , Rci, and Rfi in General Formula (2).

[Chem. 6]

[0081] Specific examples of the compound (G) are shown below with molecular weights and fluorination ratios (% by mass).

[Chem. 7]

[Chem.8] [Chem. 9]

[Chem. 10]

[0082] The compound (G) can be used either alone or as a combination of two or more kinds.

[0083] The content of the compound (G) in the composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and still more preferably 0.4 to 3% by mass, based on the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition.

[0084] Furthermore, when the composition of the present invention contains an acid generator (compound (B)) to be described later, the ratio between the acid generator and the compound (G) used in the composition is preferably the acid generator/the compound (G) (molar ratio)=2.5 to 300, more preferably 5.0 to 200 and still more preferably 7.0 to 150.

[0085] [2] (A) Resin which is capable of being decomposed by the action of an acid so that the solubility in a developer containing an organic solvent decreases

[0086] The composition of the present invention may contain a resin which is capable of being decomposed by the action of an acid so as to increase polarity and thereby the solubility in a developer containing an organic solvent decreases. An example of this resin may include a resin having a group which is capable of being decomposed by the action of an acid and produces a polar group (hereinafter, also referred to as an "acid decomposable group") in the main chain or a side chain of the resin, or in both the main chain and a side chain (hereinafter, also referred to as "acid-degradable resin" or "resin (A)").

[0087] The acid decomposable group preferably has a structure in which a polar group is protected by a group which is decomposed and desorbed by the action of an acid.

[0088] The polar group is not particularly limited as long as it is a group which is sparingly soluble or insoluble in a developer containing an organic solvent, but examples thereof may include acidic groups (groups which dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide that is used as a conventional developer for resists) such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably, a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an

(alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group; or alcoholic hydroxyl groups.

[0089] Meanwhile, an alcoholic hydroxyl group means a hydroxyl group bonded onto a hydrocarbon group, and is a hydroxyl group other than the hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), but as a hydroxyl group, an aliphatic alcohol in which the a-position has been substituted with an electron-withdrawing group such as a fluorine atom (for example, a fluorinated alcohol group (a hexafluoroisopropanol group or the like)) is excluded. As the alcoholic hydroxyl group, a hydroxyl group of which pKa is greater than or equal to 12 and less than or equal to 20 is preferable.

[0090] Preferred examples of the polar group may include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

[0091] The group preferable as the acid decomposable group is a group in which hydrogen atoms of these groups are substituted with a group desorbed by acid.

[0092] As the group desorbed by acid, for example, -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(Roi)(Ro ₂ )(OR 9), or the like, may be included.

[0093] In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

[0094] Roi and Ro ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0095] The alkyl group of R ₃₆ to R ₃ , Roi and Ro ₂ is preferably an alkyl group having 1 to 8 carbon atoms and, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, an octyl group, or the like, may be included.

[0096] The cycloalkyl group of R ₃₆ to R ₃₉ , Roi and RQ ₂ may be monocyclic or polycyclic. As the monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferable and, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, or the like, may be included. As the polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferable and, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, an androstanyl group, or the like, may be included. In addition, at least one of the carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

[0097] The aryl group of R ₃₆ to R ₉ , Roi and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms and, for example, a phenyl group, a naphthyl group, an anthryl group, or the like may be included.

[0098] The aralkyl group of R ₃₆ to R ₃₉ , oi and Ro ₂ is preferably an aralkyl group having 7 to 12 carbon atoms and, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, or the like, may be included. [0099] The alkenyl group of R ₃₆ to R39, Roi and Ro ₂ is preferably an alkenyl group having 2 to 8 carbon atoms and, for example, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, or the like, may be included.

[0100] As the ring formed by R ₃ and R ₃₇ being bonded, a cycloalkyl group (monocyclic or polycyclic) is preferable. As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

[0101] The acid decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, the acid decomposable group is a tertiary alkyl ester group.

[0102] As a repeating unit having an acid decomposable group which the resin (A) contains, a repeating unit represented by the following General Formula (I) is preferable.

[Chem. 11]

In General Formula (I) described above,

Ro represents a hydrogen atom or a straight chain or branched alkyl group.

R] to R ₃ each independently represent a straight chain or branched alkyl group or a monocyclic or polycyclic cycloalkyl group.

Two of Ri to R ₃ may be bonded and form a monocyclic or polycyclic cycloalkyl group.

[0103] The straight chain or branched alkyl group in Ro may have a substituent, is preferably a straight chain or branched alkyl group having 1 to 4 carbon atoms and may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and the like. Examples of the substituent may include a hydroxyl group, a halogen atom (for example, a fluorine atom) and the like.

[0104] As Ro, a hydrogen atom, a methyl group, a trifluoromethyl group or a hydro xymethyl group is preferable. [0105] As an alkyl group of Ri to R ₃ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group or the like having 1 to 4 carbon atoms is preferable.

[0106] As a cycloalkyl group of Ri to R ₃ , monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.

[0107] As a cycloalkyl group that two of Ri to R ₃ form by binding to each other, monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group are preferable. A monocyclic cycloalkyl group having 5 or 6 carbon atoms is particularly preferable.

[0108] As a preferred aspect, an aspect in which R\ represents a methyl group or an ethyl group, and R ₂ and R ₃ are bonded and form a cycloalkyl group may be exemplified.

[0109] The respective groups described above may have a substituent and examples of the substituent may include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like. A substituent having 8 or less carbon atoms is preferable.

[0110] As a particularly preferred aspect of the repeating unit represented by General Formula (I), an aspect in which Ri, R ₂ , and R ₃ each independently represent a straight chain or branched alkyl group is exemplified.

[0111] In this aspect, as straight chain or branched alkyl groups of Ri, R ₂ , and R ₃ , an alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and the like.

[0112] As Ri, a methyl group, an ethyl group, an n-propyl group or an n-butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

[0113] As R ₂ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is particularly preferable.

[0114] As R ₃ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group is preferable, a methyl group, an ethyl group, an isopropyl group or an isobutyl group is more preferable, and a methyl group, an ethyl group or an isopropyl group is particularly preferable.

[0115] Preferred specific examples of the repeating unit having the acid decomposable group will be shown below, but the present invention is not limited to these.

[0116] Among the specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Each of Rxa and Rxb represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent and if present in plural numbers, plural numbers of Z may be the same as or different from each other, p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that may be carried by each group of Ri to R ₃ .

[Chem. 12]

[0117] Furthermore, it is also preferable that the repeating unit having an acid decomposable group be a repeating unit represented by the following General Formula (IB), which is capable of being decomposed by an acid and produces a carboxyl group, and thereby, a pattern forming method which is excellent in the roughness performance such as line width roughness, local uniformity of the pattern dimensions, and the exposure latitude, and can further suppress a decrease in the film thickness of the pattern areas formed by development, that is, so-called film thinning, can be obtained.

[Chem. 13]

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

Ryi to Ry ₃ each independently represent an alkyl group or a cycloalkyl group. Any two of Ryi to Ry ₃ may be joined together to form a ring.

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

Li and L ₂ each independently represent a single bond or divalent linking group.

n represents an integer of 1 to 3.

[0118] When n is 2 or 3, plural L ₂ s, plural Ryis, plural Ry ₂ s, and plural Ry ₃ s may be the same as or different from each other.

[0119] The alkyl group of Xa may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably, a fluorine atom).

[0120] The alkyl group of Xa preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, and the like. However, the alkyl group is preferably a methyl group.

[0121] Xa is preferably a hydrogen atom or a methyl group.

[0122] The alkyl group of Ryi to Ry ₃ may be chainlike or branched, and an alkyl group having

1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group, is preferred.

[0123] The cycloalkyl group of Ryi to Ry ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. [0124] The ring which is formed by two of Ryi to Ry ₃ that are bonded together is preferably a monocyclic hydrocarbon ring such as a cyclopentane ring or a cyclohexane ring; or a polycyclic hydrocarbon ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. A monocyclic hydrocarbon ring having 5 to 6 carbon atoms is particularly preferable.

[0125] Ryi to Ry ₃ are each independently preferably an alkyl group, and more preferably a chainlike or branched alkyl group having 1 to 4 carbon atoms. In addition, the total number of carbon atoms of the chainlike or branched alkyl group as Ryi to Ry ₃ is preferably 5 or less.

[0126] Ryi to Ry ₃ may further have substituents, and examples of the substituents may include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like. A substituent having 8 or less carbon atoms is preferable. Among these, a substituent which does not have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom is more preferable (for example, a group which is not an alkyl group substituted with a hydroxyl group or the like is more preferable) from the viewpoint of further improving dissolution contrast for a developer containing an organic solvent before and after acid decomposition, a group formed only from hydrogen atoms and carbon atoms is even more preferable and a straight chain or branched alkyl group, or a cycloalkyl group is particularly preferable.

[0127] The linking group having a polycyclic hydrocarbon structure of Z may be a ring assembly hydrocarbon ring group or a bridged cyclic hydrocarbon ring group, and examples thereof may include a group obtained by removing any (n+1) hydrogen atoms from a ring assembly hydrocarbon ring, and a group obtained by removing any (n+1) hydrogen atoms from a bridged cyclic hydrocarbon ring.

[0128] Examples of the ring assembly hydrocarbon ring group may include bicyclohexane ring group or a perhydronaphthalene ring group and the like. Examples of the bridged cyclic hydrocarbon ring group may include bicyclic hydrocarbon ring groups such as a pinane ring group, a bornane ring group, a norpinane ring group, a norbornane ring group, and a bicyclooctane ring group, (a bicyclo[2.2.2]octane ring group, a bicyclo[3.2.1]octane ring group, or the like); tricyclic hydrocarbon ring groups such as a homobrendane ring group, an adamantane ring group, a tricyclo[5.2.1.0 ² ' ⁶ ]decane ring group, and a tricyclo[4.3.1.1 ² ' ⁵ ]undecane ring group; and tetracyclic hydrocarbon ring groups such as a tetracyclo[4.4.0.1 ² ' ⁵ . l ⁷ ' ¹⁰ ]dodecane ring group, and a perhydro-l,4-methano-5,8-methanonaphthalene ring group. In addition, as the bridged cyclic hydrocarbon ring group, a condensed cyclic hydrocarbon ring group, for example, a condensed cyclic group in which a plurality of 5- to 8-membered cycloalkane ring groups such as a perhydronaphthalene (decalin) ring group, a perhydroanthracene ring group, a perhydrophenanthrene ring group, a perhydroacenaphthene ring group, a perhydrofluorene ring group, a perhydroindene ring group, a perhydrophenalene ring group are condensed, may be included.

[0129] Preferred examples of the bridged cyclic hydrocarbon ring group may include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, and a tricyclo[5.2.1.0 ² ' ⁶ ]decane ring group or the like. As the more preferable bridged cyclic hydrocarbon ring group, a norbornane ring group or an adamantane ring group may be included.

[0130] The linking group represented by Z having a polycyclic hydrocarbon structure may have a substituent. Examples of the substituent that can be carried by Z may include substituents such as an alkyl group, a hydroxyl group, a cyano group, a keto (=0) group, an acyloxy group, -COR, -COOR, -CON(R) ₂ , -S0 ₂ R, -S0 ₃ R, and -S0 ₂ N(R) ₂ . Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

[0131] The alkyl group, alkylcarbonyl group, acyloxy group, -COR, -COOR, -CON(R) ₂ , -S0 ₂ R, -S0 ₃ R, and -S0 ₂ N(R) ₂ as the substituents which may be carried by Z may further have substituents, and examples of the substituents may include a halogen atom (preferably, a fluorine atom).

[0132] In the linking group having a polycyclic hydrocarbon structure represented by Z, the carbon atoms constituting the polycyclic ring (carbon atoms contributing to ring formation) may be carbonyl carbon atoms. In addition, a polycycle thereof, as described above, may have a hetero atom such as an oxygen atom, sulfur atom, or the like as a ring member.

[0133] Examples of the linking group represented by L[ and L ₂ may include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -0-, -S-, -SO-, -S0 ₂ -, an alkylene group (preferably, having 1 to 6 carbon atoms), a cycloalkylene group (preferably, having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a linking group combining plural groups of these, while a linking group having 12 or less carbon atoms in total is preferable.

[0134] Li is preferably a single bond, an alkylene group, -COO-, -OCO-, -CO H-, -NHCO-, an -alkylene group-COO-, an -alkylene group-OCO-, an -alkylene group-CONH-, an -alkylene group- HCO-, -CO-, -0-, -S0 ₂ -, or an -alkylene group-O-, and more preferably a single bond, an alkylene group, an -alkylene group-COO-, or an -alkylene group-O-.

[0135] L ₂ is preferably a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, a -COO-alkylene group-, a -OCO-alkylene group-, a -CONH-alkylene group-, a -NHCO-alkylene group-, -CO-, -0-, -S0 ₂ -, a -O-alkylene group-, or a -O-cycloalkylene group, and more preferably a single bond, an alkylene group, a -COO-alkylene group-, a -O-alkylene group-, or a -O-cycloalkylene group.

[0136] In the method described above, the bond "-" at the left end means that in the case of Li, the linking group is connected to the ester bond on the main chain side, while in the case of L ₂ , the linking group is connected to Z. The bond "-" at the right end means that in the case of

Li, the linking group is connected to Z, while in the case of L ₂ , the linking group is bonded to the ester bond that is connected to a group represented by (Ryi)(Ry ₂ )(Ry ₃ )C-.

[0137] Meanwhile, Li and L ₂ may be bonded to the same atom constituting the polycyclic ring for Z.

[0138] n is preferably 1 or 2, and more preferably 1.

[0139] Specific examples of the repeating unit represented by General Formula (IB) will be shown below, but the present invention is not limited to these. In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

[Chem. 14]

[0140] The repeating unit having an acid decomposable group of the resin (A) may be of one kind, or two or more kinds may be used in combination.

[0141] In the present invention, it is preferable that the resin (A) have the repeating unit having an acid decomposable group described above (if the resin has plural kinds of repeating units, the sum) in which the molecular weight of the desorbed substance that is generated as the group which degrades by the action of an acid and produces a polar group (acid decomposable group) is decomposed (when plural kinds of desorbed substance are generated, the weighted average value of the molecular weights based on the molar fractions(hereinafter, also referred to as a molar average value)), is 140 or less, in an amount of 50 mol% or more based on total content the repeating units in the resin. Thereby, in the case of forming a negative type image, since the exposed areas remain as the pattern, a decrease in the film thickness of the pattern areas can be prevented by decreasing the molecular weight of the desorbed substance.

[0142] In the present invention, "the desorbed substance generated by the acid decomposable group being decomposed" is the one desorbed by being decomposed by the action of an acid, corresponding to a group desorbed by being decomposed by the action of an acid. For example, in the case of a repeating unit (a) that will be described below (the first repeating unit from the upper left in the examples described below), the desorbed substance refers to the alkene (H ₂ C=C(CH ₃ ) ₂ ) that is generated as the t-butyl moiety is decomposed.

[0143] In the present invention, the molecular weight of the desorbed substance generated as the acid decomposable group is decomposed (when plural kinds of desorbed substances are generated, the molar average value) is more preferably 100 or less, from the viewpoint of preventing a decrease in the film thickness of the pattern areas.

[0144] Furthermore, there are no particular limitations on the lower limit of the molecular weight of the desorbed substance (when plural kinds of desorbed substances are generated, the average value) generated as the acid decomposable group is decomposed, but from the viewpoint of allowing the acid decomposable group to exhibit its function, the lower limit of the molecular weight is preferably 45 or greater, and more preferably 55 or greater.

[0145] In the present invention, from the viewpoint of more reliably maintaining the film thickness of the pattern areas as the exposed areas, it is more preferable that the resin (A) have the repeating unit (in the case of containing plural kinds of repeating units, the sum) having an acid decomposable group in which the molecular weight of the desorbed substance generated as the acid decomposable group is decomposed is 140 or less, in an amount 60 mol% or more, even more preferably 65 mol% or more, and still more preferably 70 mol% or more, based on the total content of the repeating units in the resin. Furthermore, there are no particular limitations on the upper limit, but the upper limit of the content is preferably 90 mol% or less, and more preferably 85 mol% or less.

[0146] The content in total of the repeating units having an acid decomposable group is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 45 mol% or more, and particularly preferably 50 mol% or more, based on the total content of the repeating units in the resin (A).

[0147] Furthermore, the content in total of the repeating units having an acid decomposable group is preferably 90 mol% or less, and more preferably 85 mol% or less, based on the total content of the repeating units in the resin (A).

[0148] The resin (A) may further include a repeating unit having a lactone structure or a sultone structure.

[0149] As the lactone structure or the sultone structure, any compound can be used as long as it has a lactone structure or a sultone structure, but is preferably a 5- to 7-membered cyclic lactone structure, and more preferably a structure in which another cyclic structure is fused with a 5- to 7-membered cyclic lactone structure in the form of forming a bicyclo structure or a spiro structure. It is more preferable to have a repeating unit having a lactone structure represented by any one of the following General Formulae (LCl-1) to (LCl-17) or a sultone structure represented by any one of the following General Formulae (SLl-1) to (SL1-3). In addition, the lactone structure or the sultone structure may be bonded directly to a main chain. Preferred lactone structures include (LCl-1), (LCI -4), (LCI -5), (LCI -6), (LCl-13), (LCI- 14), and (LCl-17), and a particularly preferred lactone structure is (LCI -4). When these specific lactone structures are used, the LWR and the development defects are ameliorated.

[Chem. 15]

SL1-2 SL1-3

SL1-1

[0150] The lactone structure or the sultone structure part may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid decomposable group. An alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-decomposable group is more preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or greater, the plural substituents (Rb ₂ ) may the same as or different from each other. Also, plural substituents (Rb ₂ ) may be bonded with each other to form a ring.

[0151] The repeating unit having a lactone structure or a sultone structure typically includes optical isomers, however, any optical isomer may be used. In addition, one kind of optical isomer may be used alone or a plurality of optical isomers may be mixed and used. If one kind of optical isomer is mainly used, optical purity (ee) thereof is preferably 90% or more, and more preferably 95% or more.

[0152] The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following General Formula (All).

[Chem. 16]

In General Formula (All),

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

[0153] As the preferable substituent the alkyl group of Rb ₀ may have, a hydro xyl group or a halogen atom may be included. As the halogen atom of Rb ₀ , a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, may be included. Rbo is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0154] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group combining these. Ab is preferably a single bond or a divalent linking group represented by -Abi-C0 ₂ -.

[0155] Abi represents a straight chain or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0156] V represents a group having a lactone structure or a sultone structure. Specifically, for example, V represents a group having a structure represented by any one of General Formulae (LCl-1) to (LCl-17) and (SLl-1) to (SL1-3) described above.

[0157] When the resin (A) includes a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 65 mol%, even more preferably in the range of 5 to 60 mol%, particularly preferably in the range of 3 to 50 mol%, and most preferably 10 to 50 mol%, based on the total content of the repeating units of the resin (A).

