TW200923574A - Fluorine-containing compound, resist composition for immersion exposure, and method of forming resist pattern - Google Patents

Abstract

A resist composition for immersion exposure including a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid, an acid-generator component (B) which generates acid upon irradiation, and a fluorine-containing compound (C) having a group represented by general formula (c) shown below and containing at least one fluorine atom: [Chemical Formula 1] wherein Q represents a group in which one hydrogen atom has been removed from a monovalent hydrophilic group; and R1 represents a hydrocarbon group of 2 or more carbon atoms Which may have a fluorine atom.

Description

200923574 IX. Description of the Invention [Technical Field] The present invention relates to a fluorine-containing compound, a resist composition for liquid immersion exposure containing the fluorine-containing compound, and a photoresist composition using the immersion exposure Method for forming a photoresist pattern of a material. The present invention is a special wish 2007 which was applied for in Japan on August 3, 2007, in the Japanese Patent Application No. 2007-203 1 77, and January 1, 2007. The priority is claimed on the basis of the Japanese Patent Application No. 2008-080695, filed on Jan. [Prior Art] In the lithography technique, a photoresist film obtained by a photoresist material is generally formed on a substrate, and a mask of a specific pattern is formed on the photoresist film by light, an electron beam, or the like. The selective exposure of the radiation is carried out by applying a development treatment to form the photoresist film into a specific shape of the photoresist pattern. With the miniaturization of semiconductor elements, the short wavelength of the exposure light source and the high number of openings (high NA) of the projection lens have been developed. At present, an ArF excimer laser having a wavelength of 193 nm has been developed as a light source NA = 〇· 84 exposure machine. Along with the short wavelength of the exposure light source, the photoresist material has sought to have a sensitivity to the exposure light source, and it is possible to reproduce the lithographic etching characteristics such as the resolution of the fine size pattern. A photo-resistance material that meets this demand is generally used as a chemically amplified photoresist which contains a base resin which changes the alkali solubility by an action of an acid, and an acid generator which generates an acid based on exposure. At present, the base resin of the chemically amplified photoresist used in the ArF excimer laser lithography etching, for example, has excellent transparency in the vicinity of 193 nm, and the like, and generally uses a main chain having a (meth) A resin (acrylic resin) of a structural unit derived from acrylate. Here, "(meth)acrylic acid" means one or both of a acrylic acid having a hydrogen atom bonded to the α-position and a methacrylic acid having a methyl group bonded to the α-position. The "(acrylic acid ester)" refers to one or both of the acrylate of the hydrogen atom at the alpha position and the methacrylate of the methyl group. "(Meth)acrylic acid acrylate" means an acrylate having a hydrogen atom bonded to the α-position, or a methacrylate having a methyl group bonded to a methyl group or both. One of the methods for lifting the analytic upwards, for example, lithography etching between an objective lens of an exposure machine and a sample, exposure (immersion exposure) under a liquid having a higher refractive index than air (immersion medium) The method, that is, generally referred to as Liquid Immersion Lithography (hereinafter also referred to as immersion exposure) (for example, Non-Patent Document 1). When using immersion exposure, it is known that even if a light source of the same exposure wavelength is used, it can achieve the same high resolution as in the case of using a light source of a shorter wavelength or a case of using a high NA lens, and further, it does not Reduce the focus depth of field. Further, the immersion exposure can be carried out using an existing exposure apparatus. Therefore, the immersion exposure is presumably at a low cost, and it is possible to realize a photoresist pattern having a high resolution of -6 - 200923574 and having an excellent focal depth of field. In the manufacture of semiconductor components requiring a large investment in equipment, the cost is incurred. From the viewpoint of the lithographic etching characteristics such as the resolution, there are considerable concerns about how much the semiconductor industry can be provided. The immersion exposure is effective in the formation of the pattern shape, and it can also be combined with super-analytical techniques such as the phase shift method and the deformation illumination method which are currently studied. At present, the immersion exposure technique is mainly active in the study of the use of ArF quasi-molecular lasers as a light source. Also, at present, the infiltration medium is mainly for the study of water. In recent years, various fluorine-containing compounds have been developed in various technical fields since they have been characterized by water repellency and transparency. For example, in the field of photoresist materials, in the base resin which is a positive type of chemically amplified photoresist, it has been studied in fluorine-containing molecular compounds, and methoxymethyl, tert-butyl, tert-butyl is introduced. An acid labile group such as an oxocarbonyl group. However, when the fluorine-based polymer compound is used as a base resin of a positive-type photoresist composition, a large amount of out gas is generated after exposure, and the resistance to dry etching gas (dry etching resistance) is insufficient. . Recently, a report has been made of a fluorine-containing polymer compound having excellent etching resistance, that is, a fluorine-containing polymer compound containing an acid-labile group having a cyclic hydrocarbon group (for example, Non-Patent Document 2). [Non-Patent Document 1] Proceedings of SPIE, Vol. 5754, pp. 1 1 9 - 1 28 (2005). [Non-Patent Document 2] Proceedings of SPIE, Vol. 4690, pp. 76-83 (2002). 200923574 SUMMARY OF THE INVENTION In the immersion exposure, in addition to the usual lithographic etching characteristics (sensitivity, decomposability, etching resistance, etc.), a photoresist material having characteristics compatible with the immersion exposure technique is sought. For example, in the immersion exposure, when the photoresist film is in contact with the immersion medium, the substance in the photoresist film may be dissolved in the immersion medium (the substance is eluted). When the substance is eluted, the deterioration of the photoresist layer, the change in the refractive index of the immersion medium, and the like are caused, and the lithography engraving characteristics are deteriorated. The amount of elution of the substance is affected by the characteristics of the surface of the photoresist film (e.g., hydrophilicity, hydrophobicity, etc.). For example, when the hydrophobicity of the surface of the photoresist film is increased, the elution of the substance can be reduced. Further, in the case where the liquid immersion medium is water or the like, when the immersion light is applied by the scanning type immersion type exposure machine described in Non-patent Document 1, the liquid immersion medium is sought to follow the movement of the lens to achieve water followability. The lower the water followability, the lower the exposure speed, and there are doubts that affect productivity. This water followability is presumed to increase as the hydrophobicity of the photoresist film increases (watering). Thus, by increasing the hydrophobicity of the surface of the photoresist film, reducing the elution of the substance or improving the water followability, it is presumed that the problems unique to the immersion exposure technique can be solved. However, when the photoresist film is hydrophobized, it adversely affects the lithographic etching characteristics and the like. For example, when the hydrophobicity of the photoresist film is increased, the photoresist film after alkali development is liable to cause problems such as defects. In particular, in the case of a positive-type photoresist composition, defects are likely to occur in the unexposed portion. The defect refers to, for example, all the defects detected when the surface defect observation device (trade name "KLA") of KLA Tankel is used to observe from the surface of the developed photoresist pattern 200923574. This is missing, for example, scum after development, air bubbles, waste, bridging (overlap structure between photoresist patterns), stains, precipitates, residue, and the like. The hydrophobicity at the time of immersion exposure is presumed to solve these problems as long as a material having a hydrophilic property at the time of development is used, but there is hardly any knowledge of the material having the above characteristics. In the light of the above, the present invention provides a novel fluorine-containing compound which can be used as an additive for a photoresist composition for immersion exposure, and a photoresist composition for immersion exposure containing the fluorine-containing compound, and The method for forming a photoresist pattern of the resist composition for immersion exposure is aimed at achieving the above object, and the present invention adopts the following constitution. That is, the first aspect of the present invention is a photoresist composition for immersion exposure characterized by comprising a substrate component (A) which changes the solubility of an alkali developer by an action of an acid, and An acid generator component (B) which generates an acid by exposure, and a fluorine-containing compound (C) having a group represented by the following formula (c) and containing at least one fluorine atom; 'Faguang base uses the photon shape to expose the original type of hydrogen type. Figure dip 1Rl j /—\ & In addition to the base light sample to one of the hydrocarbon species, one parent thinks that C) is the second (the valence state before the "1 carbon" for the R1Q The first contains |, the original package o = -c in the fluorine, Q--form has a | t with the intrinsic one for its 200923574 composition to form a photoresist film on the support, the aforementioned photoresist a step of performing a immersion exposure of the film, and a step of alkali developing the photoresist film to form a photoresist pattern. The third aspect of the present invention is a fluorine-containing compound characterized by having the following formula ( C) The group represented by at least one fluorine atom.