[0158] One kind of the repeating unit having a lactone structure or a sultone structure may be used, or two or more kinds may be used in combination.

[0159] Specific examples of the repeating unit having a lactone structure or a sultone structure will be shown below, but the present invention is not limited to these.

[Chem. 17]

(In the formulae, x represents H, CH3, CHjOH, or CF3.)

[Chem. 18] (In the formulae, Rx represents H, C¾. CH2OH, or CF3.)

[0160] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. Thereby, the adhesiveness to substrates and the affinity to developers are enhanced. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably a repeating unit having no acid decomposable groups.

[0161] Furthermore, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably different from the repeating unit represented by General Formula (All) described above.

[0162] In the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, the alicyclic hydrocarbon structure is preferably an adamantyl group, a diadamantyl group, or a norbornane group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include the partial structures represented by the following General Formulae (Vila) to (Vlld).

Chem. 20]

In General Formulae (Vila) to (VIIc),

R ₂ c to R4C each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R4C represents a hydroxyl group, or a cyano group. Preferably, one or two of R ₂ c to R4C is a hydroxyl group, and the rest is a hydrogen atom. In General Formula (Vila), more preferably, two of R ₂ c to R_,c are hydroxyl groups and the rest are a hydrogen atom.

[0163] As the repeating unit having a partial structure represented by General Formulae (Vila) to (Vlld), a repeating structure represented by following General Formulae (Alia) to (Alld) may be included.

[Chem. 21]

(AHb)

In General Formulae (Alia) to (Alld),

Ric represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to Ric are synonymous with R ₂ c to R4C in General Formulae (Vila) to (VIIc).

[0164] The resin (A) may or may not include a repeating unit having a hydroxyl group or a cyano group, but when the resin (A) includes a repeating unit having a hydroxyl group or a cyano group, the content of the repeating unit having a hydroxyl group or a cyano group is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, and even more preferably 5 to 25 mol%, based on the total content of the repeating units in the resin (A).

[0165] Specific examples of the repeating unit having a hydroxyl group or a cyano group will be shown below, but the present invention is not limited to these.

[Chem. 22]

[0166] The resin (A) may have a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol in which the a-position has been substituted with an electron-withdrawing group (for example, a hexafluoroisopropanol group), and it is more preferable that the resin (A) have a repeating unit having a carboxyl group. When the resin (A) includes a repeating unit having an acid group, the resolution for the use in contact hole increases. As the repeating unit having an acid group, any of repeating units in which the acid group is bonded directly to the main chain of the resin such as a repeating unit by acrylic acid or methacrylic acid, a repeating unit in which the acid group is bonded to the main chain of the resin through a linking group, or introducing the repeating unit to the end of the polymer chain using a polymerization initiator or a chain transfer agent having an acid group when polymerized is preferable, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. A repeating structure by acrylic acid or methacrylic acid is particularly preferable.

[0167] The resin (A) may or may not include a repeating unit having an acid group, but when the resin (A) includes the repeating unit, the content of the repeating unit having an acid group is preferably 15 mol% or less, and more preferably 10 mol% or less, based on the total content of the repeating units in the resin (A). When the resin (A) includes a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.

[0168] Specific examples of the repeating unit having an acid group will be shown below, but the present invention is not limited to these.

[0169] In the specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Chem. 23]

[0170] The resin (A) of the present invention can further have a repeating unit which has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group or cyano group described above), and which does not exhibit acid degradability. Thereby, elution of low molecular components from the resist film to immersion liquid during the immersion exposure may be reduced, and solubility of the resin may be properly adjusted during the development using the developer including an organic solvent. As the repeating unit such as this, a repeating unit represented by General Formula (IV) may be included.

[Chem. 24]

In General Formula (IV), R ₅ represents a hydrocarbon group which has at least one cyclic structure and do not have a polar group.

Ra represents a hydrogen atom, an alkyl group or -CH ₂ -0-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferable.

[0171] The cyclic structure, which R ₅ has, includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkyl groups having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and cycloalkenyl groups having 3 to 12 carbon atoms, such as a cyclohexenyl group. The preferable monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms and more preferably includes a cyclopentyl group or a cyclohexyl group.

[0172] The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group or a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, a bicyclic hydrocarbon ring such as pinane, bornane, norpinane, norbornane or a bicyclooctane ring (a bicyclo[2.2.2]octane ring or a bicyclo[3.2.1]octane ring or the like), a tricyclic hydrocarbon ring such as homobrendane, adamantane, a tricyclo [5.2.1.0 ² ' ⁶ ] decane ring or a tricyclo [4.3. l. l ² ' ⁵ ] undecane ring, a tetracyclic hydrocarbon ring such as a tetracyclo [4.4.0.1 ² ' ⁵ .1 ⁷ ' ¹⁰ ] dodecane ring or a perhydro-l,4-methano-5,8-methanonaphthalene ring, or the like, may be included. In addition, as the bridged cyclic hydrocarbon ring, a condensed cyclic hydrocarbon ring, for example, a condensed cyclic ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydronaphthalene (decalin) ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a perhydroacenaphthene ring, a perhydrofluorene ring, a perhydroindene ring, a perhydrophenalene ring are condensed, may be also included. [0173] As the preferable bridged cyclic hydrocarbon ring, a norbornyl group, an adamantyl

2 6

group, a bicyclo octanyl group, a tricyclo [5.2.1.0 ' ] decanyl group, or the like, may be included. As the more preferable bridged cyclic hydrocarbon ring, a norbornyl group or an adamantyl group may be included.

[0174] These alicyclic hydrocarbon group may have a substituent, and as the preferable substituent, a halogen atom, an alkyl group, a hydroxyl group of which hydrogen atom is substituted, an amino group of which hydrogen atom is substituted or the like may be included. As the preferable halogen atom, a bromine atom, a chlorine atom or a fluorine atom may be included, and as the preferable alkyl group, a methyl group, an ethyl group, a butyl group or a t-butyl group may be included. The above alkyl group may further have substituents, and as the substituent which the alkyl group may further has, a halogen atom, an alkyl group, a hydroxyl group of which hydrogen atom is substituted, an amino group of which hydrogen atom is substituted may be included.

[0175] As the substituent of the hydrogen atom, for example, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, or the like may be included. As the preferable alkyl groups, an alkyl group having 1 to 4 carbon atoms may be included, as the preferable substituted methyl group, a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group or a 2-methoxyethoxymethyl group, as the preferable substituted ethyl group, a 1-ethoxyethyl group or a 1 -methyl- 1-methoxyethyl group may be included, as the preferable acyl group, an aliphatic acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group or a pivaloyl group may be included, and as the alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms or the like may be included.

[0176] The resin (A) may or may not include a repeating unit which has an alicyclic hydrocarbon structure that does not have a polar group, and which does not exhibit acid degradability, but when the resin (A) includes the repeating unit, the content of this repeating unit is preferably 1 to 40 mol%, and more preferably 1 to 20 mol%, based on the total content of the repeating units in the resin (A).

[0177] Specific examples of the repeating unit which has an alicyclic hydrocarbon structure that does not have a polar group, and which does not exhibit acid degradability will be shown below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Chem. 25]

[0178] The resin (A) used in the composition of the present invention can have various repeating structural units, in addition to the repeating structural units described above, for the purpose of controlling dry etching resistance, suitability to standard developers, adhesiveness to substrates, resist profile, and other general characteristics required by a resist, such as resolution, heat resistance, and sensitivity.

[0179] The repeating structural unit such as this may include a repeating structural unit corresponding to the following monomers, however, are not limited to these.

[0180] As a result, fine-tuning of the performances required for a resin used in the composition of the present invention, particularly,

(1) solubility in a coating solvent,

(2) film- forming properties (glass transition point),

(3) alkali developability,

(4) film thinning (selection of hydrophilicity or hydrophobicity, or alkali-solubility),

(5) adhesiveness to the substrate at unexposed areas,

(6) dry etching resistance,

or the like, becomes possible.

[0181] Examples of such a monomer may include compounds having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, aryl compounds, vinyl ethers, vinyl esters and the like.

[0182] In addition to these, addition-polymerizable unsaturated compounds, which are copolymerizable with monomers corresponding to a variety of repeating structural units described above, may be copolymerized.

[0183] In the resin (A) used in the composition of the present invention, the molar content ratio of the respective repeating structural units is appropriately set so as to control the dry etching resistance, suitability to standard developers, and adhesiveness to substrates of the resist, the resist profile, and general performances required by a resist such as resolution, heat resistance, and sensitivity.

[0184] The form of the resin (A) in the present invention may be any of random type, block type, comb type and star type. The resin (A) can be synthesized by, for example, radical, cation, or anion polymerization of unsaturated monomers corresponding to the respective structures. A target resin may also be obtained from a polymerization reaction after polymerization using unsaturated monomers corresponding to the precursors of each structure.

[0185] When the composition of the present invention is intended for exposure to ArF, from the viewpoint of transparency to ArF light, it is preferable that the resin (A) used in the composition of the present invention substantially do not have an aromatic ring (specifically, the proportion of a repeating unit having an aromatic group in the resin be preferably 5 mol% ~ or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, the resin have no aromatic group), and it is preferable that the resin (A) have a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0186] Moreover, a CLogP value of the resin (A) is not particularly limited, but, from the viewpoint of sufficiently expressing an effect by using a resin (D) to be described later, the CLogP value thereof is preferably 0 to 6, more preferably 1 to 5, and still more preferably 1 to 4.

[0187] An absolute value of a difference between a CLogP value of the resin (A) and a CLogP value of the resin (D) is preferably larger than 0, more preferably 1 or larger, and still more preferably 2 or larger.

[0188] When the absolute value of a difference between a CLogP value of the resin (A) and a CLogP value of the resin (D) is large, segregation of the resin (D) easily occurs on the surface of a resist film during forming the resist film. Therefore, it is possible to enhance effects of the present invention (film thickness uniformity and residual water defect decrease). [0189] Herein, the CLogP value of the resin (A) is the computer-calculated value of LogP which is the water-n-octanol partition coefficient P expressed by a common logarithm, and is used as an indicator showing the degree of hydrophilicity/hydrophobicity of a material. The CLogP of each polymerization unit of the resin (A) can be calculated using, for example, software, Chem Draw Ultra ver. 8.0, produced by Cambridge Soft Corporation. An arithmetic average value of values of respective polymerization units is defined as the CLogP value of the copolymerization composition.

[01 0] Furthermore, from another viewpoint, when the composition of the present invention contains a resin (D) described below, it is preferable that the resin (A) do not contain a fluorine atom and a silicon atom from the viewpoint of compatibility with the resin (D).

[0191] A preferred example of the resin (A) used in the composition of the present invention is a resin in which the repeating units entirely consist of (meth)acrylate-based repeating units. In this case, any of the resin (A) in which all repeating units are methacrylate-based repeating units, the resin (A) in which all repeating units are acrylate-based repeating units, and the resin (A) in which all repeating units are methacrylate-based repeating units or acrylate-based repeating units may be used, however, the content of acrylate-based repeating unit is preferably 50 mol% or less based on the total content of the repeating units in the resin (A). In addition, a copolymer, including 20 to 50 mol% of the (meth)acrylate-based repeating unit having an acid decomposable group, 20 to 50 mol% of the (meth)acrylate-based repeating unit having a lactone group, 5 to 30 mol% of the (meth)acrylate-based repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and further including 0 to 20 mol% of other (meth)acrylate-based repeating units, is also preferable.

[0192] When the composition of the present invention is irradiated with KrF excimer laser light, an electron beam, X-rays, a high energy light (EUV or the like) having a wavelength of 50 nm or less, it is preferable that the resin (A) further have a hydroxystyrene-based repeating unit. It is more preferable to include a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected by an acid decomposable group and an acid decomposable repeating unit such as tertiary alkyl (meth)acrylic ester.

[0193] Examples of the repeating unit having a preferable hydroxystyrene-based acid decomposable group may include a repeating unit by t-butoxycarbonyloxy styrene, 1-alkoxyethoxy styrene, tertiary alkyl (meth)acrylic ester or the like may be included, and a repeating unit by 2-alkyl-2-adamantyl (meth)acrylate and dialkyl(l-adamantyl)methyl (meth)acrylate is more preferable.

[0194] The resin (A) of the present invention can be synthesized according to a routine method (for example, by radical polymerization). For example, as the general synthesis method, a bulk polymerization method in which polymerization is carried out by dissolving monomer species and an initiator in a solvent and heating the solution, a dropwise adding polymerization method in which a solution of monomer species and an initiator is added dropwise to a heating solvent over 1 to 10 hours, or the like may be included, and a dropwise adding polymerization method is preferable. Examples of the reaction solvent may include a solvent which dissolves the composition of the present invention such as ethers such as tetrahydrofuran, 1,4-dioxane or diisopropyl ether, ketones such as methylethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethyl formamide or dimethyl acetamide, propylene glycol mono methyl ether acetate described later, propylene glycol monomethyl ether or cyclohexanone. It is more preferable to perform polymerization using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, generation of the particles during storage can be suppressed.

[0195] It is preferable that the polymerization reaction be carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, commercially available radical initiators (an azo-based initiator, peroxide, or the like) are used to initiate the polymerization. As the radical initiator, an azo-based initiator is preferable, and the azo-based initiator having an ester group, a cyano group or a carboxyl group is preferable. Preferable initiators may include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methyl propionate), or the like. The initiator is added or added in installments, when necessary, and the desired polymer is recovered after the reaction is complete by being added to a solvent and using a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass and preferably 10 to 30% by mass. The reaction temperature is normally 10°C to 150°C, preferably 30°C to 120°C, and more preferably 60°C to 100°C.

[0196] After the reaction is complete, the resultant is allowed to cool to room temperature and purified. Purification may be carried out using common methods such as a liquid-liquid extraction method in which residual monomers and oligomer components are removed by washing with water or combining appropriate solvents, a purification method in a solution state such as ultrafiltration in which only those with less than or equal to a specific molecular weight are extracted and removed, a re-precipitation method in which residual monomers and the like are removed by coagulating the resin in a poor solvent through dropwise addition of the resin solution to a poor solvent, and a purification method in a solid state in which separated resin slurry is washed with a poor solvent. For example, the resin is precipitated as solids by contacting the resin with a sparingly soluble or insoluble solvent (a poor solvent) in 10 times or less of the volume of the reaction solution, and preferably 5 to 10 times of the volume.

[0197] The solvent used during precipitation or reprecipitation from the polymer solution (precipitation or reprecipitation solvent) may be a poor solvent of the polymer, and may be appropriately selected and used from hydrocarbons, halogenated hydrocarbons, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, and a mixed solvent including these solvents, depending on the type of polymer. Among these, as the precipitation or reprecipitation solvent, a solvent containing at least alcohols (particularly, methanol or the like) or water is preferable.

[0198] The amount of the precipitation or reprecipitation solvent used may be appropriately selected considering efficiency and yield, however, is 100 to 10,000 parts by mass, preferably 200 to 2,000 parts by mass, and is more preferably 300 to 1,000 parts by mass with regard to 100 parts by mass of the polymer solution, in general.

[0199] The precipitation or re-precipitation temperature may be appropriately selected considering efficiency and operability, however, is normally 0°C to 50°C, and preferably around room temperature (for example, approximately, 20°C to 35°C). Precipitation or re-precipitation operation may be carried out by well-known methods of batch-type or continuous-type using a common mixing vessel such as a stirring tank.

[0200] Typically, the precipitated or reprecipitated polymer is provided for use after being subjected to common solid-liquid separation such as filtration and centrifugation, and then dried. Filtration is carried out using a filtration material with solvent resistance, preferably under pressure. Drying is carried out at a temperature of approximately 30°C to 100°C, preferably approximately 30°C to 50°C under normal pressure or reduced pressure (preferably under reduced pressure).

[0201] In addition, after the resin is precipitated and separated once, the resin is re-dissolved in a solvent, and the resin may be contacted with a sparingly soluble or insoluble solvent. In other words, after the radical polymerization reaction above is complete, a method may be used in which the polymer is brought into contact with a sparingly soluble or insoluble solvent, and the resin is precipitated (step a), the resin is separated from the solution (step b), then, the resin is re-dissolved in a solvent and the resin solution A is prepared (step c), after that, the resin solid is precipitated by contacting the resin solution A with the sparingly soluble or insoluble solvent in 10 times or less volume of the resin solution A (preferably 5 times or less volume) (step d), and the resin precipitated is separated (step e).

[0202] In addition, in order to suppress aggregation of the resin after the composition is prepared, a step, in which the resin synthesized is dissolved in a solvent so as to prepare a solution, and the solution is heated at approximately 30°C to 90°C for approximately 30 minutes to 4 hours, may be added as disclosed in, for example, JP2009-037108A.

[0203] The weight average molecular weight of the resin (A) used in the composition of the present invention as a value calculated relative to polystyrene standards according to the GPC method is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 70,000, and particularly preferably 5,000 to 50,000. By keeping the weight average molecular weight as 1,000 to 200,000, deterioration of heat resistance and dry etching resistance may be prevented and developability deterioration or deterioration of film formability due to high viscosity may be prevented.

[0204] The degree of dispersion (molecular weight distribution) is generally in the range of 1.0 to 3.0. The range is preferably 1.0 to 2.6, more preferably 1.1 to 2.5, even more preferably 1.2 to 2.4, particularly preferably 1.3 to 2.2, and more particularly preferably 1.4 to 2.0. If the molecular weight distribution meets the above range, the resolution and the resist shape are excellent, the side wall of the resist pattern is also smooth, and the roughness property is excellent.

[0205] In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the mixing ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, and more preferably 60 to 95% by mass, of the total solids content.

[0206] Furthermore, the resin (A) of the present invention may be used individually, or plural resins may be used in combination.

[0207] [3] Compound (B) which generates an acid by irradiation of actinic rays or radiation [0208] The composition according to the present invention may contain a compound (B) which generates an acid by irradiation of actinic rays or radiation (hereinafter, also referred to as "acid generator" or "compound (B)"). The compound (B) which generates an acid by irradiation of actinic rays or radiation is preferably a compound which generates an organic acid by irradiation of actinic rays or radiation.

[0209] As the acid generator, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photo-decoloring agent for coloring agents, photo-discoloring agent, or a known compound which generates an acid by irradiation of actinic rays or radiation, or a mixture of such compounds, which is used in microresists or the like can be appropriately selected and used.

[0210] For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, imide sulfonate, oxime sulfonate, diazo disulfone, disulfone, o-nitrobenzyl sulfonate may be included.

[0211] Preferable compounds for the acid generator include a compound represented by following General Formulae (ZI), (ZII), and (ZIII).

[Chem. 27]

In General Formula (ZI) described above,

R201 , R202, and R ₂ o3 each independently represent an organic group.

[0212] The number of carbons of the organic group as R ₂₀ i, R ₂₀₂ and R ₂₀₃ is generally 1 to 30, and preferably 1 to 20.