Q— [wherein, Q is a group in which a hydrophilic group of one valence removes one hydrogen atom, and R1 is a hydrocarbon group which may have fluorine (having a carbon number of 2 or more of the atom). Further, the structural unit in the specification and the patent application scope "The meaning of the monomer unit (monomer unit) constituting the resin component (polymer, copolymer). "Exposure" includes the general commemoration of radiation irradiation. "Alkyl", unless otherwise specified, includes a linear, branched, and cyclic monovalent saturated hydrocarbon group. "Lower alkyl" means an alkyl group having 1 to 5 carbon atoms. The present invention provides a suitable photoresist for immersion exposure. A novel fluorine-containing compound for an additive for a composition, a resist composition for immersion exposure containing the fluorine-containing compound, and a method for forming a photoresist pattern using the resist composition for immersion exposure. Compound -10-200923574 First, a fluorine-containing compound (hereinafter also referred to as a fluorine-containing compound (C)) of the present invention will be described. The fluorine-containing compound (C) is a photoresist composition for immersion exposure of the present invention. Composition Implants of additive compounds which resist composition suitable for immersion exposure for the fluorine-containing compound (C), the group having the formula (C) represented by the, and containing at least one fluorine atom.

In the formula (C), in the Q, the monovalent hydrophilic group only needs to have at least one hydrogen atom, for example, a hydroxyl group (monoOH), a carboxyl group (_C(=〇)〇H), an amine group (- NH2) and so on. Q is a group obtained by removing one hydrogen atom from the above monovalent hydrophilic group. For example, when the monovalent hydrophilic group is an OH, Q is -Ο. Further, in the case where the 1-valent hydrophilic group is -C(=0)0H, Q is -C(=0)0-. also,! When the hydrophilic group of the valence is an NH2, Q is an NH-. Q is preferably a 0 - or a C (=0) 0 - and a Ο - is best. R1 is a hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom. The fluorine-containing compound (C) is a compound having at least one fluorine atom in its structure. Therefore, when a portion other than R1 of the fluorine-containing compound (C) (for example, R2 in the formula (C-1) described later) does not contain a fluorine atom, Ri is a fluorine-substituted hydrocarbon group. When a portion other than R1 of the fluorine-containing compound (C) contains a fluorine atom, 'R1' may be an unsubstituted hydrocarbon group or a fluorine-substituted hydrocarbon group. The hydrocarbon group of R1 may be a hydrocarbon group formed only of a carbon atom and a hydrogen atom, or a fluorine-substituted hydrocarbon group which may be partially or wholly replaced by a fluorine atom of a hydrogen atom in the unsubstituted thio group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. -11 - 200923574 The "aliphatic" in the scope of the patent application and the description of the present invention is a relative concept of aromatics, and is defined as a group having no aromaticity, a compound or the like. The aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. The aliphatic hydrocarbon group may be either saturated or unsaturated, and it is usually preferred to saturate. That is, the aliphatic hydrocarbon group is preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group. The unsubstituted alkyl group may be linear, branched or cyclic, or may be a combination of a linear or branched alkyl group and a cyclic alkyl group. The unsubstituted linear alkyl group is preferably, for example, a carbon number of 2 to 1 Å, more preferably a carbon number of 2 to 8. Specifically, for example, ethyl, n-propyl, n-butyl, η-pentyl, n-hexyl, n-heptyl, η-octyl, η-fluorenyl, η-fluorenyl and the like. The unsubstituted branched alkyl group is preferably a carbon number of 3 to 10, more preferably a carbon number of 3 to 8. The branched alkyl group is preferably a third-order alkyl group, and particularly preferably a group represented by the following formula (c-1). [Chemical 3] R7 ——^-R8 R9 (c _ 1 ) wherein R7 to R9 are each a straight-chain alkyl group having an independent carbon number of 〜5. The alkyl group of R7 to R9 is preferably an ethyl group or a methyl group, particularly preferably a methyl group. -12- 200923574 Unsubstituted cyclic alkyl group, for example, a monocyclic chain, or a group obtained by removing one hydrogen atom from a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane . Specifically, for example, a monocyclic ring group such as a cyclopentyl group or a cyclohexyl group, or a polycycloalkyl group such as an adamantyl group, a norbornyl group, an isobornyl group, a tricyclic fluorene group, or a tetracyclododecyl group. . An unsubstituted linear or branched alkyl group may be combined with a cyclic building group, for example, a linear or branched alkyl group bonded to a ring-based base group as a substituent, and a ring The base of the compound is bonded to a base of a linear or branched alkyl group as a substituent. The fluorine-substituted alkyl group is, for example, a group in which one or all of hydrogen atoms in the above-mentioned unsubstituted compound group is substituted by a fluorine atom. a fluorine-substituted alkyl group which may be a group in which a part or all of a hydrogen atom in an unsubstituted alkyl group is substituted by a fluorine atom, or a group in which an alkyl group in an unsubstituted alkyl group is completely substituted by a fluorine atom (all Fluoroalkyl) is also acceptable. The fluorine-substituted alkyl group in R1 is preferably a linear or branched fluorine-substituted alkyl group, particularly R41-R42 (wherein R41 is an unsubstituted alkyl group having 1 to 9 carbon atoms' R42 is The fluorine-substituted alkyl group having 1 to 9 carbon atoms; preferably, the total of the carbon numbers of R41 and R42 is 10 or less. In the formula, R41 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group or a propyl group. R42 is preferably a linear or branched fluorine-substituted alkyl group having 1 to 5 carbon atoms. Specifically, a perfluoroalkyl group is preferred, and a trifluoromethyl group or a tetrafluoroethyl group is preferred. The fluorine-containing compound (C) of the present invention is not particularly limited as long as it has a compound represented by the above formula (c) - 13 to 200923574 and contains a fluorine atom. For example, a polymer compound (polymer, copolymer) having a side chain having a group represented by the formula (C) may be used, or a low molecular compound (non-polymer) may be used. When the fluorine-containing compound (C) is a low molecular compound, the compound (c)' is preferably a compound represented by the following formula (c-i) (hereinafter, also referred to as a compound (C-1)). When the fluorine-containing compound (C) is a polymer compound, the fluorine-containing compound (C) has the following general formula (cl—i—〇, ( cl _ 1 _ 2 }, ( c 1−1−3) or ( The polymer compound of the structural unit represented by c 1 -1 - 4 ) (hereinafter also referred to as polymer compound (c 1 )) is preferred. [Chemical 4] 〇R2—Q—C—R3 (c _ 丄[wherein Q is the same as Q in the above formula (C)] R2 is an organic group containing an aromatic ring group which may have a fluorine atom, and r3 is a carbon number which may have a fluorine atom of 2 or more a hydrocarbon group, at least one of R2 and R3 having a fluorine atom]. -14- 200923574