[0213] In addition, two of R ₂₀ i to R ₂₀₃ may be bonded to form a ring structure, and may include an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group in the ring. As the group formed by two of R ₂₀ i to R ₂ o ₃ being bonded, an alkylene group (for example, a butylene group or a pentylene group) may be included.

[0214] Z ^" represents a non-nucleophilic anion.

[0215] The non-nucleophilic anion as Z ^" , for example, a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion or the like may be included.

[0216] The non-nucleophilic anion is an anion of which capacity to initiate a nucleophilic reactions is extremely low, and an anion capable of suppressing decomposition over time by an intramolecular nucleophilic reaction. According to this, the temporal stability of the actinic ray-sensitive or radiation- sensitive resin composition is improved.

[0217] As the sulfonate anion, for example, an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, or the like, may be included.

[0218] Examples of the carboxylate anion may include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion or the like.

[0219] The aliphatic site in the aliphatic sultanate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, is preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, and may include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a bornyl group, or the like.

[0220] The aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion may preferably include an aryl group having 6 to 14 carbon atoms, and may include, for example, a phenyl group, a tolyl group, a naphthyl group, or the like.

[0221] The alkyl group, the cycloalkyl group, and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion may have a substituent. As the substituent of the alkyl group, the cycloalkyl group, and the aryl group in the aliphatic sultanate anion and the aromatic sulfonate anion, for example, a nitro group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably 6 to 20 carbon atoms), an alkyl aryloxysulfonyl group (preferably 7 to 20 carbon atoms), a cycloalkyl aryloxysulfonyl group (preferably 10 to 20 carbon numbers), an alkyloxy alkyloxy group (preferably 5 to 20 carbon atoms), a cycloalkyl alkyloxy alkyloxy group (preferably 8 to 20 carbon atoms), or the like, may be included. Regarding the aryl group and the ring structure each group has, an alkyl group (preferably 1 to 15 carbon atoms) or a cycloalkyl group (preferably 3 to 15 carbon atoms) may be further included as a substituent.

[0222] The aralkyl group in the aralkyl carboxylate anion may preferably include an aralkyl group having 7 to 12 carbon atoms, and may include, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl- group, or the like.

[0223] The alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group in the aliphatic carboxylate anion, the aromatic carboxylate anion and the aralkyl carboxylate anion may have a substituent. As this substituent, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group or the like, the same as those in the aromatic sulfonate anion.

[0224] As the sulfonylimide anion, for example, a saccharin anion may be included.

[0225] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms, and may include, for example, a methyl group, an ethyl group, a propyl group, an iso propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, or the like. As the substituent of these alkyl groups of these is preferably a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkyl aryloxysulfonyl group substituted with a halogen atom, or the like may be included, and an alkyl group substituted with a fluorine atom is preferable.

[0226] Examples of other non-nucleophilic anions may include fluorophosphate (for example, PF ₆ ^" ), fluoroborate (for example, BF ₄ ^" ), fluoroantimonate (for example, SbF ₆ ^" ) or the like.

[0227] As the non-nucleophilic anion of Z ^" , an aliphatic sulfonate anion in which at least a-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion of which alkyl group is substituted with a fluorine atom or a tris(alkylsulfonyl)methide anion of which alkyl group is substituted with a fluorine atom is preferable. The non-nucleophilic anion is more preferably a perfluoro aliphatic sulfonate anion having 4 to 8 carbon atoms or a benzene sulfonate anion having a fluorine atom, and is even more preferably a nonafluorobutane sulfonate anion, a perfluorooctane sulfonate anion, a pentafluorobenzene sulfonate anion or 3,5-bis(trifluoromethyl)benzene sulfonate anion.

[0228] The acid generator is preferably a compound which generates an acid represented by the following General Formula (IIIB) or (IVB), by irradiation of actinic rays or radiation. Since a compound which generates an acid represented by the following General Formula (IIIB) or (IVB) has a cyclic organic group, resolution and roughness performance can be further improved.

[0229] As the non-nucleophilic anion, an anion generating an organic acid represented by the following General Formula (1IIB) or (IVB) can be used.

Chem. 28]

(1MB) (IVB)

In General Formulae described above,

Xfs each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom.

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

Ls each independently represent a divalent linking group.

Cy represents a cyclic organic group.

Rf is a group including a fluorine atom.

x represents an integer of 1 to 20.

y represents an integer of 0 to 10.

z represents an integer of 0 to 10.

[0230] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, more preferably 1 to 4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0231] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F , C5F11, C ₆ F _{) 3} , C ₇ Fi ₅ , C ₈ Fi7, CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F _S , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , or CH ₂ CH ₂ C ₄ F9, and more preferably a fluorine atom or CF ₃ . In particular, it is preferable that both Xfs are fluorine atom.

[0232] R] and R ₂ , each dependently, represent a hydrogen atom, a fluorine atom, or an alkyl group. This alkyl group may have a substituent (preferably a fluorine atom) and is preferably an alkyl group having 1 to 4 carbon atoms. More preferably, this alkyl group is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent as Ri and R ₂ , may include, for example, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ Fn, C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , or CH ₂ CH ₂ C ₄ F ₉ , and among these, CF ₃ is preferable.

[0233] L represents a divalent linking group. As this divalent linking group, for example, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -0-, -S-, -SO-, -S0 ₂ -, an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), a divalent linking group combining a plurality of these or the like may be included. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -0-, -S0 ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group- or -NHCO-alkylene group-, is preferable, and -COO-, -OCO-, -CONH-, -S0 ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferable.

[0234] Cy represents a cyclic organic group. As the cyclic organic group, for example, an alicyclic group, an aryl group, and a heterocyclic group may be included.

[0235] The alicyclic group may be monocyclic or polycyclic. As the monocyclic alicyclic group, for example, a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group may be included. As the polycyclic alicyclic group, for example, a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group may be included. Among these, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group is preferable from the viewpoint of suppressing diffusivity in a film in PEB step (heating after exposure) and improving MEEF (Mask Error Enhancement Factor).

[0236] The aryl group may be monocyclic or polycyclic. As this aryl group, for example, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group may be included. Among these, a naphthyl group of which light absorbance at 193 nm is relatively low is preferable.

[0237] The heterocyclic group may be monocyclic or polycyclic, however, a polycyclic heterocyclic group can suppress diffusion of acid more. In addition, the heterocyclic group may or may not have aromaticity. As the heterocyclic group which has aromaticity, for example, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring and pyridine ring may be included. As the heterocyclic group which does not have aromaticity, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, or a decahydroisoquinoline ring may be included. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Furthermore, examples of the lactone ring and the sultone ring may be the lactone structure and the sultone structure illustrated for the above-described resin (A).

[0238] The above cyclic organic group may have a substituent. Examples of this substituent may include an alkyl group (may be chainlike or branched, and preferably having 1 to 12 carbon atoms), a cycloalkyl group (may be monocyclic, polycyclic or spirocyclic, and preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, an ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the ring formation) may also be carbonyl carbon.

[0239] x is preferably 1 to 8, preferably 1 to 4 among these, and particularly preferably 1. y is preferably 0 to 4 and more preferably 0. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.

[0240] As the group containing a fluorine atom represented by Rf, for example, an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom may be included.

[0241] These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom or may be substituted with other substituents containing a fluorine atom. If Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, the other substituents containing a fluorine atom may include, for example, an alkyl group substituted with at least one fluorine atom.

[0242] In addition, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent which does not contain a fluorine atom. As this substituent, for example, substituents which do not contain a fluorine atom among the substituents described above for Cy may be included.

[0243] As the alkyl group having at least one fluorine atom represented by Rf, for example, the same alkyl group substituted with at least one fluorine atom represented by Xf described above may be included. As the cycloalkyl group having at least one fluorine atom represented by Rf, for example, a perfluorocyclopentyl group and a perfiuorocyclohexyl group may be included. As the aryl group having at least one fluorine atom represented by Rf, for example, a perfluorophenyl group may be included.

[0244] In General Formulae described above, as a particularly preferred aspect, an aspect in which x is 1, two of Xfs represent a fluorine atom, y is 0 to 4, all of Ris and R ₂ s represent a hydrogen atom, and z is 1 may be exemplified. In this aspect, fluorine atoms are present in a small amount and the compound is not likely to be unevenly distributed in the surface of the resist film during forming the resist film. Therefore, the compound is likely to be uniformly dispersed in the resist film.

[0245] As the organic group represented by R ₂₀ i, R ₂₀₂ , and R ₂₀₃ , for example, corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later may be included.

[0246] In addition, the organic group may be a compound having a plurality of structures represented by General Formula (ZI). For example, a compound having a structure in which at least one of R ₂₀ i to R ₂₀₃ of the compound represented by General Formula (ZI) is bonded to at least one of R ₂₀ i to R ₂₀₃ of another compound represented by General Formula (ZI) through a single bond or a linking group may be included.

[0247] The more preferable (ZI) component may include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

[0248] The compound (ZI-1) is an aryl sulfonium compound in which at least one of R ₂₀ i to R ₂₀₃ of General Formula (ZI) described above is an aryl group, that is, a compound in which the aryl sulfonium is a cation.

[0249] In the aryl sulfonium compound, all of R ₂₀ i to R ₂₀₃ may be an aryl group, or a part of R ₂₀ i to R ₂₀ 3 may be an aryl group and the rest is an alkyl group or a cycloalkyl group.

[0250] The aryl sulfonium compound may include, for example, a triarylsulfonium compound, a diaryl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diaryl cycloalkyl sulfonium compound or an aryl dicycloalkyl sulfonium compound.

[0251] As the aryl group of the aryl sulfonium compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. The heterocyclic structure may include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, a benzothiophene residue, or the like. When the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same as or different from each other.

[0252] The alkyl group or the cycloalkyl group which the aryl sulfonium compound has when necessary is preferably a straight chain or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, and may include, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, or the like.

[0253] The aryl group, the alkyl group, and the cycloalkyl group of R ₂₀ i to R ₂₀₃ may have an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group as a substituent. The substituent is preferably a straight chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a straight chain, branched, or cyclic alkoxy group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The substituent may substitute any one of three R ₂₀ i to R ₂₀₃ , or may substitute all three. In addition, when R ₂ oi to R ₂₀₃ are an aryl group, the substituent preferably substitutes p-position of the aryl group.

[0254] Next, a compound (ZI-2) will be described.

[0255] The compound (ZI-2) is a compound in which R ₂₀ i to R ₂₀₃ in the Formula (ZI) each independently represent an organic group which does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

[0256] In the organic group which does not contain an aromatic ring as R ₂₀ i to R ₂₀₃ , the number of carbon atoms is generally 1 to 30 and the number of carbon atoms is preferably 1 to 20.

[0257] R ₂₀ i to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a straight chain or branched 2-oxo alkyl group, a 2-oxo cycloalkyl group, an alkoxycarbonyl methyl group, and particularly preferably a straight chain or branched 2-oxo alkyl group.

[0258] As the alkyl group and the cycloalkyl group of R ₂₀ i to R ₂₀₃ , a straight chain or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group), a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group or a norbonyl group) may be preferably included. As the more preferable alkyl group, a 2-oxo alkyl group or an alkoxycarbonyl methyl group may be included. As the more preferable cycloalkyl group, a 2-oxo cycloalkyl group may be included.

[0259] The 2-oxo alkyl group may be either straight chain or branched and preferably include a group having >C=0 at 2-position of the above alkyl group.

[0260] The 2-oxo cycloalkyl group may preferably include a group having >C=0 at 2-position of the above cycloalkyl group.

[0261] The alkoxy group in the alkoxycarbonyl methyl group may preferably include an alkoxy group having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group).

[0262] R ₂₀ i to R ₂ o3 may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0263] Next, a compound (ZI-3) will be described.

[0264] The compound (ZI-3) is a compound represented by General Formula (ZI-3) below, and is a compound having a phenacylsulfonium salt structure.

[Chem. 29]

In General Formula (Zl-3),

Ri _c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

R _f c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, and a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonyl alkyl group, an allyl group or a vinyl group.

[0265] Two or more of Ri _c to R _5c , R _5c and R^, R^ and R _7c , R _5c and R _x , and R _x and R _y , may be bonded to each other to form a ring structure, and this ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.

[0266] The ring structure may include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic condensed ring formed by two or more of these rings being combined. As the ring structure, 3- to 10-membered ring may be included, 4- to 8-membered ring is preferable, and 5- or 6-membered ring is more preferable.

[0267] The group formed by two or more of Ri _c to R _5c , R6 _C and R _7c , and R _x and R _y being bonded may include a butylene group, pentylene group or the like.

[0268] The group formed by R _5c and R^, and R _5c and R _x being bonded may preferably include a single bond or an alkylene group, and as an alkylene group, a methylene group, an ethylene group or the like may be included.

[0269] Zc ^" represents a non-nucleophilic anion, and may include the same non-nucleophilic anion as Z ^" in General Formula (ZI).

[0270] The alkyl group as Ri _c to R _7c may be either straight chain or branched, and may include, for example, an alkyl group having 1 to 20 carbon atoms, preferably a straight chain or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a straight chain or branched propyl group, a straight chain or branched butyl group, or a straight chain or branched pentyl group), and the cycloalkyl group may include a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group or a cyclohexyl group).

[0271] The aryl group as Ri _c to R _5c preferably has 5 to 15 carbon atoms, and may include, for example, a phenyl group or a naphthyl group.

[0272] The alkoxy group as Ri _c to R _5c may be any of straight chain, branched and cyclic, and may include, for example, an alkoxy group having 1 to 10 carbon atoms, preferably, a straight chain and branched alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a straight chain or branched propoxy group, a straight chain or branched butoxy group, or a straight chain or branched pentoxy group), a cyclic alkoxy group having 3 to 10 carbon atoms (for example, a cyclopentyloxy group or a cyclohexyloxy group).

[0273] Specific examples of the alkoxy group in the alkoxycarbonyl group as Ri _c to R _5c are the same as specific examples of the alkoxy group as R] _C to R _5c described above.

[0274] Specific examples of the alkyl group in the alkylcarbonyloxy group and the alkylthio group as Ri _c to R _5c are the same as specific examples of the alkyl group as Ri _c to R _5c described above.

[0275] Specific examples of the cycloalkyl group in the cycloalkyl carbonyloxy group as Ri _c to R _5c are the same as specific examples of the cycloalkyl group of Ri _c to R _5c described above.

[0276] Specific examples of the aryl group in the aryloxy group and the arylthio group as Ri _c to Rs _c are the same as specific examples of the aryl group Ri _c to Rs described above.

[0277] Preferably, any of R _{i c} to R _5c is a straight chain or branched alkyl group, a cycloalkyl group, or a straight chain, branched or cyclic alkoxy group, and more preferably, the sum of the number of carbon atoms in Ri _c to R _5c is 2 to 15. As a result, solvent solubility is further improved and the generation of particles is suppressed when stored. [0278] As the ring structure which may be formed by two or more of Ri _c to R _5c being bonded to each other, 5-membered or 6-membered ring may be preferably included, and a 6-membered ring (for example, a phenyl ring) may be particularly preferably included.

[0279] The ring structure which may be formed by R _5c and R<5c being bonded to each other may include a 4-membered ring or more (particularly preferably 5- to 6-membered ring) formed together with a carbonyl carbon atom and a carbon atom in General Formula (I) by R _5c and R6c being bonded to each other and constituting a single bond or an alkylene group (a methylene group, an ethylene group, or the like).

[0280] The aryl group as R^ and R _7c preferably has 5 to 15 carbon atoms, and may include, for example, a phenyl group or a naphthyl group.

[0281] As an aspect of R6c and R _7c , it is preferable that both of them be an alkyl group. In particular, it is preferable that each of R^ and R _7c be a straight chain or branched alkyl group having 1 to 4 carbon atoms, and particularly, it is preferable that both be a methyl group.

[0282] In addition, when R^ and R _7c are bonded to each other to form a ring, the group formed by R _f c and R _7c being bonded and is preferably an alkylene group having 2 to 10 carbon atoms, and may include, for example, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, or the like. In addition, the ring formed by R6 _C and R _7c being bonded may have a hetero atom such as an oxygen atom in the ring.

[0283] The alkyl group and the cycloalkyl group as R _x and R _y may include the same alkyl group and the cycloalkyl group as Ri _c to R _7c .

[0284] The 2-oxoalkyl group and the 2-oxocycloalkyl group as R _x and R _y may include the group having >C=0 at 2-position of the alkyl group and the cycloalkyl group as Ri _c to R _7c .

[0285] The alkoxy group in the alkoxycarbonyl alkyl group as R _x and R _y may include the same alkoxy group in Ri _c to R _5c , and the alkyl groups may include, for example, an alkyl group having 1 to 12 carbon atoms, and preferably include a straight chain alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

[0286] The allyl group as R _x and R _y is not particularly limited, however, an unsubstituted allyl group, or an allyl group substituted with a monocyclic or polycyclic cycloalkyl group

(preferably a cycloalkyl group having 3 to 10 carbon atoms) is preferable.

[0287] The vinyl group as R _x and R _y is not particularly limited, however, an unsubstituted vinyl group, or a vinyl group substituted with a monocyclic or polycyclic cycloalkyl group

(preferably a cycloalkyl group having 3 to 10 carbon atoms) is preferable.

[0288] The ring structure which may be formed by R _5c and R _x being bonded to each other may include a 5-membered ring or more (particularly preferably 5-membered ring) formed together with a sulfur atom and a carbonyl carbon atom in General Formula (I) by R _c and R _x being bonded to each other and constituting a single bond or an alkylene group (a methylene group, an ethylene group, or the like).

[0289] The ring structure which may be formed by R _x and R _y being bonded to each other may include a 5-membered or 6-membered ring, particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring) formed by divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group or the like) together with a sulfur atom in General Formula (ZI-3).

[0290] R _x and R _y are preferably an alkyl group having 4 or more carbon atoms or a cycloalkyl group, and are an alkyl group having more preferably 6 or more, even more preferably 8 or more carbon atoms, or a cycloalkyl group.

[0291] i _c to R _7c , R _x , and R _y may have further substitueiits and the substituent such as this may include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an arylcarbonyl group, an alkoxyalkyl group, an aryloxy alkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an aryloxy carbonyloxy group, or the like.

[0292] Ri _c , R _2c , R-i _c , and R _5c in General Formula (ZI-3) described above each independently represent a hydrogen atom, and, more preferably, R _3c represents a group other than a hydrogen atom, that is, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

[0293] As the cation in the compound (ZI-2) or (ZI-3) according to the present invention, the cations described in paragraphs [0130] to [0134] of JP2010-256842A, paragraphs [0136] to [0140] of JP2011-76056A, and the like may be exemplified.

[0294] Next, a compound (ZI-4) will be described.

[0295] The compound (ZI-4) is represented by the following General Formula (ZI-4).

[Chem. 30]

In General Formula (ZI-4),

Ri ₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a group having a cycloalkyl group. These groups may have a substituent.

If Ri ₄ is present in plural numbers, Ri ₄ s each independently represent a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a cycloalkyl group. These groups may have a substituent.

Ri ₅ s each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R15S may be bonded to each other to form a ring. These groups may have a substituent.

1 represents an integer of 0 to 2.

r represents an integer of 0 to 8.

Z ^" represents a non-nucleophilic anion, and may include the same non-nucleophilic anion as Z ^" in General Formula (ZI).

[0296] In General Formula (ZI-4), the alkyl group of R13, RH, and R ₁₅ has a straight chain shape or a branched shape, preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0297] The cycloalkyl group of R] ₃ , Ri ₄ , and Ri ₅ may include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and is preferably cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0298] The alkoxy group of Ri ₃ and R14 has a straight chain shape or a branched shape, preferably has 1 to 10 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, or the like.

[0299] The alkoxycarbonyl group of R13 and R14 has a straight chain shape or a branched shape, preferably has 2 to 11 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, or the like.

[0300] As the group having a cycloalkyl group of R13, and RH, may include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), and may include, for example, a monocyclic or polycyclic cycloalkyloxy group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

[0301] As the monocyclic or polycyclic cycloalkyloxy group of Ri ₃ , and Rn, the number of total carbon atoms is preferably 7 or more, the number of total carbon atoms is more preferably greater than or equal to 7 and less than or equal to 15, and, furthermore, having a monocyclic cycloalkyl group is preferable. The monocyclic cycloalkyloxy group having 7 or more total carbon atoms is a monocyclic cycloalkyloxy group in which a cycloalkyloxy group such as a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclododecanyloxy groups has an arbitrary substituent such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group, a 2-ethylhexyl group, an isopropyl group, a sec-butyl group, a t-butyl group or an iso-amyl group, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group or a butoxy group, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group or a benzoyl group, an acyloxy group such as an acetoxy group or a butyryloxy group, a carboxyl group, or the like, and represents a monocyclic cycloalkyloxy group in which the number of total carbon atoms combined with an arbitrary substituent on the cycloalkyl group is 7 or more.

[0302] In addition, the polycyclic cycloalkyloxy group having a 7 or more total carbon atoms may include a norbonyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantyloxy group, or the like.

[0303] As the alkoxy group having a monocyclic or polycyclic cycloalkyl group of Ri ₃ , and RH, the number of total carbon atoms is preferably 7 or more, the number of total carbon atoms is more preferably greater than or equal to 7 and less than or equal to 15, and, furthermore, an alkoxy group having a monocyclic cycloalkyl group is preferable. The alkoxy group having a monocyclic cycloalkyl group having 7 or more total carbon atoms is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptoxy group, an octyloxy group, a dodecyloxy group, a 2-ethylhexyloxy group, an isopropoxy group, a sec-butoxy group, a t-butoxy group or an iso-amyloxy group substituted with the monocyclic cycloalkyl group described above, and represents a group in which the number of total carbon atoms including the substituent is 7 or more. For example, a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group or the like may be included, and a cyclohexylmethoxy group is preferable.

[0304] In addition, the alkoxy group having a polycyclic cycloalkyl group having a 7 or more total carbon atoms may include a norbornylmethoxy group, a norbornylethoxy group, a tricyclodecanylmethoxy group, a tricyclodecanylethoxy group, a tetracyclodecanylmethoxy group, a tetracyclodecanylethoxy group, an adamantylmethoxy group, an adamantylethoxy group or the like, and is preferably a norbornylmethoxy group, a norbornylethoxy group, or the like.

[0305] As the alkyl group of the alkylcarbonyl group of RH, the same specific examples as R _{] 3} to Ri5 described above may be included.

[0306] The alkylsulfonyl group and the cycloalkylsulfonyl group of Ri ₄ have a straight chain shape, a branched shape or a cyclic shape, and preferably has 1 to 10 carbon atoms, and is preferably, for example, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentane sulfonyl group, a cyclohexanesulfonyl group, or the like.

[0307] As the substituent which each group described above may have, a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group or the like may be included.

[0308] The alkoxy group includes, for example, a straight chain, branched, or cyclic alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, a cyclopentyloxy group a cyclohexyloxy group, or the like.

[0309] The alkoxyalkyl group includes, for example, a straight chain, branched, or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group or a 2-ethoxyethyl group, or the like.

[0310] The alkoxycarbonyl group includes, for example, a straight chain, branched, or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, a 1-methylpropoxycarbonyl group, a t-butoxycarbonyl group, a cyclopentyloxycarbonyl group or a cyclohexyloxycarbonyl group, or the like.

[0311 ] The alkoxycarbonyloxy group includes, for example, a straight chain, branched, or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, an n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, cyclopentyloxycarbonyloxy group or a cyclohexyloxycarbonyloxy, or the like.

[0312] The ring structure which may be formed by two Ri ₅ s being bonded to each other may include a 5-membered or 6-membered ring, particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring) formed by two R ₁₅ s together with a sulfur atom in General Formula (ZI-4), and may be ring condensed with an aryl group or cycloalkyl group. This divalent Ri ₅ may have a substituent, and examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. The substituent for the ring structure may be present in plural numbers and these may be bonded to each other to form a ring (an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, or a polycyclic condensed ring formed by combining two or more of these rings).

[0313] Ri5 in General Formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two Ri ₅ s are bonded to each other and form a tetrahydrothiophene ring structure together with a sulfur atom, or the like.

[0314] The substituent which Ri ₃ and Ri ₄ may have is preferably a hydroxyl group, an alkoxy group an alkoxycarbonyl group, or a halogen atom (particularly, a fluorine atom).

[0315] As 1, 0 or 1 is preferable, and 1 is more preferable.

[0316] As r, 0 to 2 is preferable.

[0317] Examples of the cation of the compound represented by General Formula (ZI-4) according to the present invention include the cations described in paragraphs [0121], [0123] and [0124] of JP2010-256842A, paragraphs [0127], [0129] and [0130] of JP2011-76056A, and the like.

[0318] Next, General Formulae (ZII) and (ZIII) will be described.

[0319] In General Formulae (ZII) and (ZIII), R ₂₀₄ to R-207 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.

[0320] The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may also be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. As the skeleton of the aryl group having a heterocyclic structure, for example, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, or the like, may be included.

[0321] The alkyl group and the cycloalkyl group in R ₂₀ 4 to R ₂₀₇ may preferably include a straight-chain or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group), a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group, a norbonyl group).

[0322] The aryl group, the alkyl group, and the cycloalkyl group of R ₂₀₄ to R ₂ o ₇ may have a substituent. As the substituent, the aryl group, the alkyl group, and the cycloalkyl group of R ₂ 04 to R ₂₀₇ may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group, or the like, may be included.

[0323] Z ^" represents a non-nucleophilic anion, and may include the same non-nucleophilic anion as Z ^" in General Formula (ZI).

[0324] As the acid generator, compounds represented by the following General Formulae (ZIV), (ZV) and (ZVI) may also be exemplified.

[Chem. 31]

In General Formulae (ZIV) to (ZVI),

Ar ₃ and Ar ₄ each independently represent an aryl group.

208, R209, and R ₂ io each independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

[0325] Specific examples of the aryl group of Ar ₃ , Ar ₄ , R208, R209, and R210 may include the same specific examples of the aryl group of R ₂₀₁ , R ₂₀₂ , and R ₂₀₃ in General Formula (ZI-1) described above.

[0326] Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R209, and R ₂ i ₀ may include the same specific examples of the alkyl group and the cycloalkyl group of R ₂₀ i, R ₂₀₂ , and R ₂₀₃ in General Formula (ZI-2) described above, respectively.

[0327] The alkylene group of A may include an alkylene group having 1 to 12 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, or the like), the alkenylene group of A may include an alkenylene group having 2 to 12 carbon atoms (for example, an ethenylene group, a propenylene group, a butenylene group, or the like), and the arylene group of A may include an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, a naphthylene group, or the like), respectively.

[0328] In the acid generator, a compound represented by General Formulae (ZI) to (ZIII) is more preferable.

[0329] In addition, the acid generator is preferably a compound which generates acid having one sulfonate group or imide group, more preferably a compound which generates monovalent perfluoroalkanesulfonic acid, a compound which generates monovalent aromatic sulfonic acid substituted with a fluorine atom or a group containing a fluorine atom, a compound which generates monovalent imide acid substituted with a fluorine atom or a group containing a fluorine atom, and even more preferably fluorine- substituted alkanesulfonic acid, fluorine-substituted benzenesulfonic acid, fluorine-substituted imide acid, or a sulfonium salt of fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkanesulfonic acid, a fiuorinated substituted benzenesulfonic acid, or a fluorinated substituted imide acid, which generates an acid having a pKa of-1 or less, and the sensitivity is enhanced.

[0330] Among the acid generators, particularly preferable examples are shown below.

[Chem. 32]

[Chem. 33]

[Chem. 34]

[Chem. 35]

[0331] The acid generator can be synthesized by well-known methods, and, for example, can be synthesized in accordance with the method disclosed in JP2007- 161707 A.

[0332] The acid generator can be used either alone or as a combination of two or more.

[0333] The content of the compound which generates an acid by irradiation of actinic rays or radiation in the composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass, based on the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition.

[0334] Furthermore, when the acid generator is represented by General Formula (ZI-3) or (ZI-4) described above, the content of the acid generator is preferably 5 to 35% by mass, more preferably 8 to 30% by mass, still more preferably 9 to 30% by mass, and particularly preferably 9 to 25% by mass, based on the total solids content of the composition.

[0335] [4] Solvent (C)

[0336] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a solvent. The solvent is not particularly limited as long as it is a solvent which can be used when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is prepared, but examples thereof may include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a cyclic structure (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0337] Specific examples of these solvents may include those disclosed in [0441] to [0455] of US2008/0187860 A.

[0338] In the present invention, a mixed solvent in which a solvent containing a hydroxyl group in the structure is mixed with a solvent not containing a hydroxyl group may be used as an organic solvent.

[0339] The solvent containing a hydroxyl group and the solvent not containing a hydroxyl group may be appropriately selected from the compounds exemplified above, however, as a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate or the like is preferable, and propylene glycol monomethyl ether (PGME, alias l-methoxy-2-propanol) or ethyl lactate is more preferable as a solvent containing a hydroxyl group. In addition, alkylene glycol mono alkyl ether acetate or alkyl alkoxy propionate, a monoketone compound which may also have a ring, cyclic lactone, alkyl acetate or the like is preferable as the solvent not containing a hydroxyl group, propylene glycol monomethyl ether acetate (PGMEA, alias l-methoxy-2-acetoxypropane), ethyl ethoxy propionate, 2-heptanone, γ-butyro lactone, cyclohexanone or butyl acetate is particularly preferable, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, or 2-heptanone is the most preferable.

[0340] The mixing ratio (mass) of the solvent containing a hydroxyl group and a solvent containing no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably is a 20/80 to 60/40. The mixed solvent containing 50% by mass or more of the solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.

[0341] The solvent may preferably contain propylene glycol monomethyl ether acetate, and is preferably a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[0342] [5] Hydrophobic resin (D) which is different from the resin (A)

[0343] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a hydrophobic resin which is different from the resin (A) (hereinafter, also referred to as "hydrophobic resin (D)" or simply as "resin (D)"), particularly when the actinic ray-sensitive or radiation-sensitive resin composition is applied to immersion exposure.

[0344] Thereby, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static/dynamic contact angle of the surface of the resist film against water is increased, and thereby the conformity to the immersion liquid can be enhanced.

[0345] It is preferable that the hydrophobic resin (D) be designed so as to be unevenly distributed at the interface as described above. However, since the hydrophobic resin (D) is different from surfactants, it is not necessary for the hydrophobic resin to have a hydrophobic group in the molecule, and the hydrophobic resin may not contribute to uniform mixing of polar/non-polar substances.

[0346] From the viewpoint of being unevenly distributed in the film surface layer, it is preferable that the hydrophobic resin (D) contain any one or more kind of a "fluorine atom", a "silicon atom", and a "CH ₃ partial structure contained in a side chain moiety of the resin", and the hydrophobic resin (D) may contain two or more kinds thereof.

[0347] When the hydrophobic resin (D) contains a fluorine atom and/or a silicon atom, the fluorine atom and/or the silicon atom in the hydrophobic resin (D) may be included in the main chain of the resin, or may be included in a side chain.

[0348] When the hydrophobic resin (D) contains a fluorine atom, the resin preferably has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom, as a partial structure containing a fluorine atom.

[0349] The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms and more preferably 1 to 4 carbon atoms) is a straight chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may have further substituents in addition to a fluorine atom. [0350] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may have further substituents in addition to a fluorine atom.

[0351] The aryl group having a fluorine atom is an aryl group such as a phenyl group, a naphthyl group, in which at least one hydrogen atom is substituted with a fluorine atom, and may have further substituents in addition to a fluorine atom.

[0352] As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom, preferably, a group represented by following General Formulae (F2) to (F4) may be included, however, the present invention is not limited to these.

[Chem. 37]

(F2) (F3) (F4)

In General Formulae (F2) to (F4),

R ₅₇ to Reg each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight chain or branched). However, at least one of R ₅₇ to R<5 i , at least one of R^ to R6 ₄ and at least one of R^ to R^ each independently represent a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably 1 to 4 carbon atoms).

[0353] R ₅₇ to R<3i and R^ to R^ _? are preferably all fluorine atoms. R^, R6 ₃ , and R^ are preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. ¾ ₂ and ¾ ₃ may be bonded to each other to form a ring.

[0354] Specific examples of the group represented by General Formula (F2) may include, for example, a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di(trifluoromethyl)phenyl group.

[0355] Specific examples of the group represented by General Formula (F3) may include, for example, a trifluoro methyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro(2-methyl)isopropyl group, a nonafluorobutyl group, an octafluoroisobutyl group, a nonafluorohexyl group, a nonafuruoro-t-butyl group, a perfluoroalkyl isopentyl group, a perfluorooctyl group, a perfluoro(trimethyl)hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group, a perfluorocyclohexyl group, or the like. A hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro(2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafuruoro-t-butyl group or a perfluoro isopentyl group is preferable, and a hexafluoroisopropyl group or a heptafluoroisopropyl group is more preferable.

[0356] Specific examples of the group represented by General Formula (F4) may include -C(CF ₃ ) ₂ OH, -C(C ₂ F ₅ ) ₂ OH, -C(CF ₃ )(CH ₃ )OH, -CH(CF ₃ )OH, or the like, and -C(CF ₃ ) ₂ OH is preferable.

[0357] The partial structure including a fluorine atom may be bonded directly to the main chain, or may be bonded to the main chain through a group selected from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a ureylene bond, or a group combining two or more of these.

[0358] Specific examples of the repeating unit having a fluorine atom are shown below, however, the present invention is not limited to these.

[0359] In the specific examples, Xi represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

[Chem. 38]

[Chem. 39]

[0360] The hydrophobic resin (D) may contain a silicon atom. As a partial structure having a silicon atom, a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure is preferable.

[0361] The alkylsilyl structure or the cyclic siloxane structure may include, specifically, a group represented by the following General Formulae (CS-1) to (CS-3).

Chem. 40]

(CS-1) (CS-2) (CS-3)

In General Formulae (CS-1) to (CS-3),

Ri2 to R ₂₆ each independently represent a straight chain or branched alkyl group (preferably 1 to 20 carbon atoms) or a cycloalkyl group (preferably 3 to 20 carbon atoms).

[0362] L ₃ to L5 represent a single bond or a divalent linking group. As the divalent linking group, a single group or a combination of two or more groups (preferably 12 or less total carbon atoms) selected from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a urea bond, may be included.

[0363] n represents an integer of 1 to 5. n is preferably an integer of 2 to 4. [0364] Specific examples of the repeating units having a group represented by General Formulae (CS-1) to (CS-3) are shown below, however, the present invention is not limited to these. In addition, in the specific examples, Xj represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

[Chem. 41]

aCH3, CgHg, C3H7, C^Hg

[0365] Furthermore, as described above, it is also preferable that the hydrophobic resin (D) contain the CH ₃ partial structure in a side chain moiety of the resin.

[0366] As described herein, the CH ₃ partial structure which the side chain moiety in the resin (D) has (hereinafter, simply referred to as a "side chain CH ₃ partial structure") includes a CH ₃ partial structure which an ethyl group, a propyl group, and the like have.

[0367] On the other hand, a methyl group which is bonded directly to the main chain of the resin (D) (for example, an a-methyl group of a repeating unit having a methacrylic acid structure) is not included in the CH ₃ partial structure of the present invention because of small contribution to the uneven distribution of the resin (D) at a surface due to an effect of the main chain.

[0368] More specifically, when the resin (D) includes a repeating unit derived from a monomer having a polymerizable moiety, which has a carbon-carbon double bond, such as a repeating unit represented by the following General Formula (M) and Rn to RH represent CH ₃ "itself, the CH ₃ is not included in the CH ₃ partial structure which the side chain moiety of the present invention has.

[0369] On the other hand, a CH ₃ partial structure which is present from a C-C main chain through any atoms corresponds to the side chain CH ₃ partial structure of the present invention. For example, when Ri i represents an ethyl group (CH ₂ CH ₃ ), Ri i is considered to have "one" side chain CH ₃ partial structure of the present invention.

[Chem. 42]

In General Formula (M) described above,

Rii to Ri ₄ each independently represent a side chain moiety.

[0370] As R _H to Ri ₄ of the side chain moiety, a hydrogen atom, a monovalent organic group and the like are exemplified.

[0371] As the monovalent organic group in Rn to Ri ₄ , an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group and the like are exemplified. These groups may further have substituents.

[0372] The hydrophobic resin (D) is preferably a resin which has a repeating unit having a CH ₃ partial structure in the side chain moiety and it is more preferable that the resin have, as this repeating unit, at least one kind of repeating unit (x) among a repeating unit represented by the following General Formula (II) and a repeating unit represented by the following General Formula (III). [0373] Hereinafter, the repeating unit represented by General Formula (II) will be described in detail.

[Chem. 43]

(I I )

[0374] In General Formula (II) described above, XM represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom and R ₂ represents an organic group which has one or more CH ₃ partial structures and is stable to acid. As described herein, more specifically, the organic group stable to acid is preferably an organic group not having a "group which is capable of being decomposed by the action of an acid and produces a polar group" described in the resin (A).

[0375] The alkyl group of X _b i preferably has 1 to 4 carbon atoms and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, or the like. Among these, a methyl group is preferable.

[0376] X _b i is preferably a hydrogen atom or a methyl group.

[0377] As R ₂ , an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group which have one or more CH ₃ partial structures are exemplified. The above-described cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.

[0378] R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group which has one or more CH ₃ partial structures.

[0379] The organic group which has one or more CH ₃ partial structures and is stable to acid, as R ₂ , preferably has more than or equal to 2 and less than or equal to 10 CH ₃ partial structures and more preferably has more than or equal to 2 and less than or equal to 8 CH ₃ partial structures.