Wherein R51 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R52 to R5 5 are each independently a hydrogen atom or a fluorine atom; at least one of R52 to R55 is a fluorine atom, and R56 is a fluorine atom. a hydrocarbon group having 2 or more carbon atoms; R01 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R62 to R65 are each independently a hydrogen atom or a fluorine atom, and R66 is a hydrocarbon group having a fluorine atom having a carbon number of 2 -15 to 200923574 or more ]. Hereinafter, the compound (C-1) and the polymer compound (c1) will be described in more detail. [Compound (C-1)] In the formula (c-1), the organic group of R2 is a group containing an aromatic ring group, and may be composed of only an aromatic ring group or an aromatic ring group. It may be composed of a base other than the aromatic ring group. The organic group of R2 is preferably a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring having a substituent. The ring skeleton of the aromatic hydrocarbon ring is preferably a carbon number of 6 to 15, for example, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring or the like. Among them, the benzene ring is the best. The number of the substituents having an aromatic hydrocarbon ring may be one, or two or more, and preferably one. The substituent having a carbacyclic ring is preferably a substituent containing a polymerizable group. The polymerizable group is a group in which a compound having such a polymerizable group can be subjected to polymerization such as radical polymerization. Polymerizable Group 'In general, a polymerizable group used as a monomer, for example, a group having an ethylenically unsaturated double bond, such as a group having an ethylenically unsaturated double bond, for example, CH2 = qRG" _ ( CH2)b—the base of the table, CH2 = C(R°3) — C( = Ο) - 〇—the base expressed, etc., which is represented by CH2=C(RQ3) — (CH2)b The base of -16-200923574 ch2= c(rG3) - c(= 〇) - 〇 - is preferably a group. In the formula, 'rG3 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group. The lower alkane of rQ3 a specific linear chain such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl or neopentyl Or a branched alkyl group. Further, a halogenated lower alkyl group, for example, a group in which a part or all of a hydrogen atom of the lower alkyl group is substituted by a halogen atom, etc. The halogen atom, for example, a fluorine atom, A chlorine atom, a bromine atom, an iodine atom, etc., particularly preferably a fluorine atom. R133 is preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group, and is a hydrogen atom or Preferably, b is an integer of 0 to 2, preferably 〇 or 1 and 〇 is the most preferable. The substituent containing a polymerizable group may be a base composed only of a polymerizable group or may be The polymerizable group may be a group composed of a group other than the polymerizable group. The polymerizable group 'and a group other than a polymerizable group', for example, the above-mentioned polymerizable group, and a bivalent A group consisting of a linking group, etc. The linking group of a valence is, for example, a hydrocarbon group or a group containing a hetero atom. The hydrocarbon group is, for example, the same as the alkyl group of the above RG1. The hetero atom is a carbon atom and hydrogen. An atom other than an atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc. A group containing a hetero atom, for example, a 0-, a C (=〇) a '-C (=0) - ◦-, - NH—, —NR°4 (R°4 is an alkyl group)—, one NH—C(=0)—, =N-, a combination of these groups with a divalent hydrocarbon group, etc. -17- 200923574 In the present invention The organic group of R2 is preferably a substituent which is obtained by removing one hydrogen atom from an aromatic hydrocarbon ring having a substituent containing a polymerizable group. The substituent of the polymerizable group is preferably a base represented by the formula of the formula ch2 = C(R03) - (CH2)b - or the formula - C (= 0) - 〇 - in the formula. R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R The alkoxy group, the halogenated lower alkyl group, the oxygen atom (=Ο), etc. In the present invention, the substituent of the aromatic hydrocarbon ring preferably has at least one fluorine atom. In this case, the fluorination rate of the aromatic hydrocarbon ring, that is, the ratio (%) of the number of fluorine atoms in the total number of hydrogen atoms and fluorine atoms contained in the square smog ring, is 1 0~ 1 0 0 % is preferable, and 5 0 to 1 〇〇% is more preferable, and 1 〇〇% is the best. That is, it is preferred that all of the hydrogen atoms in the aromatic hydrocarbon ring are replaced by fluorine atoms. R3' is, for example, the same as the above R1. The compound (c-1) is a compound having at least one fluorine atom in its structure. Therefore, when R2 does not have a fluorine atom, R3 has a fluorine atom. In the case where the above R2 has a fluorine atom, R3 may have a fluorine atom or may have no fluorine atom. Further, when R3 does not have a fluorine atom, 'r2 has a fluorine atom. When R3 has a fluorine atom, R2 may have a fluorine atom or may have no fluorine atom. The compound (C~:l), especially the compound -18- represented by the following formula (C-1 - 1), (C_ 1 ~ 2), (C_1-3) or (c: - 1-4) 200923574 The thing is better. 【化6】

R53 R55 R63

(C-1 - 2}

O

Ό—C—R 56 (C-1 - 3) O -〇—C—R66 R65 (C-1 - 4) wherein R51 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R52 R55 At least one of R52 to R5 5 is a fluorine atom, and R56 is a hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom, which are independent hydrogen atoms or fluorine atoms. R61 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R62 to R65 are each independently a hydrogen atom or a fluorine atom, and R66 is a hydrocarbon group having a fluorine atom of -19-200923574 having a carbon number of 2 or more. R51' is the same as the aforementioned RG3, for example. R5i is preferably a hydrogen atom, a low-grade courtyard group or a fluorinated lower-grade courtyard group, and further preferably a hydrogen atom or a methyl group, R52 to R55 are independent hydrogen atoms or fluorine atoms, and at least 1 of r52 to r55. One is a fluorine atom. When R52 to R55 are considered to be easy to manufacture, it is preferable to use all of the fluorine atoms. R56 is, for example, the same as the aforementioned R3. In particular, it is preferably an unsubstituted or fluorine-substituted branched alkyl group, and the unsubstituted or fluorine-substituted third-order alkyl group or the above-mentioned one represented by R41 to R4 2 is more preferable. The unsubstituted or fluorine-substituted third-order alkyl group is preferably a group represented by the above formula (c-1). R01 is, for example, the same as the aforementioned R51. R62 to R65 are each independently a hydrogen atom or a fluorine atom. R62 to r65 are preferably all fluorine atoms or all hydrogen atoms in consideration of easiness of production. R66 is, for example, the same as the hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom as exemplified in the above R56, and may have the same fluorine atom. The compound (C-1), in the above compound, is preferably a compound represented by the formula (C-1-1) or (C-1 to 4). Further, the compound represented by the following formula (c-l-ll), (C-1-12), (C-1-41)' or (C-l-42) is more preferable. -20- 200923574 【化7】

R64 R65 (c - 1 - 4 2) wherein R51, R7 to R9, R61 to R65, and R41 to R42 are the same as those described above. The compound (C-1) can be used as an additive for the photoresist composition without further treatment. Further, the compound (C-1) is as the compound represented by the above formula (C-1 to 1), (C-1 - 2 ), (C-1 to 3) or (C-1 to 4), In the case of a compound containing a polymerizable group, the compound (C-1) can be used as a polymer compound by polymerization alone or in combination with other polymerizable compounds. This polymer compound is suitable as an additive for a photoresist composition for immersion exposure, similar to the compound (C-1).

In the above, the compound represented by the formula (C-1-1), (c-1 - 2), (C-1 to 3) or (C-1 to 4) may be used in the production of the polymer described later. For the compound (C1). [Polymer compound (C1)] The polymer compound (C1) has the above formula (cl-1 - 1), (cl - 1 - 2 ), (cl - 1 - 3) or (Cl - 1 - 4) The structural unit represented (hereinafter also referred to as structural unit (c 1 )). R51 to R56 and R61 to R66 in the formula (cl-1 to 1) to (cl-1 to 4) are respectively R51 in the above formula (C-1 to 1) to (C-1 to 4) ~R56, RW~R66 are the same content. In the polymer compound (C 1 ), the structural unit (c 1 ) is preferably a structural unit represented by the above formula (c 1 -1 -1 ) or (c 1 -1 - 2 ), and has a formula ( The structural unit represented by c 1 - 1 - 1 ) is more preferable. In particular, it is preferably a structural unit represented by the following formula (cl - 1 - 11) or (cl - i - 12). -22- 200923574 【化8】