[0380] The alkyl group having one or more CH partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms. Preferred specific examples of the alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl- 3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l ,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like. An isobutyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a

3.5- dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a

2.6- dimethylheptyl group, a l,5-dimethyl-3-heptyl group, and a 2,3,5,7-tetramethyl-4-heptyl group are more preferable.

[0381] The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples thereof may include a group having 5 or more carbon atoms and having a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number thereof is preferably 6 to 30 and particularly preferably 7 to 25. Preferred examples of the cycloalkyl group may include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group. An adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group and a tricyclodecanyl group are more preferable. A norbornyl group, a cyclopentyl group, a cyclohexyl group are still more preferable.

[0382] The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a straight chain or branched alkenyl group having 1 to 20 carbon atoms and more preferably a branched alkenyl group.

[0383] The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms and examples thereof may include a phenyl group and a naphthyl group. A phenyl group is preferable.

[0384] The aralkyl group having one or more CH partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms and examples thereof may include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.

[0385] Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, a 3,5-dimethylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-t-butylcyclohexyl group, an isobornyl group and the like. An isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, a 3,5-dimethylcyclohexyl group, a 3,5-di-tert-butylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-t-butylcyclohexyl group and an isobornyl group are more preferable.

[0386] Preferred specific examples of the repeating unit represented by General Formula (II) will be shown below. In addition, the present invention is not limited to these.

[Chem. 44]

[0387] A repeating unit represented by General Formula (II) is preferably a repeating unit stable to acid (acid nondecomposable repeating unit) and, specifically, a repeating unit which is capable of being decomposed by the action of an acid and does not have a group producing a polar group is preferable.

[0388] Hereinafter, a repeating unit represented by General Formula (III) will be described in detail.

[Chem. 45]

( I II)

In General Formula (III) described above, Xb ₂ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom; R ₃ represents an organic group which has one or more CH ₃ partial structures and is stable to acid; and n represents an integer of 1 to 5.

[0389] The alkyl group of X ₂ preferably has 1 to 4 carbon atoms and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group or the like. A hydrogen atom is preferable.

[0390] X _b2 is preferably a hydrogen atom.

[0391] Since R ₃ represents an organic group stable to acid, more specifically, it is preferable that R ₃ be an organic group not having a "group which is capable of being decomposed by the action of an acid and produces a polar group" described in the resin (A).

[0392] As R ₃ , an alkyl group having one or more CH ₃ partial structures is exemplified.

[0393] The organic group which has one or more CH partial structures and is stable to acid, as R ₃ , preferably has more than or equal to 1 and less than or equal to 10 CH ₃ partial structures, more preferably has more than or equal to 1 and less than or equal to 8 CH ₃ partial structures and still more preferably has more than or equal to 1 and less than or equal to 4 CH ₃ partial structures.

[0394] The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms. Preferred specific examples of the alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, 3-hexyl group, a 2-methyl- 3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dirnethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like. An isobutyl group, a t-butyl group, a

2- methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a

3.5- dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a

2.6- dimethylheptyl group, a l,5-dimethyl-3-heptyl group, and a 2,3,5,7-tetramethyl-4-heptyl group are more preferable.

[0395] Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2,3-dimethylbutyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like. The alkyl group more preferably has 5 to 20 carbon atoms and examples thereof include an isopropyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a

3- methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, and a 2,6-dimethylheptyl group.

[0396] n represents an integer of 1 to 5, more preferably represents an integer of 1 to 3, and still more preferably represents an integer of 1 or 2.

[0397] Preferred specific examples of the repeating unit represented by General Formula (III) will be shown below. In addition, the present invention is not limited to these.

[Chem. 46]

[0398] A repeating unit represented by General Formula (III) is preferably a repeating unit stable to acid (acid nondecompo sable repeating unit) and, specifically, a repeating unit which is capable of being decomposed by the action of an acid and does not have a group producing a polar group is preferable.

[0399] When the resin (D) has a CH ₃ partial structure in a side chain moiety and, further, does not have a fluorine atom and a silicon atom, the content of at least one kind of repeating unit (x) among a repeating unit represented by the following General Formula (II) and a repeating unit represented by the following General Formula (III) is preferably 90 mol% or more and more preferably 95 mol% or more, based on the total content of the repeating units in the resin (D). The content of the repeating unit is typically 100 mol% or less, based on the total content of the repeating units in the resin (D).

[0400] When the resin (D) contains 90 mol% or more of at least one kind of repeating unit (x) among a repeating unit represented by the following General Formula (II) and a repeating unit represented by the following General Formula (III) based on the total content of the repeating units in the resin (D), the surface free energy of the resin (D) increases. As a result, the resin (D) is not likely to be unevenly distributed in the resist film surface layer and the static/dynamic contact angle of the surface of the resist film against water is increased. Therefore, the conformity to the immersion liquid can be enhanced.

[0401] Furthermore, the hydrophobic resin (D) may have at least one group selected from the group of the following (x) to (z), in (i) a case where the hydrophobic resin (D) contains a fluorine atom and/or a silicon atom and in (ii) a case where a CH ₃ partial structure is contained in a side chain moiety of the resin,

(x) an acid group,

(y) a group having a lactone structure, an acid anhydride group, or an acid imide group, and

(z) a group which is capable of being decomposed by the action of an acid.

[0402] As the acid group (x), a phenolic hydroxyl group, a carboxylate group, a fluorinated alcohol group, a sulfonate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl) methylene group, an (alkylsulfonyl)(alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, a tris(alkylsulfonyl) methylene group or the like, may be included.

[0403] The preferable acid group may include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonamide group, and a bis(alkylcarbonyl)methylene group.

[0404] As the repeating unit having an acid group (x), a repeating unit in which the acid group is bonded directly to the main chain of the resin such as a repeating unit by acrylic acid or methacrylic acid, or a repeating unit in which the acid group is bonded to the main chain of the resin through a linking group, or the like, may be included, or introducing the repeating unit to the end of the polymer chain using a polymerization initiator or a chain transfer agent having an acid group when polymerized is also possible, and any of the cases is preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

[0405] The content of the repeating unit having an acid group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, and even more preferably 5 to 20 mol%, based on the total content of the repeating units in the hydrophobic resin (D).

[0406] Specific examples of the repeating unit having an acid group (x) are shown below, however, the present invention is not limited to these. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

[Chem. 47]

[Chem. 48]

[0407] As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.

[0408] The repeating unit including these groups is, for example, a repeating unit in which this group is bonded directly to the main chain of the resin, such as a repeating unit by acrylate and methacrylate. This repeating unit may alternatively be a repeating unit in which this group is bonded to the main chain of the resin through a linking group. This repeating unit may also be introduced at the end of the resin using a polymerization initiator or a chain transfer agent having this acid group when polymerized.

[0409] Examples of the repeating unit having a group having a lactone structure may include the same repeating units as those having a lactone structure, which have been described previously in the section for the acid-degradable resin (A).

[0410] The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol%, more preferably 3 to 98 mol%, and even more preferably 5 to 95 mol%, based on the total content of the repeating units in the hydrophobic resin (D).

[0411] In the hydrophobic resin (D), the repeating unit having a group (z) which is capable of being decomposed by the action of an acid may be the same as the repeating unit having an acid decomposable group as mentioned for the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) which is capable of being decomposed by the action of an acid in the hydrophobic resin (D) is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and still more preferably 20 to 60 mol%, based on the total content of the repeating units in the resin (D).

[0412] The hydrophobic resin (D) may further have a repeating unit represented by the following General Formula (V).

[Chem. 49]

[0413] In General Formula (V), R^i represents a hydrogen atom, an alkyl group (may be substituted with a fluorine atom or the like), a cyano group, or a -CH ₂ -0-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. Rc ₃₁ is preferably a hydrogen atom, a methyl group, a hydro xymethyl group or a trifluoro methyl group, and particularly preferably a hydrogen atom or a methyl group.

[0414] Rc ₃₂ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.

[0415] L _c3 represents a single bond or a divalent linking group.

[0416] In General Formula (V), the alkyl group of Rc ₃ 2 is preferably a straight chain or branched alkyl group having 3 to 20 carbon atoms.

[0417] The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

[0418] The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

[0419] The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

[0420] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.

[0421] Rc ₃₂ is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

[0422] The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (a group represented by -COO-).

[0423] The content of the repeating unit represented by General Formula (V) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, and even more preferably 30 to 70 mol%, based on the total content of the repeating units in the hydrophobic resin.

[0424] Furthermore, it is also preferable that the hydrophobic resin (D) have a repeating unit represented by the following General Formula (CII-AB). [Chem. 50]

( C I I - A B )

In the formula (CII-AB),

Rci i' and R _c i ₂ ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc' represents an atomic group to form an alicyclic structure, including two carbon atoms bonded (C-C).

[0425] The content of the repeating unit represented by General Formula (CII-AB) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, and even more preferably 30 to 70 mol%, based on all repeating units in the hydrophobic resin.

[0426] Specific examples of the repeating units represented by General Formulae (V) and (CII-AB) will be shown below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ , or CN.

[Chem. 51]

[0427] When the hydrophobic resin (D) has fluorine atoms, the content of the fluorine atoms is preferably 5 to 80% by mass, and more preferably 10 to 80% by mass, based on the weight average molecular weight of the hydrophobic resin (D). In addition, the content of the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, and more preferably 30 to 100 mol%, based on the total content of the repeating units included in the hydrophobic resin (D).

[0428] When the hydrophobic resin (D) has silicon atoms, the content of the silicon atoms is preferably 2 to 50% by mass, and more preferably 2 to 30% by mass, based on the weight average molecular weight of the hydrophobic resin (D). In addition, the content of the repeating unit containing a silicon atom is preferably 10 to 100 mol%, and more preferably 20 to 100 mol%, based on the total content of the repeating units included in the hydrophobic resin (D).

[0429] On the other hand, particularly, when the resin (D) contains the CH ₃ partial structure in a side chain moiety thereof, it is also preferable that the resin (D) do not substantially contain a fluorine atom and a silicon atom. In this case, specifically, the content of the repeating units having a fluorine atom and a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and and ideally 0 mol%, that is, the resin has no fluorine atom and silicon atom, based on the total content of the repeating units in the resin (D). In addition, it is preferable that the resin (D) substantially consist of only repeating units consisting of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the content of the repeating units consisting of only atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom is preferably 95 mol% or more, more preferably 97 mol% or more, still more preferably 99 mol%, and ideally 100 mol%, based on the total content of the repeating units in the resin (D).

[0430] The weight average molecular weight of the hydrophobic resin (D) relative to polystyrene standards is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.

[0431] Furthermore, the hydrophobic resin (D) may be used individually, or plural resins may be used in combination.

[0432] The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass, based on the total solids content of the composition of the present invention.

[0433] For the hydrophobic resin (D), it is natural that the resin contains less impurities such as metals, as in the case of the resin (A), and the content of the residual monomer or oligomer components is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.05 to 1% by mass. Thus, an actinic ray-sensitive or radiation-sensitive resin composition that does not have temporal changes in the impurities in the liquid or sensitivity or the like may be obtained. In addition, a molecular weight distribution (Mw/Mn, also referred to as degree of dispersion) is preferably in the range of 1 to 5, more preferably 1 to 3, and even more preferably is in the range of 1 to 2 from the viewpoint of resolution, a resist shape, a sidewall of the resist pattern, roughness, and the like.

[0434] In regard to the hydrophobic resin (D), various commercially available products can be used, or the resin can be synthesized according to a routine method (for example, by radical polymerization). For example, as the general synthesis method, a bulk polymerization method in which polymerization is carried out by dissolving monomer species and an initiator in a solvent and heating the solution, a dropwise adding polymerization method in which a solution of monomer species and an initiator is added dropwise to a heating solvent over 1 to 10 hours, or the like may be included, and a dropwise adding polymerization method is preferable.

[0435] Matters concerning the reaction solvent, polymerization initiator, reaction conditions (temperature, concentration, and the like), and the purification method after reaction, are the same as those described with regard to the resin (A), however, in the synthesis of the hydrophobic resin (D), the concentration of the reaction is preferably 30 to 50% by mass.

[0436] Specific examples of the hydrophobic resin (D) will be shown below. In addition, the molar ratio of the repeating unit in each resin (corresponding to each repeating unit from left to right), the weight-average molecular weight, and the degree of dispersion are shown in the tables below.

[Chem. 52]

[Chem. 53]

(HR-36) (HR-37) (HR-36) (HR-39)

₍ ( _H H _R R- ₄ 4 ₃ 3 ₎ ) ^Y (HR- 44)

(HR-45) (HR-46) (HR- 7) (HR- 48)

[Chem. 54]

(HR-49) (nfj.joj (HR-51) (HR-S2)

(HR-64) (HR-B6)

[Chem. 55]

(H -78) (HR-79) (HR-80) (HR-81)

[Chem.56]

[Chem. 57]

[Chem. 58]

[Table 3-1]

Resin Composition Mw Mw/Mn

HR-1 50/50 4900 1.4

HR-2 50/50 5100 1.6

HR-3 50/50 4800 1.5

HR-4 50/50 5300 1.6

HR-5 50/50 4500 1.4

HR-6 100 5500 1.6

HR-7 50/50 5800 1.9

HR-8 50/50 4200 1,3

HR-9 50/50 5500 1.8

HR-10 40/60 7500 1.6

HR-11 70/30 6600 1.8

HR-12 40/60 3900 1.3

HR-13 50/50 9500 1.8

HR-14 50/50 5300 1.6

HR-15 100 6200 1.2

HR-16 100 5600 1.6

HR-17 100 4400 1.3

HR-18 50/50 4300 1.3

HR-19 50/50 6500 1.6

HR-20 30/70 6500 1.5

HR-21 50/50 6000 1.6

HR-22 50/50 3000 ^• 1.2

HR-23 50/50 5000 1.5

HR-24 50/50 4500 1.4

HR-25 30/70 5000 1.4

HR-26 50/50 5500 1.6

HR-27 50/50 3500 1.3

HR-28 50/50 6200 1.4 HR-29 50/50 6500 1.6

HR-30 50/50 6500 1.6

HR-31 50/50 4500 1.4

HR-32 30/70 5000 1.6

HR-33 30/30/40 6500 1.8

HR-34 50/50 4000 1.3

HR-35 50/50 6500 1.7

HR-36 50/50 6000 1.5

HR-37 50/50 5000 1.6

HR-38 50/50 4000 1.4

HR-39 20/80 6000 1.4

HR-40 50/50 7000 1.4

HR-41 50/50 6500 1.6

HR-42 50/50 5200 1.6

HR-43 50/50 6600 1.4

HR-44 70/30 5500 1.6

HR-45 50/20/30 4200 1.4

HR-46 30/70 7500 1.6

HR-47 40/58/2 4300 1.4

HR-48 50/50 6800 1.6

HR-49 100 6500 1.5

HR-50 50/50 6600 1.6

HR-51 30/20/50 6800 1.7

HR-52 95/5 5900 1.6

HR-53 40/30/30 4500 1.3

HR-54 50/30/20 6500 1.8

HR-55 30/40/30 7000 1.5

HR-56 60/40 5500 1.7

HR-57 40/40/20 4000 1.3

HR-58 60/40 3800 1.4

HR-59 80/20 7400 1.6

HR-60 40/40/15/5 4800 1.5

HR-61 60/40 5600 1.5

HR-62 50/50 5900 2.1

HR-63 80/20 7000 1.7

HR-64 100 5500 1.8

HR-65 50/50 9500 1.9

[Table 3-2]

Resin Composition Mw Mw/Mn

HR-66 50/50 9600 1.74

HR-67 60/40 34500 1.43

HR-68 30/70 19300 1.69

HR-69 90/10 26400 1.41

HR-70 100 27600 1.87

HR-71 80/20 4400 1.96

HR-72 100 16300 1.83

HR-73 5/95 24500 1.79

HR-74 20/80 15400 1.68 HR-75 50/50 23800 1.46

HR-76 100 22400 1.57

HR-77 10/90 21600 1.52

HR-78 100 28400 1.58

HR-79 50/50 16700 1.82

HR-80 100 23400 1.73

HR-81 60/40 18600 1.44

HR-82 80/20 12300 1.78

HR-83 40/60 18400 1.58

HR-84 70/30 12400 1.49

HR-85 50/50 23500 1.94

HR-86 10/90 7600 1.75

HR-87 5/95 14100 1.39

HR-88 50/50 17900 1.61

HR-89 10/90 24600 1.72

HR-90 50/40/10 23500 1.65

HR-91 60/30/10 13100 1.51

HR-92 50/50 21200 1.84

HR-93 10/90 19500 1.66

[Table 3-3]

Resin Composition Mw Mw/Mn

HR-94 50/50 16500 1.72

HR-95 10/50/40 18000 1.77

HR-96 5/50/45 27100 1.69

HR-97 20/80 26500 1.79

HR-98 10/90 24700 1.83

HR-99 10/90 15700 1.99

HR-100 5/90/5 21500 1.92

HR-101 5/60/35 17700 2.1

HR-102 35/35/30 25100 2.02

HR- 103 70/30 19700 1.85

HR-104 75/25 23700 1.8

HR-105 10/90 20100 2.02

HR-106 5/35/60 30100 2.17

HR-107 5/45/50 22900 2.02

HR-108 15/75/10 28600 1.81

HR-109 25/55/20 27400 1.87

HR-110 100 25000 1.62

HR-111 3/3/80/14 39600 1.83

HR-112 15/80/5 5500 1.76

HR-113 5/70/25 16000 1.66

HR-114 30/65/5 25400 1.65

HR-115 30/65/5 22000 1.71

[0437] [6-1] Basic compound or ammonium salt compound (N) of which basicity is decreased by irradiation of actinic rays or radiation

[0438] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound or an ammonium salt compound (hereinafter, also referred to as a "compound (N)") of which basicity is decreased by irradiation of actinic rays or radiation.

[0439] The compound (N) is preferably a compound (N-l) having a basic functional group or an ammonium group, and a group generating an acidic functional group by irradiation of actinic rays or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group generating an acidic functional group by irradiation of actinic rays or radiation, or an ammonium salt compound having an ammonium group and a group generating an acidic functional group by irradiation of actinic rays or radiation.

[0440] Specifically, a compound in which an anion, in which a proton is desorbed from the basic functional group or the ammonium group, and the acidic functional group of the compound having an acidic functional group, and an onium cation form a salt, or the like, may be included.

[0441] Here, as the basic functional group, for example, an atomic group containing a structure such as a crown ether, a primary to tertiary amine, a nitrogen-containing heterocyclic ring (pyridine, imidazole, pyrazine, or the like) may be included. In addition, as the preferable structure of the ammonium group, for example, an atomic group containing a structure such as primary to tertiary ammonium, pyridinium, imidazolinium, pyrazinium or the like, may be included. In addition, as the basic functional group, a functional group having a nitrogen atom is preferable, a structure having a primary to tertiary amino group or a nitrogen-containing heterocyclic structure is more preferable. In these structures, all the atoms adjacent to the nitrogen atom included in the structure are preferably a carbon atom or a hydrogen atom from the viewpoint of improving basicity. In addition, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, or the like) be not directly bonded to the nitrogen atom.

[0442] As the acidic functional group, a carboxylate group, a sulfonate group, a group having -X-NH-X- (X=CO or S0 ₂ ) structure, or the like, may be included.

[0443] As the onium cation, a sulfonium cation, an iodonium cation, or the like, may be included. More specifically, those described as the cation part of General Formulae (ZI) and (ZII) of the (B) acid generator, or the like, may be included.

[0444] More specifically, as the compound (N) or (N-l) generated by decomposition by irradiation of actinic rays or radiation, and of basicity is decreased, a compound represented by the following General Formula (PA-I), (PA-II), or (PA-III), and a compound represented by the following General Formula (PA-II) or (PA-III) is particularly preferable from the viewpoint of highly balancing excellent effects regarding LWR, local pattern dimension uniformity, and DOF.

[0445] First, a compound represented by General Formula (PA-I) will be described.

In General Formula (PA-I),

Ai represents a single bond or a divalent linking group.

Q represents -S0 ₃ H, or -C0 ₂ H. Q is equivalent to an acidic functional group generated by irradiation of actinic rays or radiation.

X represents -S0 ₂ -, or -CO-,

n represents 0 or 1.

B represents a single bond, an oxygen atom, or -N(Rx)-.

Rx represents a hydrogen atom or a monovalent organic group.

R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

[0446] The divalent linking group in Ai is preferably a divalent linking group having 2 to 12 carbon atoms, and may include, for example, an alkylene group, a phenylene group or the like. An alkylene group having at least one fluorine atom is more preferable, and the number of carbon atoms is preferably 2 to 6 and the number of carbon atoms is more preferably 2 to 4. A linking group such as an oxygen atom or a sulfur atom may be included in the alkylene chain. Particularly, the alkylene group is preferably an alkylene group in which 30% to 100% of the number of hydrogen atoms is substituted with a fluorine atom, and it is more preferable that the carbon atom bonded to a Q site have a fluorine atom. Furthermore, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group, is more preferable.

[0447] The monovalent organic group in Rx has preferably 4 to 30 carbon atoms and examples thereof may include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or the like.

[0448] The alkyl group in Rx may have a substituent, is preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, a nitrogen atom in the alkyl chain.

[0449] As the alkyl group having a substituent, a group in which a straight chain or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor-residue, or the like) may be included.

[0450] The cycloalkyl group in Rx may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

[0451] The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

[0452] The aralkyl group in Rx may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms.

[0453] The alkenyl group in Rx may have a substituent, and may include, for example, a group having a double bond at any position of the alkyl group included as Rx.

[0454] The preferable partial structure of the basic functional group may include, for example, crown ether, a primary to tertiary amine, nitrogen-containing heterocyclic ring (pyridine, imidazole, pyrazine, or the like).

[0455] The preferable partial structure of the ammonium group may include, for example, primary to tertiary ammonium, pyridinium, imidazolinium, pyrazinium or the like.

[0456] In addition, as the basic functional group, a functional group having a nitrogen atom is preferable, a structure having a primary to tertiary amino group or a nitrogen-containing heterocyclic structure is more preferable. In these structures, all the atoms adjacent to the nitrogen atom included in the structure are preferably a carbon atom or a hydrogen atom from the viewpoint of improving basicity. In addition, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, or the like) be not directly bonded to the nitrogen atom.

[0457] The monovalent organic group in the monovalent organic group including such a structure (R group) preferably has 4 to 30 carbon atoms, and may include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or the like, and each group may have a substituent.

[0458] The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group in the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group including the basic functional group or the ammonium group in R are the same alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group included as Rx, respectively.

[0459] As the substituent each group described above may have, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 20 carbon atoms), an aminoacyl group (preferably, 2 to 20 carbon atoms), or the like, may be included. For a cyclic structure in the aryl group, the cycloalkyl group, and the like, the substituent may further include an alkyl group (preferably 1 to 20 carbon atoms). For the aminoacyl group, the substituent may further include one or two alkyl groups (preferably 1 to 20 carbon atoms).

[0460] When B is -N(Rx)-, it is preferable that R and Rx may be bonded to each other to form a ring. By forming the ring structure, stability is improved and storage stability of the composition using this is improved. The number of carbon atoms forming a ring is preferably 4 to 20, the ring may be a monocyclic type or a polycyclic type, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

[0461] The monocyclic structure may include a 4- to 8-membered ring containing a nitrogen atom. As the polycyclic structure, a structure formed by combining two, three or more monocyclic structures. The monocyclic structure and the polycyclic structure may have a substituent, and is preferably, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 15 carbon atoms), an acyloxy group (preferably 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably 2 to 15 carbon atoms), an aminoacyl group (preferably 2 to 20 carbon atoms), or the like. For a cyclic structure in the aryl group, the cycloalkyl group, and the like, the substituent may further include an alkyl group (preferably 1 to 15 carbon atoms). For the aminoacyl group, the substituent may further include one or two alkyl groups (preferably 1 to 15 carbon atoms).

[0462] Among the compounds represented by General Formula (PA-I), compounds of which Q site is sulfonic acid can be synthesized using a general sulfonamide reaction. For example, a method in which a sulfonamide bond is formed by selectively reacting one of the sulfonyl halide parts of a bissulfonyl halide compound with an amine compound, and then, the other sulfonyl halide part is hydrolyzed, or a method in which a cyclic sulfonic acid anhydride is reacted with an amine compound and is ring-opened, may be used.

[0463] Next, a compound represented by General Formula (PA-II) will be described. Q _! -X,-NH-X ₂ -Q ₂ (PA-II)

In General Formula (PA-II),

Qi and Q ₂ each independently represent a monovalent organic group. However, any one of Qi and Q ₂ has a basic functional group. Qi and Q ₂ are bonded to each other forming a ring, and the ring formed may have a basic functional group.

Xi and X ₂ each independently represent -CO- or -S0 ₂ -.

In addition, -ΝΉ- is equivalent to an acidic functional group generated by irradiation of actinic rays or radiation.

[0464] In General Formula (PA-II), the monovalent organic group as Qj and Q ₂ preferably has 1 to 40 carbon atoms, and may include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or the like.

[0465] The alkyl group in Qi and Q ₂ may have a substituent, is preferably a straight chain or branched alkyl group having 1 to 30 carbon atoms, and may have an oxygen atom, a sulfur atom, a nitrogen atom in the alkyl chain.

[0466] The cycloalkyl group in Qi and Q ₂ may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms and may include an oxygen atom and a nitrogen atom in the ring.

[0467] The aryl group in Qj and Q ₂ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

[0468] The aralkyl group in Qj and Q ₂ may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms.

[0469] The alkenyl group in Qj and Q ₂ may have a substituent, and may include, for example, a group having a double bond at any position of the above alkyl group.

[0470] As the substituent each group described above may have, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 20 carbon atoms), an aminoacyl group (preferably, 2 to 10 carbon atoms), or the like, may be included. For a cyclic structure in the aryl group, the cycloalkyl group, and the like, the substituent may further include an alkyl group (preferably 1 to 10 carbon atoms). For the aminoacyl group, the substituent may further include an alkyl groups (preferably 1 to 10 carbon atoms). The alkyl group having a substituent may include, for example, a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group or a perfluorobutyl group.

[0471] As a preferable partial structure of the basic functional group at least one of Qi and Q ₂ may have, the same partial structure described as the basic functional group R of General Formula (PA-I) has may be included.

[0472] As the structure in which Q] and Q ₂ are bonded to each other forming a ring and the ring formed may have a basic functional group, for example, a structure in which the organic group of Qi and Q ₂ is further bonded to an alkylene group, an oxy group, an imino group or the like, may be included.

[0473] In General Formula (PA-II), at least one of Xj and X ₂ is preferably -S0 ₂ -.

[0474] Next, a compound represented by General Formula (PA-III) will be described.

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

In General Formula (PA-III),

Qi and Q ₃ each independently represent a monovalent organic group. However, any one of Qi and Q ₃ has a basic functional group. Qi and Q ₃ are bonded to each other forming a ring, and the ring formed may have a basic functional group.

Xi, X ₂ and X ₃ each independently represent -CO- or -S0 ₂ -.

A ₂ represents a divalent linking group.

B represents a single bond, an oxygen atom or -N(Qx)-.

Qx represents a hydrogen atom or a monovalent organic group.

When B is -N(Qx)-, Q ₃ and Qx may be bonded to each other to form a ring.

m represents 0 or 1.

In addition, -NH- is equivalent to an acidic functional group generated by irradiation of actinic rays or radiation.

Qi is synonymous with Qj in General Formula (PA-II).

[0475] The organic group of Q ₃ may include the same organic group of Qj and Q ₂ in General Formula (PA-II).

[0476] As the structure in which Qi and Q ₃ are bonded to each other forming a ring and the ring formed may have a basic functional group, for example, a structure in which the organic group of Qi and Q ₃ is further bonded to an alkylene group, an oxy group, an imino group or the like, may be included.

[0477] The divalent linking group in A ₂ is preferably a divalent linking group (1 to 8 carbon atoms) having a fluorine atom, and may include, for example, an alkylene group (1 to 8 carbon atoms) having a fluorine atom, a phenylene group having a fluorine atom or the like. An alkylene group having a fluorine atom is more preferable, and the number of carbon atoms is preferably 2 to 6 and the number of carbon atoms is more preferably 2 to 4. A linking group such as an oxygen atom or a sulfur atom may be included in the alkylene chain. The alkylene group is preferably an alkylene group in which 30% to 100% of the number of hydrogen atoms are substituted with a fluorine atom, more preferably a perfluoroalkylene group, is preferable, and particularly preferably a perfluoroalkylene group having 2 to 4 carbon atoms.

[0478] The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and may include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, or the like. The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group are the same as Rx in the above Formula

(PA-I).

[0479] In General Formula (PA-III), X _u X ₂ , and X ₃ are preferably -S0 ₂ -.

[0480] The compound (N) is preferably a sulfonium salt compound of the compound represented by General Formula (PA-I), (PA-II) or (PA-III), or an iodonium salt compound of the compound represented by General Formula (PA-I), (PA-II) or (PA-III), and more preferably a compound represented by the following General Formula (PAl) or (PA2).

[Chem. 59]

(PA1 ) (PA2)

In General Formula (PAl),

R'201, R'202 and R' ₂₀₃ each independently represent an organic group, and specifically, is the same R ₂ oi, R202 and R ₂₀₃ of Formula ZI in the above (B) component.

X ^" represents a sulfonate anion or a carboxylate anion in which a hydrogen atom of the -S0 ₃ H site or the -COOH site of the compound represented by General Formula (PA-I) is desorbed, or an anion in which a hydrogen atom of the -NH- site of the compound represented by General Formula (PA-II) or (PA-III) is desorbed.

In General Formula (PA2),

R' ₂ 04 and R' ₂₀ 5 each independently represent an aryl group, an alkyl group or a cycloalkyl group, and specifically, is the same R ₂₀₄ and R ₂₀₅ of Formula ZII in the above (B) component.

X ^" represents a sulfonate anion or a carboxylate anion in which a hydrogen atom of the -S0 ₃ H site or the -COOH site of the compound represented by General Formula (PA- 1) is desorbed, or an anion in which a hydrogen atom of the -NH- site of the compound represented by General Formula (PA-II) or (PA-III) is desorbed.

[0481] The compound (N) is decomposed by irradiation of actinic rays or radiation, and produces, for example, a compound represented by General Formula (PA-I), (PA-II) or (PA-III).

[0482] The compound represented by General Formula (PA-I) is a compound of which basicity is reduced, eliminated, or changed to from basicity to acidity compared to the compound (N), by having a sulfonate group or a carboxylate group with a basic functional group or an ammonium group.

[0483] The compound represented by General Formula (PA-II) or (PA-III) is a compound of which basicity is reduced, eliminated, or changed from basicity to acidity compared to the compound (N), by having an organic sulfonylimino group or an organic carbonylimino group with a basic functional group.

[0484] In the present invention, basicity being reduced by irradiation of actinic rays or radiation means that an acceptor property of the compound (N) for protons (acid generated by irradiation of actinic rays or radiation) is reduced by irradiation with actinic rays or radiation. The acceptor property being reduced means that, when an equilibrium reaction in which a non-covalent bond complex, a proton adduct, is produced from the compound having a basic functional group and a proton, or an equilibrium reaction in which a counter-cation of the compound having an ammonium group is exchanged with a proton, an equilibrium constant in chemical equilibrium thereof is reduced.

[0485] As described above, when the compound (N) in which basicity is reduced by irradiation of actinic rays or radiation is incorporated in the resist film, the acceptor property of the compound (N) is sufficiently expressed in the unexposed areas, and the unintended reaction between the acid that has diffused from exposed areas or the like and the resin (A) can be suppressed. Also, in the exposed areas, since the acceptor property of the compound (N) is decreased, the intended reaction between the acid and the resin (A) occurs more reliably, and there is also contribution of such an operating mechanism. Thus, it is speculated that a pattern which is excellent in the line width roughness (LWR), local uniformity of the pattern dimensions, the depth of focus (DOF), and the pattern shape may be obtained. [0486] In addition, basicity can be confirmed by a pH measurement, and the calculated value can be determined by commercially available software.

[0487] Hereinafter, specific examples the compound (N) which produces a compound represented by General Formula (PA-I) by irradiation of actinic rays or radiation are shown below, however, the present invention is not limited to these.

[Chem. 60]

[Chem. 61]

[0488] These compounds can be readily synthesized using a salt-exchange method disclosed in JPl 999-501909A (JP-H11-501909A) or JP2003-246786A from a compound represented by General Formula (PA-I), or a lithium, a sodium and a potassium salt thereof, and a hydroxide, a bromide, or a chloride of iodonium or sulfonium. In addition, it can be synthesized in accordance with the synthesis methods disclosed in JP1995-333851A (JP-H07-333851A).

[0489] Hereinafter, specific examples the compound (N) which produces a compound represented by General Formula (PA-II) or (PA-III) by irradiation of actinic rays or radiation are shown below, however, the present invention is not limited to these.

[Chem. 62]

[Chem. 63]

[0490] These compounds may be readily synthesized by using a general sulfonic acid esterification reaction or a sulfonamide reaction. For example, a method in which a sulfonamide bond or a sulfonate bond is formed by selectively reacting one of the sulfonyl halide part of a bissulfonyl halide compound with, amine, alcohol or the like including a partial structure represented by General Formula (PA-II) or (PA-III), and then, the other sulfonyl halide part is hydrolyzed, or a method in which a cyclic sulfonic acid anhydride is ring-opened by amine or alcohol including a partial structure represented by General Formula (PA-II), may be used. The amine or alcohol including a partial structure represented by General Formula (PA-II) or (PA-III) may be synthesized by reacting amine or alcohol with an anhydride such as (R'0 ₂ C) ₂ 0 or (R'S0 ₂ ) ₂ 0, or an acid chloride compound such as R'0 ₂ CC1 or R'S0 ₂ C1 (R' is a methyl group, an n-octyl group, a trifluoromethyl group, or the like) under a basic condition. In particular, these compounds can be synthesized in accordance with the synthesis examples disclosed in JP2006-330098A.

[0491] A molecular weight of the compound (N) is preferably 500 to 1,000.

[0492] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the compound (N), however, when the composition contains the compound (N), the content of the compound (N) having an acid group is preferably 0.1 to

20% by mass and more preferably 0.1 to 10% by mass, based on the total solids of the actinic ray-sensitive or radiation-sensitive resin composition.

[0493] [6-2] Basic compound (Ν')

[0494] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a basic compound (Ν') which is different from the above-described compound (N), in order to reduce any change in the performance over time from the exposure to the heating.

[0495] Preferred examples of the basic compound (Ν') include compounds having structures represented by the following formulae (A) to (E).

[Chem. 64]

In General Formulae (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same as or different from each other, represent a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 6 to 20 carbon atoms), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same as or different from each other, and represent an alkyl group having 1 to 20 carbon atoms.

[0496] For the above alkyl group, an alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.

[0497] The alkyl group in General Formulae (A) and (E) is preferably an unsubstituted alkyl group.

[0498] As the preferable compound, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, amino morpholine, aminoalkyl morpholine, piperidine or the like may be included, and as the more preferable compound, a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like, may be included.

[0499] The compound having an imidazole structure may include imidazole, 2,4,5-triphenyl imidazole, benzimidazole, or the like. The compound having a diazabicyclo structure may include l,4-diazabicyclo[2,2,2]octane, l,5-diazabicyclo[4,3,0]nona-5-ene, l,8-diazabicyclo[5,4,0]undeca-7-ene, or the like. The compound having an onium hydroxide structure may include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxo alkyl group, specifically, triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, or the like. A compound having an onium carboxylate structure is a compound in which the anion moiety of a compound having an onium hydroxide structure has been converted to carboxylate, and examples thereof may include acetates, adamantane-l-carboxylates, perfluoroalkylcarboxylates, and the like. The compounds having a trialkylamine structure may include tri(n-butyl)amine, tri(n-octyl)amine, or the like. The compound having an aniline structure may include 2,6-diisopropyl aniline, Ν,Ν-dimethyl aniline, N,N-dibutyl aniline, Ν,Ν-dihexyl aniline, or the like. The alkylamine derivative having a hydroxyl group and/or an ether bond may include ethanolamine, diethanolamine, triethanolamine, and tris(methoxyethoxyethyl)amine, or the like. The aniline derivative having a hydroxyl group and/or an ether bond may include N,N-bis(hydroxyethyl)aniline, or the like.

[0500] Preferred examples of the basic compound (Ν') may include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

[0501] In the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group, at least one alkyl group is bonded to the nitrogen atom. In addition, it is preferable that an oxygen atom be included and an oxyalkylene group be formed in the alkyl chain. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. As the oxyalkylene group, a structure of -CH ₂ CH ₂ 0-, -CH(CH ₃ )CH ₂ 0-, or -CH ₂ CH ₂ CH ₂ 0- is preferable.

[0502] Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group include the compounds (Cl-1) to (C3-3) exemplified in [0066] of US2007/0224539A, however, are not limited to these.

[0503] Furthermore, as one kind of the basic compound (Ν'), a nitrogen-containing organic compound having a group which is capable of being desorbed by the action of an acid can also be used. Examples of this compound may include a compound represented by the following General Formula (F). Meanwhile, a compound represented by the following General Formula (F) exhibits effective basicity in the system, when the group that is desorbed by the action of an acid is desorbed.

[Chem. 65]

[0504] In General Formula (F), R _a s each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. In addition, when n=2, the two R _a s may be the same as or different from each other, two of R _a s may be bonded to each other and form a divalent heterocyclic hydrocarbon group (preferably 20 or less carbon atoms) or a derivative thereof.

[0505] R _b S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. However, in -C(R )(R )(R _b ), when one or more of R _b S are a hydrogen atom, at least one of the rest ¾s is a cyclopropyl group or a 1-alkoxyalkyl group.