[In the formula, R51, R7 to R9, R61 to R65, and R41 to R42 are the same contents as described above]. The ratio of the structural unit (c 1 ) in the polymer compound (c 1 ) is preferably 3 〇 〜1 〇〇 mol % of the total structural unit constituting the polymer compound (C 1 ), and is preferably 5 0 〜1 〇 〇 Moile% is better, 100% Mo is the best. The polymer compound (C1) may have a structural unit other than the structural unit (c 1 ) without impairing the effects of the present invention. The structure is not particularly limited, and it is preferably a structural unit of a compound copolymerizable with a compound represented by any one of the above formula (C-1 1 -1 - 1 - 4 ). The structural unit, for example, the infiltrated exposure composition described later may have a structural unit derived from the structural unit (a1), the listed units (a 1 ) to (a4 ), and the structural styrene derived from hydroxystyrene. Wait. In particular, the structural unit (a) -23- 1-12) and the example, the phase, in units of 4 60~ range, ~ (C-derived light light structure position, benzene) is better 200923574 polymer compound The mass average molecular weight (Mw) of (c 1 ) (polystyrene conversion standard of gel permeation chromatography) is not particularly limited, and it is preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000, and is 5 0 00~20000 is the best. When it is less than the upper limit of the range, when it is used as a photoresist, sufficient solubility is obtained for the resist solvent, and when it is larger than the lower limit of the range, good dry etching resistance or a good resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (Mw/Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3 Å, and most preferably 1.2 to 2.5. Further, Μη is a number average molecular weight. The polymer compound (C 1 ) ' is suitably used as an additive for a photoresist composition for immersion exposure. &lt;Production Method of Fluorinated Compound (C)&gt; The fluorine-containing compound (C) of the present invention may be, for example, a hydrophilic group of a compound having a hydrophilic group represented by a QH [Q system and the same content as described above] It is manufactured by introducing a base represented by one (: (=0) - rUri is the same as the above). A method of introducing a base represented by c (=0) - Ri can be a conventionally known method. For example, when the compound (C-1) represented by the above formula (C-1) is exemplified, the compound represented by the following formula (I) (hereinafter, also referred to as the compound (I)), The compound represented by the above formula (11) (hereinafter, also referred to as compound (π)) is reacted to produce a compound -2423, 2009 (574). [Chem. 9] 3 RI o = c I xh R2 QH (i) wherein R2, Q, and R3 are the same as those of R2, Q, and R3 in the above formula (C-1), and xh is a halogen atom or a hydroxyl group. a bromine atom, a chlorine atom, an iodine atom, a fluorine atom, etc. Xh has an excellent reactivity, and a bromine atom or a chlorine atom is used. Preferably, the chlorine atom is preferred. The method for reacting the compound (I) with the compound (II) is not particularly limited. For example, the compound (I) and the compound can be obtained in the presence of a base in a reaction solvent. (II) a method of contacting, etc. In the method, when xh is a halogen atom, for example, a compound (11) may be added to a solution in which a reaction solvent of the compound (I) is dissolved in the presence of a base. Further, in the case where Xh is a hydroxyl group, for example, in the presence of a base and a condensing agent, in a solution obtained by dissolving a reaction solvent of the compound (II), a compound is obtained by adding a compound (ί) a reaction with a compound (II) (condensation reaction). Further, when xh is a hydroxyl group, for example, in the presence of an acid, a compound (I is added in a solution of a reaction solvent of 丨n) In the embodiment, the compound (I) is allowed to react with the compound (11) (condensation reaction), etc. The compound (I) or the compound (II) can be, for example, a commercially available compound or a synthetic compound can be used. The solvent should be a solvent which can dissolve the compound (I) of the starting material and the compound-25-200923574 (11), specifically, for example, tetrahydrofuran (THF), acetone, dimethylformamide (DMF), Dimethyl acetamide, dimethyl hydrazine (DMSO), acetonitrile, etc. Alkali, such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine and other organic bases; sodium hydride, K2C〇3, An inorganic base such as Cs2C〇3, etc. The acid may be, for example, an acid commonly used for dehydration condensation, specifically, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, or p. - Organic acids such as toluenesulfonic acid. They may be used singly or in combination of two or more types. a condensing agent such as ethyldiisopropylaminocarbonyldiamine imide hydrochloride (EDC1), dicyclohexylcarboximine (DCC), diisopropylcarbonyldiimide, carbonyldiimidazole, etc. A diterpene imine reagent or a tetraethyl pyrophosphate, a benzotriazole-N-hydroxytrimethylamine squamous hexafluorophosphide salt (Bop reagent) or the like. The amount of the compound (11) to be added is preferably from about 1 to 3 moles per mole of the compound (I), and more preferably from 1 to 2 moles. The reaction temperature is preferably from 20 to 40 ° C, more preferably from 0 to 30 ° C. The reaction time ' differs depending on the reactivity of the compound (1) and the compound (11), the reaction temperature, etc., usually 30 to 24 minutes, preferably 60 to 180 minutes, and a fluorine-containing compound (C). In the case of a molecular compound, a monomer which can be derivatized into a desired structural unit (for example, a compound represented by any one of the formulae (C-1 to 1) to (C-1 to 4)) can be used, for example. A radical polymerization initiator such as azobisisobutyronitrile (AIBN) can be obtained by polymerization according to a known radical -26-200923574 polymerization or the like. Further, for example, the hydrophilic group of a hydrophilic compound (such as a hydroxystyrene resin such as polyhydroxystyrene or an acrylic resin) having a hydrophilic group represented by -QH [Q is the same as the above] may be used. The above is manufactured by introducing the basis of -C(=0) - R1 [R1 is the same as described above]. The above fluorine-containing compound (C) of the present invention is a novel compound which has not been known in the past. The fluorine-containing compound (C) can be suitably used as an additive for a photoresist composition, and a photoresist composition containing a fluorine-containing compound (C) is added, which is suitable for use in an immersion exposure. The photoresist composition to which the fluorine-containing compound (C) is added is not particularly limited as long as it can be used as an immersion exposure, and for example, it may contain a solubility to an alkali developer via an action of an acid. It is preferred that the substrate component which changes, and the chemically amplified photoresist composition which generates an acid generator component of the acid by irradiation of radiation. The fluorine-containing compound (C) is particularly suitably used as the resist composition for immersion exposure of the present invention described below. <<The photoresist composition for immersion exposure>> The photoresist composition for immersion exposure of the present invention is a substrate component (A) containing a change in solubility of an alkali developer via an action of an acid (hereinafter also referred to as An acid generator component (B) (hereinafter, also referred to as (B) component) which is an acid (A) component and irradiated by radiation, and -27-200923574 has a base represented by the above formula (c) And at least one fluorine atom fluorine-containing compound (C) (hereinafter also referred to as (C) component). &lt;(A) Component&gt; (A) The organic compound to be used as a base material for a chemically amplified photoresist is used singly or in combination of two or more kinds. Here, the "substrate component" means an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film formation energy can be improved, and a photoresist pattern of a nanometer degree can be easily formed. The organic compound having a molecular weight of 500 or more can be roughly classified into an organic compound having a molecular weight of 500 or more and a low molecular weight of less than 2,000 (hereinafter also referred to as a low molecular compound), and a high molecular weight resin having a molecular weight of 2,000 or more (high Molecular material). The aforementioned low molecular compound, S is often a non-polymer. In the case of a resin (polymer, copolymer), 'molecular weight' is a mass average molecular weight converted by polystyrene using GPC (gel permeation chromatography). Hereinafter, the term "resin" as used herein means a resin having a molecular weight of 2,000 or more. As the component (A), a resin which changes the solubility of the alkali by the action of an acid or a low molecular material which changes the solubility of the alkali by the action of an acid can be used. The immersion exposure photoresist composition of the present invention is a negative photoresist composition _ ' (A) component can be used as a base component soluble in an alkali developer -28-200923574' or the negative photoresist composition Add crosslinker. When the negative photoresist composition generates an acid by the (B) component by exposure, cross-linking occurs between the substrate component and the crosslinking agent via the action of the acid, and the alkali developer is insoluble. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by applying the negative photoresist composition on the substrate is selectively exposed, the exposed portion can be converted to be insoluble to the alkali developer, The unexposed portion is formed into a photoresist pattern by alkali development without being changed to be soluble in the alkali developing solution. The component (A) of the negative resist composition is usually a resin which is soluble in an alkali developer (hereinafter also referred to as an alkali-soluble resin). The alkali-soluble resin, which is a resin having a unit derived from at least one selected from the group consisting of α-(hydroxyalkyl)acrylic acid or a lower alkyl ester of α-(hydroxyalkyl)acrylic acid, can form a good swelling with less swelling The photoresist pattern is preferred. Further, α-(hydroxyalkyl)acrylic acid is an acrylic acid obtained by bonding a hydrogen atom bonded to a carbon atom at the α position of a carboxyl group, and a hydroxyalkyl group is bonded to a carbon atom of the α-position (preferably, a carbon number of 1 to 1) The hydroxyalkyl group of 5 is one or both of the bonded alpha-hydroxyalkylacrylic acid. When the cross-linking agent ', for example, an amine-based parent-linking agent having a methylol group or an alkoxymethyl group of glycolide or the like is usually used, a good photoresist pattern having less swelling is formed, and it is preferred. The amount of the crosslinking agent to be added is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the resist composition for immersion exposure of the present invention is a positive resist composition, the component (A) can be used as a substrate component which increases the solubility to the alkali developer via the action of an acid. That is, the component (A) is poorly soluble to the base -29-200923574 before exposure, and when the acid of the component (B) is generated by exposure, the solubility to the alkali developer is increased by the action of the acid. Therefore, when the resist pattern is formed, when the photoresist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion is converted from soluble to soluble in the alkali developing solution to be soluble. The unexposed portion is in a state in which the alkali is poorly soluble, and a photoresist pattern can be formed by alkali development. In the photoresist composition of the present invention, the component (A) is preferably a component of the substrate which increases the solubility in the alkali developer via the action of an acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. The component (A) may be a resin component (A1) (hereinafter, also referred to as (A1) component) which increases the solubility to the alkali developer via the action of an acid, or is increased by the action of an acid. The low molecular weight compound (A2) (hereinafter referred to as "A2) component) which is soluble in an alkali developer may also be used, or a mixture thereof. [(A1) component] (A1) The component is usually a resin component (base resin) which is used as a substrate component for a chemically amplified photoresist, and may be used alone or in combination of two or more. In the present invention, the (A 1 ) component preferably contains a structural unit derived from an acrylate. In the specification and patent application, "the structural unit derived from acrylate" means the structural unit formed by the cracking of the ethylenic double bond of acrylic vinegar. -30- 200923574 "Cyanate ester" refers to a carbon atom in which a carbon atom is bonded to a carbon atom bonded to a hydrogen atom. (Atom or a group other than a hydrogen atom) ) The mourning of the compound. The substituent is, for example, a lower alkyl group, a halogenated lower alkyl group or the like. Further, the α-position (carbon atom of the α-position) of the structural unit derived from the acrylate means a carbon atom bonded to the carbonyl group unless otherwise specified. In the acrylate, a lower alkyl group of a substituent, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl A lower linear or branched alkyl group such as a neopentyl group. Further, the halogenated lower alkyl group is specifically a group obtained by substituting a part or all of a hydrogen atom in the above-mentioned "lower alkyl group of the α-substituted group" with a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. In the present invention, the α-position of the acrylate is preferably a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group is more preferable. It is easy to obtain a viewpoint such as a hydrogen atom or a methyl group. The component (A 1 ) is particularly preferably a structural unit (a 1 ) derived from an acrylate having an acid-dissociable dissolution inhibiting group. Further, the component (A 1 ), in addition to the structural unit (a 1 ), is preferably a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone. (A 1 ) component, in addition to the structural unit (a 1 ), or a structural unit (-31 - 200923574 a 1 ) and (a2), a structure derived from an acrylate having an aliphatic hydrocarbon group containing a polar group The unit (a3) is better. Structural unit (a 1 ) The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) is such that, as long as the component (A 1 ) has an alkali-insoluble property, the solubility inhibition property is obtained, and the dissociation after the dissociation by acid is used. The all-component (A 1 ) component may be added to the base of the alkali developer, and the acid dissociable dissolution inhibiting group which has been proposed as a base resin for a chemically amplified resist composition can be used. In general, for example, a carboxyl group in (meth)acrylic acid may form a cyclic or chain tertiary alkyl ester group, or an acetal acid dissociable dissolution inhibiting group such as an alkoxyalkyl group. Here, the "trialkyl ester", for example, a hydrogen atom of a carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester, and an oxygen atom at the terminal of the carbonyloxy group (-c(0) - 0-) is bonded. A structure obtained by the tertiary carbon atom of the aforementioned chain or ring-shaped courtyard base. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the aforementioned chain or cyclic alkyl group may have a substituent. The following is an acid dissociable group formed by a carboxyl group and a tertiary alkyl ester, which is conveniently referred to as a "trialkyl ester type acid dissociable dissolution inhibiting group". Tertiary alkyl ester type acid dissociation The dissolution inhibiting group is, for example, an aliphatic branched acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. -32- 200923574 "Alkali branched" means a branched structure having no aromaticity. The structure of the "aliphatic branched acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred to saturate. The aliphatic branched acid dissociable dissolution inhibiting group is preferably a tertiary alkyl group having 4 to 8 carbon atoms, and specifically, for example, tert-butyl, tert-pentyl, tert-heptyl or the like. The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (a 1 ) may have a substituent or may not have a substituent. The substituent is, for example, a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (= 〇). The "aliphatic cyclic group" removes the basic ring structure of the substituent, and does not limit the group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and generally it is preferably saturated. The "aliphatic cyclic group" is preferably a polycyclic group. An aliphatic cyclic group, for example, which may be substituted by a lower alkyl group, a fluorine atom or a fluorinated alkyl group, or may be substituted by a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane. More specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, norbornane, isopentane, tricyclodecane or tetracyclododecane is removed. A group obtained by one or more hydrogen atoms. -33- 200923574 An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom on a ring skeleton of a cyclic group, etc. 'specifically', for example, 2-methyl-2- King Kong Institute base, or 2-ethyl one 2-golden hospital base. Or, for example, in the structural unit represented by the following general formula (a Γ '-1) to (a 1 ′-6), the bond is bonded to the oxygen atom of the carbonyloxy group (a c(〇)-0), An aliphatic cyclic group having an adamantyl group, a cyclohexyl group, a cyclopentyl group, a norbornyl group, a tricyclodecyl group, a tetracyclododecyl group, or the like, and a branch having a tertiary carbon atom bonded thereto The base of the alkyl group, etc. [Chemical 1 0]

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R15 and R16 are an alkyl group (may be linear or branched, preferably having a carbon number of 1 to 5). In the formula (a 1 &quot; - 1 ) to (a Γ ' - 6 ), the lower alkyl group of the R or the halogenated lower alkyl group, for example, is lower than the lower alkyl group which may be bonded to the α position of the acrylate or halogenated. The alkyl group is the same content. The "acetal type acid dissociable dissolution inhibiting group" is generally an oxygen atom bonded to a hydrogen atom at the terminal of an alkali-soluble group which substitutes a carboxyl group or a hydroxyl group. Therefore, when an acid is generated by exposure, the acetal type acidolysis-34-200923574 is dissolved by the action of the acid, and the oxygen atom of the acetal type acid dissociable dissolution inhibiting group is cleaved. The key knot. The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (p 1). [Chemical Formula 1] f R2 ((1), wherein R1', R2' are each independently a hydrogen atom or a lower alkyl group, η is an integer of 0 to 3, and hydrazine is a lower alkyl group or an aliphatic cyclic group. ]. In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0. The lower alkyl group of R1' and R2' is, for example, the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferable. In the present invention, it is preferred that at least one of R1' and R2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (Ρ 1 ) is preferably a group represented by the following formula (Ρ 1 - 1 ). [1 2]

S-° -{ch^-ύ ...(ρ 1 - 1 ) [wherein, R1', η, Y are the same as the above contents]. The lower alkyl group of hydrazine is, for example, the same as the lower alkyl group of the above-mentioned R-35-200923574 γ aliphatic cyclic group ', for example, conventionally used in ArF photoresist, etc., has been proposed as a single ring or more The cyclic aliphatic cyclic group is appropriately selected and used, for example, the same as the above-mentioned "aliphatic cyclic group". Further, the acetal type acid dissociable dissolution inhibiting group 'is, for example, a group represented by the following formula (P2). [Chemical 1 3] R17 —c—Ο—R19 R18 — (p 2) [wherein, R17 and R18 are each independently a linear or branched alkyl group or a hydrogen atom, and R19 is a linear or branched chain. Or a cyclic alkyl group, or R17 and R19 are each independently a linear or branched alkyl group, and the terminal of R17 is bonded to the end of R 19 to form a ring. In R17 and R18, the alkyl group preferably has 1 to 15 carbon atoms, and may be linear or branched. The ethyl group and the methyl group are preferred, and the methyl group is most preferred. h is not preferable to any of R and R18 being a hydrogen atom, and the other being a methyl group. When R19 is a linear, branched or cyclic alkyl group, the carbon number is preferably from 1 to I5, and it may be any of a linear chain, a branched chain or a cyclic chain. When R 19 is linear or branched, the carbon number is preferably 1 to 5, and the ethyl group and the methyl group are more preferably 'ethyl. When R is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 1 carbon atoms. Specifically, it may be substituted by a fluorine atom or a fluorinated k group, or a monocyclic alkane, a bicycloalkane, a -36-200923574 tricycloalkane, a tetracyclic alkane, or the like may be substituted. A group in which one or more hydrogen atoms are removed from the alkane. Specifically, for example, one or more polycyclic alkanes such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isopentane, tricyclodecane or tetracyclododecane are removed. The base of a hydrogen atom, etc. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R19 are each independently a linear or branched alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and the end of R19 may be bonded to the end of R17. can. At this time, R17 and R19 are bonded to the oxygen atom bonded to R19, and the oxygen atom forms a cyclic group with the carbon atom bonded to R17. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. The structural unit (al) is one or more selected from the group consisting of the structural unit represented by the following general formula (al_0-1) and the structural unit represented by the following general formula (a 1 - 0 - 2 ). It is better. [化1 4]