[0506] At least two of R _b S may be bonded to each other and form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

[0507] n represents an integer of 0 to 2, m represents an integer of 1 to 3, respectively, and n+m=3.

[0508] In General Formula (F), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group representing R _a and R _b may be substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group or an oxo group, an alkoxy group, or a halogen atom.

[0509] Examples of the alkyl group, the cycloalkyl group, the aryl group, or the aralkyl group (these alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted with the functional group, alkoxy group, or halogen atom described above) of the R may include:

[0510] a group derived from a straight chain or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, or dodecane; a group obtained by substituting these alkane-derived groups with one or more kinds or one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group;

[0511] a group derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, or noradamantane; a group obtained by substituting these cycloalkane-derived groups with one or more kinds or one or more straight chain or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a t-butyl group;

[0512] a group derived from aromatic compounds such as benzene, naphthalene and anthracene; a group obtained by substituting these aromatic group-derived groups with one or more kinds or one or more straight chain or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a t-butyl group;

[0513] a group derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, and benzimidazole; a group obtained by substituting these heterocyclic compound-derived groups with one or more kinds or one or more of groups derived from a straight chain or branched alkyl group or a group derived from aromatic compounds; a group obtained by substituting a group derived from a straight chain or branched alkane and a group derived from a cycloalkane with one or more kinds or one or more groups derived from aromatic compounds such as a phenyl group, a naphthyl group, and an anthracenyl group; or a group obtained by substituting the above-described substituents with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidine group, a piperidine group, a morpholino group, or an oxo group.

[0514] Specific examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or the derivative thereof that the R _a s form by binding to each other may include the same specific examples as the specific examples of the nitrogen-containing heterocyclic ring which is formed by bonding Ra and Rci of the compound (G) in General Formula (2) described above to each other.

[0515] Specific examples of the particularly preferable nitrogen-containing organic compounds having a group desorbed by the action of an acid are shown below, however, the present invention is not limited to these.

[Chem. 66]

[0516] As the compounds represented by General Formula (F) described above, commercially available compounds may be used, or the compounds may be synthesized from commercially available amines using method described in the Protective Groups in Organic Synthesis, fourth edition, and the like. As the most general method, for example, the compounds may be synthesized in accordance with the method disclosed in JP2009- 199021 A.

[0517] Furthermore, as the basic compound (Ν'), a compound disclosed in JP2011-141494A which has a fluorine atom or a silicon atom and has basicity or exhibits increased basicity due to the action of an acid may be used. Specific examples thereof may include compounds (B-7) to (B-18) which are used in Examples of JP2011-141494 A.

[0518] The molecular weight of the basic compound (Ν') is preferably 250 to 2,000, and even more preferably 400 to 1,000. The molecular weight of the basic compound is preferably is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more from the viewpoint of further reduction of LWR and local pattern dimension uniformity.

[0519] This basic compound (Ν') may be used in combination with the compound (N) or may be used alone or in combination of two or more kinds thereof.

[0520] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the basic compound (Ν'), but when the actinic ray-sensitive or radiation-sensitive resin composition contains the basic compound (Ν'), the amount of the basic compound (Ν') used is generally 0.001 to 10% by mass, and preferably 0.01 to 5% by mass, based on the solid content of the actinic-ray-sensitive or radiation-sensitive resin composition.

[0521] The ratio between the acid generator and the basic compound (including the basic compound as the compound (N) and the basic compound (N')) used in the composition is preferably the acid generator/the basic compound (molar ratio)=2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction of the resolution by an enlargement of the resist pattern over time from the exposure to the heat treatment. The acid generator/the basic compound (molar ratio) is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

[0522] [7] Surfactant

[0523] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not include a further surfactant, however, if the composition does, may preferably contain any one of fluorine- and/or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, surfactants having both a fluorine atom and a silicon atom) or two or more types of surfactants.

[0524] By the actinic ray- sensitive or radiation- sensitive resin composition in the present invention containing a surfactant, a resist pattern with satisfactory sensitivity and resolution, therefore, less adhesion and developing defects may be obtained when exposure light source of 250 nm or less, particularly 220 nm or less, is used.

[0525] The fluorine- and/or silicon-based surfactant may include surfactants disclosed in [0276] of US2008/0248425A, and may include, for example, F-Top EF301 and EF303 (manufactured by Shin Akita Kasei Co., Ltd.), Fluorad FC430, 431, and 4430 (manufactured by Sumitomo 3M Limited), Megaface F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106, and KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300 and GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, and EF601 (manufactured by Jemco, Inc.), PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA Solutions Inc.), FTX-204G, 208G, 218Q 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos Co., Ltd.), or the like. In addition, a polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-based surfactant.

[0526] In addition, as the surfactant, a surfactant using a polymer having a fluoroaliphatic group derived from a fluoro aliphatic compound prepared by a telomerization method (also referred to as a telomer method) or an oligomerization method (also known as an oligomer method) in addition to those well-known in the art shown above may be used. The fluoro aliphatic compound may be synthesized by methods disclosed in JP2002-90991 A.

[0527] The surfactant corresponding to the above may include Megaface F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), a copolymer of acrylate (or methacrylate) having a C ₆ Fi ₃ group and (poly(oxyalkylene)) acrylate (or methacrylate), a copolymer of acrylate (or methacrylate) having a C ₃ F ₇ group, (poly(oxyethylene)) acrylate (or methacrylate), and (poly(oxypropylene)) acrylate (or methacrylate), or the like.

[0528] In addition, in the present invention, other surfactants, besides the fluorine-based and/or silicon-based surfactants, which is disclosed in [0280] of US2008/0248425A may be used.

[0529] These surfactants may be used either alone or as a combination of two or more.

[0530] If the actinic ray-sensitive or radiation-sensitive resin composition contains the surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass with regard to total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent).

[0531] On the other hand, when the amount of the surfactant added is adjusted to 10 ppm or less based on the total amount (excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition, the uneven distribution of the resin (D) according to the present invention at the surface is increased, and thereby the surface of the resist film can be made more hydrophobic. Thus, water conformity at the time of immersion exposure can be enhanced.

[0532] [8] Other additives

[0533] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not include not contain an onium salt carboxylate. The onium salt carboxylate such as this may include those described in [0605] to [0606] of US2008/0187860 A.

[0534] The onium salt carboxylate such as this can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in an appropriate solvent.

[0535] If the actinic ray-sensitive or radiation-sensitive resin composition contains the onium salt carboxylate, the content is typically 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass with regard to total solids of the composition.

[0536] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may further contain, if necessary, a dye, a plasticizer, a light sensitizer, a light absorbent, an alkali-soluble resin, a dissolution inhibitor, a compound promoting solubility for a developer (for example, a phenol compound with a molecular weight of 1,000 or less, an alicyclic compound or aliphatic compound having a carboxyl group), and the like.

[0537] The phenol compound with a molecular weight of 1,000 or less may be readily synthesized by those skilled in the art with reference to the method disclosed in, for example, JP 1992- 122938 A (JP-H04-122938A), JP1990-28531A (JP-H02-28531A), US4916210A, EP219294B, and the like.

[0538] Specific examples of the alicyclic compound or aliphatic compound having a carboxyl group may include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid or lithocholic acid, an adamantane carboxylic acid derivative, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane dicarboxylic acid, or the like, however, are not limited to these.

[0539] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used at a film thickness of 30 to 250 nm, and more preferably used at a film thickness of 30 to 200 nm from the viewpoint of improving resolution. This film thickness is possible by improving coating properties and film formability through setting the solid concentration in the composition being in an appropriate range to have a moderate viscosity.

[0540] The solid concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is typically 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By having a solid concentration in this range, the resist solution may be uniformly applied on the substrate, and forming a resist pattern with excellent line width roughness is possible. The reason for this is not clear, however, it is believed that, by having the solid concentration at 10% by mass or less and preferably 5.7 % by mass or less, aggregation of materials in the resist solution, particularly, the photoacid generator is suppressed and as a result, a uniform resist film may be formed.

[0541] The solid concentration is a weight percentage of the weight of other resist components except the solvent with regard to the total weight of the actinic ray- sensitive or radiation-sensitive resin composition.

[0542] The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is used by the above component being dissolved in a predetermined organic solvent, preferably the mixed solvent described above, filtered by a filter, and then coated on a predetermined support (substrate). The pore size of the filter used in the filtration by a filter is preferably less than 0.1 μηι or less, more preferably 0.05 μιη or less, and more preferably 0.03 μηι or less made of polytetrafluoroethylene, polyethylene, or nylon. In the filtration by a filter, filtration may be carried out by cyclical filtration or by connecting a plurality of types of filters in series or in parallel, as disclosed in JP2002-62667A. In addition, the composition may also be filtered a plurality of times. Furthermore, a degassing treatment, or the like, may be carried out on the composition before and after filtration.

[0543] [9] Pattern forming method

[0544] The pattern forming method (method for forming a negative pattern) of the present invention includes at least

(i) a step for forming a film (resist film) using the actinic ray-sensitive or radiation- sensitive resin composition of the present invention,

(ii) a step for exposing the film, and

(iii) a step for developing the exposed film using a developer that contains an organic solvent.

[0545] The exposing in the above step (ii) may be liquid immersion exposure.

[0546] The pattern forming method of the present invention preferably includes (iv) a heating step after (ii) the exposing step.

[0547] The pattern forming method of the present invention may further include (v) a developing step using an alkaline developer.

[0548] In the pattern forming method of the present invention, (ii) the exposing step may be performed a plurality of times.

[0549] In the pattern forming method of the present invention, (iv) the heating step may be performed a plurality of times.

[0550] The resist film of the present invention is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above, and more specifically, is preferably a film formed by coating the actinic ray-sensitive or radiation-sensitive resin composition on a base material. In the pattern forming method of the present invention, the step for forming a film by the actinic ray-sensitive or radiation-sensitive resin composition on a substrate, and the step for exposing the film and the developing step may be performed by generally known methods.

[0551] Before the film is exposed after being formed, the pattern forming method preferably also includes a preheating step (PB: Prebake).

[0552] It is also preferable that, a heating step (PEB: Post Exposure Bake) after the exposure be included after the exposure step and prior to the developing step.

[0553] The heating temperature for both PB and PEB is preferably 70 to 130°C, and more preferably 80 to 120°C.

[0554] The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds.

[0555] The heating can be performed using means provided to a general exposing and developing machine, and a hot plate or the like may also be used.

[0556] Sensitivity or pattern profile is improved by the reaction of the exposed area being accelerated due to bake.

[0557] The wavelength of the light source used in the exposure apparatus of the present invention is not particularly limited, however, may include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, or the like, is preferably far ultraviolet light with the wavelength of 250 nm or less, more preferably 220 nm or less and particularly preferably 1 to 200 nm, more specifically, is a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), a F ₂ excimer laser (157 nm), X-rays, EUV (13 nm), an electron beam or the like, preferably a KrF excimer laser, an ArF excimer laser, EUV or an electron beam, and more preferably an ArF excimer laser.

[0558] Ini addition, in the step for performing the exposure of the present invention, a liquid immersion exposure method may be applied.

[0559] The liquid immersion exposure method is a technology improving resolution, and is a technology of exposure in which an area between the projection lens and a sample is filled with liquid with a high refractive index (hereinafter, also referred to as "immersion liquid"). [0560] As described above, provided that λ ₀ is a wavelength of exposure light in the air, n is a refractive index of a liquid for liquid immersion with respect to the air, and that Θ is a beam convergence half angle which is NA ₀ =sin9, when the liquid immersion is performed, the "effect of liquid immersion" can be indicated by calculating the resolving power and depth of focus (DOF) from the following formulae. Here, k] and k ₂ are coefficients related to the process.

[0561] (Resolving / n) / NA ₀

[0562] (DOF)=±k ₂ ^o / ⁿ ) / ^NA o ²

[0563] That is, the effect of the liquid immersion is equivalent to the wavelength using the exposure wavelength of 1/n. In other words, for NA of the same projection optical system, the depth of focus may be made to be n times by the liquid immersion. This is valid for all pattern shapes, and furthermore, combining with super-resolution technologies such as a phase shift method or a modified illumination method currently considered is possible.

[0564] When the liquid immersion exposure is carried out, (1) after forming the film on the substrate and prior to the exposure step, and/or (2) after the step for exposing the film by the immersion liquid, and prior to the step for heating the film, a step in which the surface of the film is cleaned with a water-based chemical solution may be performed.

[0565] The liquid immersion is preferably a liquid which is transparent to the exposure wavelength and has as small a temperature coefficient of a refractive index as possible so as to minimize the distortion of an optical image projected onto the film. Particularly, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water in respect that water is easily obtained and handled, in addition to the above-described viewpoints.

[0566] When water is used, an additive (liquid) which decreases the surface tension of water and increases surfactant potency may be added in a slight proportion. This additive is preferably an additive which does not dissolve the resist layer on a wafer and can ignore the effects on the optical coat at the lower surface of the lens element.

[0567] The additive such as this is preferably an aliphatic alcohol having approximately the same refractive index as water, and specifically, may include, methyl alcohol, ethyl alcohol, isopropyl alcohol, or the like. An advantage of adding the alcohol having approximately the same refractive index as water is that changes of the refractive index of the liquid as a whole may be extremely small even when the content concentration changes by the alcohol component in water being evaporated. [0568] On the other hand, if materials opaque to light of 193 nm or impurities whose refractive index is significantly different from water are incorporated, they cause a distortion of the optical image projected on the resist, therefore, distilled water is preferable as the water used. Pure water filtered through an ion exchange filter or the like may also be used.

[0569] Electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, TOC (Total Organic Carbon) is preferably 20 ppb or less, and it is preferable that a degassing treatment be carried out.

[0570] In addition, the performance of lithography can be improved by increasing the refractive index of the immersion liquid. From this point of view, the addition of additives increasing the refractive index to water or using heavy water (D ₂ 0) instead of water is possible.

[0571] The backward contact angle of the resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention at a temperature of 23±3°C and a humidity of 45±5% is 70° or more and thus this angle is preferable in a case where the resist film is exposed through a liquid immersion medium. The backward contact angle of the film is preferably 75° or more, and more preferably 75° to 85°.

[0572] When the backward contact angle is too small, it is not possible to preferably use the resist film in a case where the resist film is exposed through a liquid immersion medium. Moreover, it is not possible to sufficiently exhibit the effect of decreasing residual water (water mark) defects.

[0573] When the resin (D) substantially does not have a fluorine atom and a silicon atom, by containing the resin (D) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, it is possible to improve the backward contact angle of the surface of the resist film.

[0574] From the viewpoint of improving the backward contact angle, it is preferable that the resin (D) have at least one of repeating units represented by General Formula (II) or (III). In addition, from the viewpoint of improving the backward contact angle, the ClogP value of the resin (D) is preferably 1.5 or more. Moreover, from the viewpoint of improving the backward contact angle, the mass content of the CH ₃ partial structure, which the side chain moiety of the resin (D) contains, in the resin (D) is preferably 12.0% or more.

[0575] In the liquid immersion exposure step, the contact angle of the immersion liquid for the resist film in a dynamic state becomes critical since the immersion liquid has to move on the wafer following the movement of the exposure head scanning on the wafer at high speed and forming an exposure pattern, therefore, the resist is required to have an ability to follow the high-speed scan of the exposure head without the remaining droplets.

[0576] The substrate forming a film in the present invention is not particularly limited, and a substrate generally used in a semiconductor manufacturing process such as IC, a circuit board manufacturing process such as liquid crystal and thermal head, and also a lithography process of photofabrication in addition to these, such as an inorganic substrate such as silicon, SiN or Si0 ₂ , or a coating-based inorganic substrate such as SOG, or the like, may be used. In addition, an organic anti-refleetive film may be formed between the film and the substrate, if necessary.

[0577] If the pattern forming method of the present invention further includes the step for developing using an alkali developer, and, as the alkali developer, for example, an alkaline aqueous solution such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammonia water, primary amines such as ethylamine or n-propyl amine, secondary amines such as diethylamine or di-n-butylamine, tertiary amines such as triethylamine or methyldiethylamine, alcohol amines such as dimethylethanolamine or triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, cyclic amines such as pyrrole or piperidine, may be used.

[0578] In addition, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution described above and used.

[0579] An alkali concentration of the alkali developer is typically 0.1 to 20% by mass.

[0580] The pH of the alkali developer is typically 10.0 to 15.0.

[0581] In particular, an aqueous solution of 2.38% by mass tetramethylammonium hydroxide is preferable.

[0582] As the rinsing solution in the rinsing treatment carried out after the alkaline development, pure water may be used, and the rinsing solution may be used adding an appropriate amount of the surfactant.

[0583] In addition, a treatment for removing the developer or the rinsing solution deposited on the pattern may be carried out by supercritical fluid after the development or the rinsing treatment.

[0584] In the pattern forming method of the present invention, as the developer (hereinafter, also referred to as an organic developer) used in the developing using a developer that contains an organic solvent, a polar solvent such as a ketone-based solvent, an ester-based solvent, an alcohol- based solvent, an amide-based solvent, or an ether-based solvent and a hydrocarbon-based solvent can be used.

[0585] Examples of the ketone-based solvents may include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diiso butyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, or the like.

[0586] Examples of the ester-based solvents may include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy butyl acetate, 3-methyl-3-methoxy butyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, or the like.

[0587] Examples of the alcohol-based solvents may include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol or n-decanol, glycol- based solvents such as ethylene glycol, diethylene glycol or triethylene glycol, glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, or the like.

[0588] Examples of the ether-based solvents may include dioxane, tetrahydrofuran, or the like, in addition to the above glycol ether-based solvents.

[0589] Examples of the amide-based solvents may include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, Ν,Ν-dimethylformamide, hexamethylphosphoric triamide, l,3-dimethyl-2-imidazolidinone, or the like.

[0590] Examples of the hydrocarbon-based solvents may include aromatic hydrocarbon-based solvents such as toluene or xylene, or aliphatic hydrocarbon-based solvents such as pentane, hexane, octane or decane.

[0591] The above solvents may be mixed plurally, or may be used being mixed with other types of solvents or water. However, in order to exert sufficient effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and practically, it is more preferable that water be not included. [0592] That is, the amount of the organic solvent used with regard to the organic-based developer is preferably greater than or equal to 90% by mass and less than or equal to 100% by mass, and more preferably greater than or equal to 95% by mass and less than or equal to 100%) by mass with regard to the total amount of the developer.

[0593] In particular, the organic-based developer is preferably a developer including at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.

[0594] Vapor pressure of the organic-based developer is preferably 5 kPa or less, more preferably 3 kPa or less, is particularly preferably 2 kPa or less, at 20°C. By making the vapor pressure of the organic-based developer be 5 kPa or less, evaporation of the developer on the substrate or in the development cup is suppressed, and temperature uniformity within the wafer surface is improved, and as a result, dimension uniformity within the wafer surface is improved.