[In the formula, R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and X is an acid dissociable dissolution inhibiting group]. -37- 200923574 【化1 5】 0=Cn. , 0

[In the formula, R is a hydrogen atom, a lower-grade or a lower-grade courtyard; χ2 is an acid-dissociable dissolution-inhibiting group; γ2 is a diasterium-based or aliphatic ring-based group; 〇 is a general formula (a 1 - 0 - 1) Among them, the lower-grade courtyard base of the R or the halogenated lower-grade courtyard base has the same meaning as the lower-grade courtyard base and the halogenated lower-grade alkyl group which can be bonded to the α-position of the acrylate. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, a tertiary alkyl ester type acid dissociable dissolution inhibiting group or an acetal type acid dissociating dissolution inhibiting group, and a tertiary alkyl group. The ester type acid dissociable dissolution inhibiting group is preferred. In the general formula (al-0-2), R has the same meaning as described above. X2 is the same as X1 in the formula (al—0-1). Y2 is preferably an alkylene group having a carbon number of 1 to 10 or a divalent aliphatic cyclic group. In the case of the aliphatic cyclic group, the same as the above-mentioned "aliphatic cyclic group" can be used, for example, in addition to the group in which two or more hydrogen atoms are removed. When Y2 is an alkylene group having a carbon number of 1 to 10, and a carbon number of 1 to 6 is more preferable. -38-200923574 is particularly preferably a carbon number of 1 to 4, and preferably has a carbon number of 1 to 3. When Y2 is a divalent aliphatic cyclic group, 'removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane The basis is especially good. In the structural unit (a 1 ), more specifically, the structural unit represented by the following general formula (a 1 -1 ) to (a 1 to 4). 【化1 6】

(a 1 - 1 ) (a 1 - 2 ) (a 1 - 3 ) (a 1 - 4 ) [In the above formula, X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; γ is a carbon number of 1 a lower alkyl group of ～5, or an aliphatic cyclic group; η is an integer of 0 to 3; Υ2 is a stretching or aliphatic ring group; R has the same meaning as above; and Rl' and R2' are each independently A hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms]. The 'X' in the formula is the same as the tertiary-grade vinegar-type acid dissociable dissolution inhibiting group exemplified in the above X1.

R1, R2', η, and Υ are respectively R1', R2', η in the general formula (pi) recited in the description of "acetal-type acid-dissociable sol-39-200923574 cleavage group" described above. And Y is the same content. Υ2, for example, is the same as Y2 in the above formula (al-〇-2). The following are specific examples of structural units represented by the above formulas (al - 1) to (al - 4), -40- 200923574

.ch2(ch2)2ch3 (a1 - 1 - 5) (al-1-6)

(a1_1—4)

(CH2)3CH3 (a1 -1-7)

(a1-1-8)

(a1~1-9)

(a1 -1-10)

! ΟΓ )4 °=K ch3 ch3 -ch2-c-^- °to . Na CH2—CH-0=( ch3 (a1—1-12) CH3 ΌΗ2—c-^- 0=\ c2h6. Lion. Loss (a 1-1-14) (a1—1 -15): CH2— Ch|· 〇 = ( c2hs. gamma (a1 - 1 - 16) -41 - 200923574 [Chemical 1 8]

(al-1-21) (a1-1-22) (a1-1-23) ch3 ch2-order + 0=^ 92H5

~~^CH2—CH^~ 0=\ C2H5°tD (a1 -1-24)

Ru CH3 ch3 v (a1_1-25) (a1-1-26) (a1 -1-27) (a1 -1-28)

42- 200923574 [Chem. 1 9]

CH3 (a1-1-34) 0

Ch3 -CH2-C-)-0=\ ?2H5 °b

(a1-1-37) (a1-1-35) (a1-1-36)

CH3 ch2—c-j-

(a1-1-39)

(a1-1 -40)

〒H3 *CH2—ChV -fcH2—CV -fcH2—ChV 〇4 〇4 〇4 (a1-1-41) 【化2 0】 0 h3ct ch3 (a1—1—42) ch3 h3c^ ch3 (a 卜1 -43) 0 o ch3 h3c^ (a1~1—44), ch3 h3c C2H5

O, ch3 C2H5 (a1-1~45)

(al-2-1) (a1-2-2) (a 1-2-3) -(ch2-ch)- 0=4

(a 1-2-4) (a1-2-5)

(a1—2-6) -43 200923574 [Chem. 2 1] ch3 —(ch2-c)~ 〇〆(a1-2-7) -(ch2-ch)-〇4 o〆(a1-2-10) °W) —- CH 卜&gt;4 ch3 -(ch2-c-)- 〇4 〇, (a1-2-8) CH3 (a1-2-9) -(ch2-ch)-0=4 ch3 — (ch2-c·)&quot; (a1U3) -°3⁄4 (a1-2-12)

(a1 - 2-14) (a1-2-15) -{ch2-ch) 〇=l 〆0

:.子 ]〇, (a 卜 2-17) ?F3 -(cH2- (a1-2-18) (a1 - 2-16)

200923574 [it 2 2] ch3 十2-汁 〇={ 0, 4ch2-chV-. 4 Bu (a1-2-24)?F3 —^CHj-C·]—〇, X) (a1-2-27) CHa 0

—^CHj—CH 〇, (a1-2-22) ch3 〇4 〇, (a1-2-25) cf3 -fcH2-cf 0==^ (a1-2-28) ch3 -(ch2-〒+ 〇~ (al-2-31) CH3 ^ch2-c-〇= ;4;

(a 1 - 2-23) -^ch2-chW &quot;O 〇~ (a1-2-26) , 0 x&gt; f3 *CH2~C·) — 〇4 〇, (a 1-2-29) - 45- 200923574 [Chem. 2 3]

(a 1-2-38) (a1-2-39) -46 200923574 [Chem. 2 4] CHa

(a1-3-2) (al-3-3)

0 Q c2h5_

(a 1-3-4)

H3c

o 0 0

(e 1 —3—5) Q C2H5·

(a1-3-1)

(al-3-β)

(a1-3-13) (al-3-14)

CH3 ch3 -(ch2-c-^ -(ch2-c^-

47- 200923574 [Chem. 2 5]

48- 200923574 [Chem. 2 6]

(a 1-4-3) (a1~4-4)

(a1-4—β) (a 1-4-7) (a 1-4-8) (a 1-4-9)

(a1,4-15) 200923574 [Chem. 2 7]

(a1-4-,8) (a1+,9) (a1-4-2® (,1-4-21) (al-4-22) (al-4-23)

(a 1-4-24)

0

(a1-4-25) (a1-4-26) (a1-4-27) (al-4-28) (a1-4-29) (a 1-4-30)

H3&lt;p h3c h3c h3c h3c h3c -CH2-CH·)- ^-CH2-CH-j——^ch2-6h·}- 十 ch2-ch+ 十ch2-ch·)- 十ch2-ch C〇° P q ο ο Ο o 〇, 〇=

(al-4-37) o (al-4-39) (a1-4-38)

UiD (al-4-40) 0

(a1-*4*-41) O: t) (a 1-4-42) -50- 200923574 In the above formula, the structural unit of the formula (al-1) is preferred. It is more preferable that at least one selected from the group consisting of the formulas (al_l-1) to (al-1-6) and the formula 35) to (al-l-41) is used. Further, the structural unit (a 1 ) is particularly represented by the following general formula (a 1 - 1 - 1) containing structural units of the formula (a 1 - 1 - 1 ) to (a 1 - 1 - 4 ) The unit, or the following formula (al-Ι-02) containing structural units of the formula (al-1 to 35) to (al-1 - 41) is preferred. [化2 8]

R 11 ··· ( a 1 - 1 - Ο 1 ) wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group R11 is a lower alkyl group. [化2 9]

cIο

a yrv XI/ 2 ο -51 - 200923574 [wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group] R12 is a lower-grade courtyard group, and h is an integer of 1 to 3). In the general formula (al-1 - 〇1), R has the same content as described above. The lower alkyl group of R11 is the same as the lower alkyl group represented by R', and a methyl group or an ethyl group is preferred. In the general formula (al - 1 - 02), R has the same contents as described above. The lower alkyl group of R12 is the same as the lower alkyl group represented by the above R, and is preferably a methyl group or an ethyl group, and preferably an ethyl group. h is preferably 1 or 2, and 2 is the best. The structural unit (a 1 ) may be used singly or in combination of two or more. In (A 1 ), the ratio of the structural unit (a 1 ) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, based on the entire structural unit constituting the component (A1). It is best to use 25~50 mol%. When it is more than the lower limit, the pattern can be easily obtained as a positive resist composition, and when it is below the upper limit, it can be balanced with other structural units. • Structural unit (a2) The structural unit (a2) is a structural unit derived from an acrylate containing a cyclic group containing a lactone. Wherein, the cyclic group containing an internal vinegar is a cyclic group containing a ring (lactone ring) of a structure of 0-c(o). The lactone ring is counted as a ring unit, and only the lactone ring is a monocyclic group. If the ring structure has a further ring structure, regardless of its structure, it is called a polycyclic group. -52- 200923574 The structural unit (a2) lactone ring group 'in the case of using (A 1 ) component for forming a photoresist film, can effectively improve the adhesion of the photoresist film to the substrate, and can effectively Improve the affinity with the developer containing water. The structural unit (a2) may be any unit without any limitation. Specifically, a lactone-containing monocyclic group such as r-butyrolactone is obtained by removing one hydrogen atom. Further, the polycyclic group having a lactone is, for example, a group obtained by removing one hydrogen atom from a bicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. In the example of the structural unit (a2), more specifically, for example, a structural unit represented by the following general formulas (a2 - 1) to (a2 - 5). [化3 0]

Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R is a hydrogen atom, a lower alkyl group, or an alkoxy group having a carbon number of 1 to 5, "It is an integer of 〇 or 1, A is a carbon number 〜5 alkyl or an oxygen atom]. R in the general formulae (a2-1) to (a2-5) has the same content as R in the above structural unit (al). The lower alkyl group of R' has the same contents as the lower stage group of r in the above structural unit (a 1 ). -53- 200923574 A alkylene group having a carbon number of 1 to 5, specifically, for example, a methyl group, an ethyl group, an η-propyl group, an iso-propyl group or the like. Among the general formulae (a2 - 1) to (a2 - 5), R' is preferably a hydrogen atom from the viewpoint of industrial availability. The following are exemplifications of specific structural units of the above general formulae (a2 - 1) to (a2 - 5). [化3 1]

(a2&lt;1&gt;1) (a2-1-2) (a2-1-3)

(a2-1-4) (a2-1-5) (a2-1-6) -54- 200923574 [Chemical 3 2] CH3 , , ?H3 9H3 -fCH2-c·)- -{ch2 ch}- - (ch2-c)- -(ch2-c·)· • 04-

(a2-2-5) Ά 1 (a2-2-2) (a2-2-3) CH3 ch3

O CH2—C·)- -fCH2—Ch}- -(cH2—c)- (a2-2-4) CH3

(a2-2-6)

°=l O 0, ch3- (a2-2-7) (a2-2-8)

200923574 【化3 3】

~(ch2- 〇=

(a2-3-10) -56- 200923574 [Chem. 3 4]

-57- 200923574 [Chem. 3 5]

In the structural unit (a2), at least one selected from the group consisting of the structural units represented by the above general formulae (a2-1) to (a2-5) is preferred, and the general formula (a2 - It is more preferable that at least one selected from the group consisting of structural units shown in (a2 - 3) is preferable. Among them, by the chemical formula (a 2 - 1 - 1 ), (a2 - 1 - 2), ( a2 - 2 - 1), ( a 2 - 2 - 2 ), (a2-3 - 1), (a2 - 3 - 2) , (a2 - 3-9) and (a2 - 3 - 1 0 ) are at least one selected from the group consisting of structural units (a2), which can be used alone. Alternatively, two or more types may be used in combination. -58- 200923574 (A1) The ratio of the structural unit (a 2 ) to the total structural unit of the component (A1) is preferably 5 to 60 mol%, and 10 to 50 mol%. Preferably, it is preferably 20 to 50 mol%. When it is more than the lower limit, the effect can be fully achieved when the structural unit (a2) is contained, and the balance with other structural units can be obtained when the upper limit is less than or equal to the upper limit. • Structural unit (a3) The structural unit (a3) is a structural unit derived from an acrylate having an aliphatic hydrocarbon group containing a polar group. When the component (A3) contains a structural unit (a3), the hydrophilicity of the component (A1) can be improved, and the affinity with the developer can be improved, and the alkali solubility of the exposed portion can be improved, and the resolution can be expected to be improved. A polar group such as a hydroxyl group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom, and the like are preferably a hydroxyl group. The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group having a carbon number of 1 to 1 Torr (preferably an alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group). The polycyclic group may be, for example, a resin which can be used for a resist composition for an ArF excimer laser, and is appropriately selected from the contents of most proposals. The polycyclic group preferably has a carbon number of from 7 to 30. Further, a structural unit derived from an acrylate having a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom is more preferable. The polycyclic group ' is, for example, a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing two or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornine-59-200923574 alkane, tricyclodecane or tetracyclododecane. In the polycyclic group, it is more suitable for industrially to remove two or more hydrogen atoms from adamantane, to remove two or more hydrogen atoms from norbornane, and to remove two or more hydrogen atoms from tetracyclododecane. use. In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a linear or branched hydrocarbon group having 1 to 1 carbon atoms, the structural unit derived from hydroxyethyl acrylate is Preferably, when the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a3 - 1 ), a structural unit represented by (a3 - 2 ), a structural unit represented by (a3 - 3), or the like is preferable. [Chem. 3 6]

(a3-3) [wherein R has the same content as described above, j is an integer of 1 to 3, 'k is an integer of 1 to 3, t' is an integer of 1 to 3, and 1 is an integer of 1 to 5' s is an integer from 1 to 3. In the formula (a3 - 1 ), j is preferably 1 or 2, and more preferably 1 is used. In the case where j is 2, it is more preferable that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is particularly preferable that the hydroxyl group is bonded to the 3 position of the adamantyl group. -60- 200923574 Among them, it is better to use j as the first one, especially the one in which the hydroxy group is bonded to the base of the King Kong Institute. In the formula (a3-2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the norbornyl group. In the formula (a3 - 3), it is preferable that t' is 1 and 1 is preferred, and s is preferably 1. It is preferred that the terminal of the carboxyl group of the above-mentioned acrylic acid is bonded to a compound of 2-norborn or 3-norborn. Preferably, the fluorinated hydrazine-based alcohol is bonded to the 5 or 6-position of the norbornyl group. The structural unit (a3) may be used alone or in combination of two or more. In the component (A1), the ratio of the structural unit (a 3 ) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the entire structural unit constituting the component (A 1 ). Take 5 to 25 m. /. For the best. When the lower limit is 値 or more, the effect of containing the structural unit (a3) can be sufficiently obtained, and when it is less than the upper limit 可, the balance with other structural units can be obtained. • The structural unit (a〇(A1) component' may further contain other structural units (a 4 ) other than the above structural units (al) to (a3) within a range not impairing the effects of the present invention. Structural unit (a4) It is not particularly limited as long as it is a structural unit other than the structural units (al) to (a3), and can be used for ArF excimer laser or KrF excimer laser (preferably ArF excimer laser). Most of the conventional structures known for use in resistive photoresists, such as -61 - 200923574. Structural units (a4), for example, structural units derived from acrylates containing non-acid dissociable aliphatic polycyclic groups Preferably, the polycyclic group 'is, for example, the same as exemplified in the case of the structural unit (a 1 ) described above. It can be used for ArF excimer laser or KrF excimer laser (preferably ArF Molecular lasers are used in many conventional structural units used for the resin component of the photoresist composition, especially by tricyclodecylalkyl, adamantyl, tetracyclododecyl, iso-spinyl, norbornyl When at least one selected from the group consisting of alkyl groups, It is preferable to obtain it commercially. These polycyclic groups may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms. The structural unit (a4), specifically, for example, The structural unit represented by the general formulae (a4 - 1) to (a4 - 5), etc. [Chem. 3 7]