[0595] Specific examples of the organic-based developer having a vapor pressure of 5 kPa or less may include ketone-based solvents such as 1-octanone, 2-octanone, 1-nonanone,

2- nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, or methyl isobutyl ketone; ester-based solvents such as butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate,

3- methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, or propyl lactate; alcohol- based solvents such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, or n-decanol; glycol-based solvents such as ethylene glycol, diethylene glycol, or triethylene glycol; glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, or methoxymethyl butanol; ether-based solvents such as tetrahydrofuran; amide-based solvents such as N-methyl-2-pyrrolidone, Ν,Ν-dimethylacetamide, or Ν,Ν-dimethylformamide; aromatic hydrocarbon-based solvents such as toluene or xylene; and aliphatic hydrocarbon-based solvents such as octane or decane.

[0596] Specific examples of the organic-based developer having a vapor pressure of 2 kPa or less which is a particularly preferable range may include ketone-based solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, or phenyl acetone; ester-based solvents such as butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, or propyl lactate; alcohol-based solvents such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, or n-decanol; glycol-based solvents such as ethylene glycol, diethylene glycol, or triethylene glycol; glycol ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, or methoxymethyl butanol; amide-based solvents such as N-methyl-2-pyrrolidone, Ν,Ν-dimethylacetamide, or Ν,Ν-dimethylformamide; aromatic hydrocarbon-based solvents such as xylene; and aliphatic hydrocarbon-based solvents such as octane or decane.

[0597] An appropriate amount of surfactant may be added to the organic-based developer, if necessary

[0598] The surfactant is not particularly limited, however, for example, an ionic or non-ionic fluorine-based and/or silicon-based surfactants or the like may be used. These fluorine-based and/or silicon-based surfactants may include surfactants, disclosed in, for example, JP1987-36663A (JP-S62-36663A), JP1986-226746A (JP-S61-226746A), JP 1986-226745 A (JP-S61-226745A), JP1987-170950A (JP-S62-170950A), JP1988-34540A (JP-S63-34540A), JP1995-230165A (JP-H07-230165A), JP 1996-62834A (JP-H08-62834A), JP1997-54432A (JP-H09-54432A), JP 1997-5988 A (JP-H09-5988A), US5405720A, US5360692A, US5529881A, US5296330A, US5436098A, US5576143A, US5294511A and US5824451A, and are preferably non-ionic surfactants. The non-ionic surfactant is not particularly limited, however, the use of fluorine-based surfactants or silicon-based surfactants is more preferable.

[0599] The amount of surfactant used is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with regard to the total amount of the developer.

[0600] As the developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is heaped up on the surface of a substrate by surface tension and developed by resting for a certain period of time (a paddle method), a method in which a developer is sprayed on the surface of the substrate (a spray method), a method in which a developer is continuously discharged on a substrate rotated at a constant rate while scanning a developer discharging nozzle at a constant rate (a dynamic dispense method), or the like, may be applied.

[0601] If the variety of developing methods described above include a step in which a developer is discharged from a development nozzle of a development apparatus toward a resist film, discharge pressure of the developer discharged (flow rate per unit area of the developer discharged) is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and even more preferably 1 mL/sec/mm or less. There is no particular lower limit of the flow rate, however, 0.2 mL/sec/mm ² or more is preferable if throughput is considered.

[0602] By making the discharge pressure of the developer discharged be in this range, defects of the pattern derived from the resist residue after development may be significantly reduced.

[0603] Details of this mechanism is not clear, however, it is believed that, by making the discharge pressure be in the above range, pressure on the resist film by the developer becomes smaller, therefore, the resist film and the resist pattern being scraped or broken carelessly is suppressed.

[0604] In addition, discharge pressure of the developer (mL/sec/mm ² ) is a value at the developing nozzle exit in the development apparatus.

[0605] The method for adjusting the discharge pressure of the developer may include, for example, a method in which discharge pressure is adjusted by a pump and the like, or a method in which pressure is adjusted by the supply from pressurized tank and changed, and the like.

[0606] In addition, a step for stopping the development may be performed, while substituted with other solvents, after the developing step using the developer including an organic solvent.

[0607] It is preferable that a step for cleaning using a rinsing solution be performed after the development step using the developer including an organic solvent.

[0608] The rinsing solution used in the rinsing step after the developing step using the developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution including general organic solvents may be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferably used.

[0609] Specific examples of the hydrocarbon solvents, the ketone-based solvents, the ester-based solvents, the alcohol-based solvents, the amide-based solvents, and the ether-based solvents may be the same as those described in the developer including an organic solvent.

[0610] After the developing step using a developer that contains an organic solvent, the cleaning step is more preferably performed using the rinsing solution containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, and amide-based solvents, the cleaning step is even more preferably performed using the rinsing solution containing alcohol-based solvents or ester-based solvents, the cleaning step is particularly preferably performed using the rinsing solution containing monohydric alcohol, and the cleaning step is most preferably performed using the rinsing solution containing monohydric alcohol having 5 or more carbon atoms.

[0611] Here, the monohydric alcohol used in the rinsing step may include a straight chain, branched, or cyclic monohydric alcohol, and specifically, 1-butanol, 2-butanol, 3-methyl-l-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol or the like, may be used, and as the particularly preferable monohydric alcohol having 5 or more carbon atoms, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-l-butanol or the like, may be used.

[0612] Each component described above may be mixed plurally, or may be used being mixed with organic solvents other than those described above.

[0613] Moisture content in the rinsing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By making the moisture content be 10% by mass or less, satisfactory development characteristics may be obtained.

[0614] Vapor pressure of the rinsing solution used after the development step using the developer containing an organic solvent is preferably greater than or equal to 0.05 kPa and less than or equal to 5 kPa, more preferably greater than or equal to 0.1 kPa and less than or equal to 5 kPa, most preferably greater than or equal to 0.12 kPa and less than or equal to 3 kPa at 20°C. By making the vapor pressure of the rinsing solution be greater than or equal to 0.05 kPa and less than or equal to 5 kPa, temperature Uniformity within the wafer surface is improved and swelling due to the penetration of the rinsing solution is suppressed, therefore, dimension uniformity within the wafer surface is improved.

[0615] An appropriate amount of surfactant may be added to the rinsing solution and used.

[0616] In the rinsing step, the wafer developed using the developer containing an organic solvent is cleaned using the rinsing solution containing an organic solvent described above. The cleaning method is not particularly limited. However, for example, a method in which a rinsing solution is continuously discharged on a substrate rotating at a constant rate (a spin coating method), a method in which a substrate is immersed in a tank filled with a rinsing solution for a certain period of time (a dip method), a method in which a rinsing solution is sprayed on a substrate surface (a spray method), or the like, may be applied, and among these, it is preferable that cleaning treatment be carried out using the spin coating method, the substrate be rotated at a rotational speed of 2,000 rpm to 4,000 rpm after cleaning, and the rinsing solution be removed from the surface of the substrate. It is also preferable that the heating step (Post Bake) be included after the rinsing step. The residual developer and the rinsing solution between and inside the patterns are removed by bake. The heating step after the rinsing step is typically performed at 40 to 160°C and preferably at 70 to 95°C, and typically for 10 seconds to 3 minutes and preferably 30 seconds to 90 seconds.

[0617] Furthermore, the present invention also relates to a method for producing an electronic device, which includes the method for forming a negative pattern of the present invention and an electronic device produced by this method.

[0618] The electronic device of the present invention is suitably installed in electrical and electronic devices (home appliances, OA and media-related apparatuses, optical apparatuses, communication apparatuses, and the like).

[0619] Examples

[0620] Hereinafter, the present invention will be more specifically described based on

Examples, but the present invention is not limited to the following Examples.

[0621] <Acid-degradable resin (A)>

[0622] (Synthesis Example 1) Synthesis of Resin A-l

[0623] 22.11 parts by mass of cyclohexanone was heated at 80°C under a nitrogen gas flow. While stirring this liquid, a mixture solution of 5.69 parts by mass of a monomer represented by the following structural formula M-l , 5.46 parts by mass of a monomer represented by the following structural formula M-2, 41.07 parts by mass of cyclohexanone, and 0.59 parts by mass of dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was further stirred for 2 hours at 80°C. After the obtained reaction solution was cooled, the reaction solution was subjected to reprecipitation with a large amount of hexane/ethyl acetate and filtered, and the obtained solid was subjected to vacuum drying, whereby 8.85 pars by mass of resin (A-l) of the present invention was obtained. [0624] The weight average molecular weight (Mw: polystyrene standards) of the obtained resin (A- 1) measured by GPC (carrier: tetrahydrofuran (THF)) was Mw= 11,500 and the degree of dispersion Mw/Mn=1.62. The compositional ratio measured by ¹³ C-NMR was 40/60.

[Chem. 67]

[0625] Resins A-2 to A- 10 were synthesized in the same manner as the resin (A-1). The synthesized polymer structures are shown below with compositional ratios, weight average molecular weights (Mw), and degrees of dispersion (Mw/Mn).

[Table 4]

[0626] <Compound (G)>

[0627] (Synthesis Example 1) Synthesis

[Chem. 68]

[0628] 20.4 g (0.089 mol) of l-(tert-butoxycarbonyl)-4-piperidine carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 g of pyridine, and 38.8 g (0.106 mol) of lH,lH,2H,2H-tridecafluoro-l-n-octanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 300 ml three-necked flask, followed by stirring in an ice bath. 20.3 g (0.106 mol) of p-toluenesulfonyl chloride powder was added to the obtained solution, and then stirred in an ice bath for 30 minutes, followed by stirring at room temperature for 2 hours to obtain reaction liquid. Thereafter, the reaction liquid was added to 500 ml of 0.5 N aqueous hydrochloric acid and the mixture was stirred, followed by extraction by using 200 ml of hexane. The organic phase was washed with 500 ml of saturated aqueous sodium bicarbonate and then washed with 500 ml of pure water. Thereafter, the organic phase was dehydrated using magnesium sulfate and a filtrate after filtration was distilled off under reduced pressure. The residue was purified through column chromatography (Si0 ₂ , hexane:ethyl acetate=20: l) to obtain 19.5 g of G-16 (yield 41.8%).

[0629] Ή-NMR (400 MHz, CDC1 ₃ ): 51.41-1.47 (s, 9H), 1.62-1.71 (m, 2H), 1.88-1.94 (m, 2H), 2.61-2.73 (m, 1H), 2.79-2.97 (m, 2H), 3.93-4.12 (br, 2H), 5.44-5.55 (t, 2H), 5.93-6.04 (t, 2H).

[0630] ¹⁹ F-NMR (400 MHz, CDC1 ₃ ): δ-129.9 (d, 3F), -128.2 (m, 2F), -126.0 (m, 2F), -123.1 (m, 2F), -118.5 (m, 4F), -97.4 (d, 2F).

[0631 ] (Synthesis Example 2) Synthesis of G-4

[Chem. 69]

Intermediate 1

[0632] 10.5 g (0.1 mol) of 2,2'-iminodiethanol and 50 ml of tetrahydroiuran were added to a 200 ml three-necked flask and 24.6 g (0.1 mol) of di-tert-amyl dicarbonate was added thereto while stirring in an ice bath. Thereafter, the mixture was stirred in an ice bath for 30 minutes and then stirred at room temperature for 2 hours. The precipitated crystals were filtered, and then the crystals were stirred under heating with 50 ml of ethyl acetate and the temperature of the crystals was returned to room temperature to precipitate crystals. The precipitated crystals were filtered to obtain 14.5 g of an intermediate 1 (yield 66.2%).

[0633] 1H-NMR (400 MHz, CDC1 ₃ ): 60.83-0.93 (t, 3H), 1.41- 1.49 (s, 6H), 1.73-1.83 (q, 2H), 3.37-3.48 (br, 4H), 3.72-3.82 (br, 4H).

[0634] 2.19 g (0.01 mol) of the intermediate 1, 1.6 g (0.02 mol) of pyridine, and 5 ml of acetonitrile were added to a 50 ml flask, followed by stirring in an ice bath. 8.2 g (0.02 mol) of heptafluorobutyric anhydride was added dropwise to the obtained solution. The reaction solution obtained by stirring the solution for 1 hour at room temperature was added to 300 ml of saturated aqueous sodium bicarbonate, followed by extraction by using 100 ml of ethyl acetate. Then, the organic phase was washed with 300 ml of saturated brine, thereafter dehydrated using magnesium sulfate and filtered. The filtrate was distilled off under reduced pressure and the residue was purified through column chromatography (Si0 ₂ /hexane:ethyl acetate=20: l) to obtain 4.0 g of G-4 (yield 65.5%).

[0635] Ή-NMR (400 MHz, CDC1 ₃ ): 50.84-0.92 (t, 3H), 1.42-1.48 (s, 6H), 1.73-1.83 (q, 2H), 3.54-3.63 (br, 2H), 4.42-4.63 (br, 4H).

[0636] ¹⁹ F-NMR (400 MHz, CDC1 ₃ ): δ-124.3 (d, 6F), -118.5 (m, 4F), -80.7 (d, 4F).

[0637] Similarly, other compounds (G) shown below were synthesized.

[Chem. 70]

[0638] <Comparative Compound>

[0639] For comparison, compounds (G-31) and (G-32) shown below were used.

[Chem. 71]

[0640] <Compound (B)>

[0641] As the acid generator, the following compounds were used.

[Chem. 72]

PAG-12

PAG-11 [Chem. 73]

[0642] <Compound (N) = photobase>

[0643] As the basic compound of which basicity is decreased by irradiation of actinic rays or radiation, the following compounds were used.

Chem. 74]

[0644] hydrophobic Resin (D)>

[0645] The hydrophobic resin (D) was used by being appropriately selected from the above-exemplified resins (HR-1) to (HR-113). In addition, the hydrophobic resin (HR-83) was synthesized based on the disclosures of the specification of US2010/0152400 A, WO2010/067905 A, WO2010/067898 A, and the like.

[0646] <Surfactant>

[0647] The following were used as the surfactant.

W-1 : Megaface F176 (manufactured by DIC CORPORATION; fluorine-based)

W-2: Megaface R08 (manufactured by DIC CORPORATION; fluorine and silicon-based)

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

W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) W-5: KH-20 (manufactured by Asahi Glass Co., Ltd.)

W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based) [0648] <Solvent>

[0649] The following were prepared as the solvent.

SL-1 : propylene glycol mono methyl ether acetate (PGMEA)

SL-2: propylene glycol mono methyl ether propionate

SL-3: 2-heptanone

SL-4: ethyl lactate

SL-5: propylene glycol monomethyl ether (PGME)

SL-6: cyclohexanone

SL-7: γ-butyro lactone

SL-8: propylene carbonate

[0650] <Developer>

[0651] The following were prepared as the developer.

SG-1 : butyl acetate

SG-2: methyl amyl ketone

SG-3: ethyl-3-ethoxypropionate

SG-4: pentyl acetate

SG-5: isopentyl acetate

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

SG-7: cyclohexanone

[0652] <Rinsing Solution>

[0653] The following were prepared as the rinsing solution.

SR-1 : 4-methyl-2-pentanol

SPv-2: 1-hexanol

SR-3: butyl acetate

SR-4: methyl amyl ketone

SR-5: ethyl-3-ethoxypropionate

[0654] <Evaluation Method>

[0655] <ArF Liquid Immersion Exposure>

[0656] <Resist preparation and isolated hole pattern formation>

[0657] The components shown in Examples were dissolved in the solvents shown in the following Table at 3.2% by mass in terms of a solid content, and the respective solutions were filtered through a polyethylene filter having a pore size of 0.03 μηι, thereby preparing actinic ray- sensitive or radiation-sensitive resin compositions (resist compositions). ARC 145 A (manufactured by Brewer Science, Inc.) for forming an organic antireflection film was coated onto a silicon wafer, followed by baking at 205°C for 60 seconds, thereby forming an antireflection film having a film thickness of 46 nm. Further, ARC113A (manufactured by Brewer Science, Inc.) for forming an organic antireflection film was coated thereon, followed by baking at 205°C for 60 seconds, thereby forming an antireflection film having a film thickness of 49 nm. The actinic ray-sensitive or radiation-sensitive resin composition was coated onto the antireflection film, followed by baking (PB: Prebake) at 100°C for 60 seconds, thereby forming a resist film having a film thickness of 80 nm.

[0658] The obtained wafer was subjected to pattern exposure through a squarely arranged halftone mask in which a hole portion was 80 nm and a pitch between holes was 480 nm by using an ArF excimer laser liquid immersion scanner (manufactured by ASML; XT 1700i, NA 1.20, C-Quad, outer sigma 0.810, inner sigma 0.65, XY deflection). Ultra-pure water was used as the immersion liquid. Thereafter, the wafer was heated (PEB: Post Exposure Bake) at 100°C for 60 seconds. Next, developing was performed by paddling the organic solvent-based developer shown in the following Table for 30 seconds, and the wafer was rinsed by paddling the rinsing liquid shown in the following Table for 30 seconds. Subsequently, by rotating the wafer at a frequency of rotation of 2,000 rpm for 30 seconds, an isolated hole pattern having a hole diameter of 50 nm was obtained. An exposure amount used at that time was set to be an optimal exposure amount.

[0659] [Uniformity of local pattern dimensions (Local CDU, nm)]

[0660] In twenty 1 μπι square areas within the range exposed in one shot using the optimum exposure amount, the hole size of arbitrary 25 holes (that is, 500 in total) in each area was measured and 3σ was calculated from standard deviations of these. The smaller the value, the smaller the variation in the dimension, and it indicates a satisfactory performance.

[0661] [Depth of focus evaluation (DOF, unit: μιη)]

[0662] The resist films obtained by the actinic ray-sensitive or radiation-sensitive resin compositions in Examples and Comparative Examples were exposed while the focus in an optimal exposure amount was changed from -0.2 μιη to 0.2 μπι. The obtained isolated hole patterns were observed using a scanning electron microscope (S9380II manufactured by Hitachi, Ltd.) and dimensions thereof were measured. Then, the focus range was calculated so as to adjust the pattern dimension to be 45 nm to 55 nm. The larger the value, the wider the depth of focus, and it indicates a satisfactory performance.

[0663] [Minimum dimension evaluation (unit: nm)]

[0664] The resist films obtained by using the actinic ray-sensitive or radiation-sensitive resin compositions in Examples and Comparative Examples were exposed while an exposure amount was changed. The obtained isolated hole patterns were observed using a scanning electron microscope (S9380II manufactured by Hitachi, Ltd.) and hole diameteres and dimensions thereof were measured. Then, a minimum pattern dimension in which the isolated hole patterns are resolved was obtained.

[0665] The smaller the measurement dimensions, the better the pattern resolution.

[Table 5]

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[Table 6]

[0666] From the above results, it was found that the contact hole pattern formed by using the method for forming a negative pattern of the present invention is excellent in depth of focus (DOF), uniformity of local pattern dimensions and resolution.

[0667] The method for forming a negative pattern of the present invention which is capable of providing an excellent pattern even in forming a contact hole pattern can be preferably used in a method for producing an electronic device.