[wherein 'R has the same content as described above]. When the component (A4) contains the structural unit (a4), the ratio of the structural unit (a 4 ) in the component (A1) to the total structural unit of the component (A 1 ) constitutes 〜3. 〇 耳 % is better, and it is better to contain 10 to 20% by mole. In the present invention, the (A 1 ) component is preferably a copolymer containing structural units (a 1 ), (a2), and (a3). The copolymer is, for example, a copolymer obtained from structural units (a 1 ), ( ), and (a3), a copolymer obtained by structural units (al), (a2), (a3), and (a4). The component (A 1 ) can be obtained by polymerization of a monomer derived from each structural unit, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization. Further, in the above-mentioned polymerization, the (A 1 ) component may be, for example, a chain transfer agent such as HS-ch2-ch2-ch2-C(CF3)2-OH, and a C(CF3)2 may be introduced at the end. OH group. Thus, a copolymer having a hydroxyalkyl group in which one of the hydrogen atoms in the alkyl group is substituted with a fluorine atom can be obtained, whereby the defect can be effectively reduced or the LER (Line Edge Roughness) can be effectively reduced. The mass average molecular weight (Mw) of the component (A1) (the polystyrene equivalent amount of the gel permeation chromatography method) is not particularly limited, and is generally preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and 5,000. ~20,000 is especially good. When it is less than the upper limit of the range, sufficient solubility is obtained for the photoresist as a photoresist, and when it is larger than the lower limit of the range, a good dry etching resistance or a resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (M w / Mn ) is preferably in the range of 1 · 0 to 5 · 0, more preferably from 1 · 〇 to 3.0, and most preferably from 1 2 to 2.5. Further, Μη is a number average molecular weight. [(A 2 ) component] -63- 200923574 (A2) component, the acid dissociable dissolution inhibiting group exemplified in the description of the above (A 1 ) component having a molecular weight of 500 or more and less than 2 Å, and A hydrophilic group of a low molecular compound is preferred. Specifically, a compound in which a part of a hydrogen atom of a hydroxyl group of a compound having a plural phenol skeleton is substituted with the above-mentioned acid dissociable dissolution inhibiting group or the like. The component (A2), for example, a sensitizer in a g-line or i-line resist which is known to be non-chemically amplified, or a part of a hydrogen atom of a hydroxyl group of a low molecular weight phenol compound of a heat-resistant enhancer is dissociated by the above acid The component substituted by the dissolution inhibiting group may be used arbitrarily. The low molecular weight cerium compound, for example, bis(4-indolyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2 _(4-hydroxyphenyl)- 2-(4,-hydroxyl Phenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2,3,4'-trihydroxyphenyl)propane, tris(4-hydroxyphenyl)methane, double (4-hydroxy-3,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, double (4 Monohydroxy-3,5-dimethylphenyl)-3,4~di residue phenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane , bis(4-hydroxy-3-methylphenyl)-3,4~dihydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyl-6-methylphenyl)-tetrahydroxyphenylmethane , bis(3-cyclohexyl-4-hydroxy-6~methylphenyl)-3,4-dihydroxyphenylmethane, hydrazine-[1 -(4-hydroxyphenyl)isopropyl]-[1, 1 A pair of bisphenol (4-hydroxyphenyl)ethyl]benzene, phenol, m-cresol, p-cresol or xylenol 2, 3, 4 nucleus of aldehyde water condensate, and the like. Of course, it is not limited to this. -64-200923574 The acid dissociable dissolution inhibiting group is not particularly limited. For example, the above may be mentioned. (A) The ingredients may be used singly or in combination of two or more. In the photoresist composition of the present invention, the content of the component (A) may be adjusted in accordance with the thickness of the photoresist film to be formed. &lt;(B) Component&gt; (B) The component is not particularly limited, and the component which has been proposed so far as an acid generator for chemically amplified photoresist can be used. The acid generator is, for example, a gun salt acid generator such as an iodonium salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonyldiazomethane, or a polysulfonate. Hydrazine-based diazomethane-based acid generator, nitrobenzyl sulfonate-based acid generator, iminosulfonate-based acid generator, diterpenoid acid generator, etc. Compound. As the onium salt acid generator, for example, a compound represented by the following formula (b-1) or (b-2) can be used. [化3 8]

Wherein R1" to R3&quot;, R5'' to R6'' are each independently an aryl group or an alkyl group; in the formula (b-1), any one of R1&quot; to R3&quot; may be bonded to each other and A ring may be formed together with a sulfur atom in the formula; R4&quot; is an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent of -65-200923574; at least one of R1&quot; to R3&quot; is an aryl group, At least one of R5&quot; to R6&quot; is an aryl group. In the formula (b-1), R1&quot; to R3&quot; are each independently an aryl group or an alkyl group; in the formula (b-1), R1&quot; to R" 'Any two can be bonded to each other and form a ring together with the sulfur atom in the formula. Further, at least one of R1" to R3&quot; is an aryl group. It is preferable that two or more aryl groups are used in R1^R3&quot; and R1&quot; to R3'' are all aryl groups. R1&quot The aryl group to R3&quot; is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, and a part or all of a hydrogen atom of the aryl group may be an alkyl group, an alkoxy group, a halogen atom, The aryl group having 6 to 10 carbon atoms is preferably used in the case where the hydroxy group or the like is substituted or unsubstituted, and the aryl group may be inexpensively synthesized. Specifically, for example, a phenyl group, a naphthyl group or the like may be used. The alkyl group of the hydrogen atom of the above aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The alkoxy group of the hydrogen atom of the aryl group is preferably a carbon number butoxy 'tert-butoxy group. The methoxy group of methoxy-5 is preferred, and the methoxy group, the ethoxy group, the η group Propyl is 〇 _ propyloxy ' η The halogen atom of the hydrogen atom of the above aryl group is preferably a fluoroprimary group or an ethoxy group, and the above substituted group is preferred. R 】 &quot; 辛 R3&quot; 〉b &lt;Hospital base, there is no particular limitation, for example, it may be a linear, branched or cyclic alkyl group having a carbon number of -66 to 200923574 to 10, etc., and has excellent analytical viewpoints, such as carbon. The number is preferably from 1 to 5. Specifically, for example, 'methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, η-pentyl, cyclopentyl, hexyl, cyclohexyl , fluorenyl group, fluorenyl group, etc. In terms of having excellent resolution and being inexpensively synthesized, it is more preferable to use a methyl group. Any one of R1&quot; to R3'' in the formula (b-1) In the case where they can be bonded to each other and form a ring together with the sulfur atom in the formula, it is preferable to form a ring of 3 to 10 members containing a sulfur atom, and it is preferable to form a ring having a ring of 5 to 7 (b- In the case of any of R1'' to R3" in 1), any two of them may be bonded to each other and form a ring together with the sulfur atom in the formula, and the remaining one is preferably an aryl group. The above aryl group is, for example, the same as the above aryl group of R1'' to R3''. R4&quot; is an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent. The alkyl group in R4&quot; may be any of a linear chain, a branched chain, and a ring. The linear or branched alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The cyclic alkyl group is preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 1 Torr, and most preferably a carbon number of 6 to 10. The halogenated alkyl group in R4&quot;, for example, a group in which a part or all of a hydrogen atom in the above linear, branched or cyclic alkyl group is substituted by a halogen atom or the like. The halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like -67-200923574 is preferably a fluorine atom. The total number of halogen atoms in the 7C group of the ruthenium telluride relative to the halogen atom and the hydrogen atom contained in the ruthenium group, and the ratio of the number of halogen atoms (halogenation rate (°/.)) is 〇 1 1 〇〇 % is better, preferably 5 0~1 0 〇%, and 1 〇〇% is the best. When the halogenation rate is higher, the stronger the strength of the acid, the more preferable. The aryl group in R4 is preferably an aryl group having 6 to 20 carbon atoms. The alkenyl group in the above R4&quot; is preferably an alkenyl group having 2 to 1 carbon atoms. The term "may have a substituent" in the above R4'' means that a part or all of the hydrogen atoms in the above linear 'chain-like or cyclic alkyl group, halogenated alkyl group, aryl group or alkenyl group are Substitution of a substituent (other than a hydrogen atom or a base) may also mean. The number of substituents in R4 may be one or two or more. The substituent ', for example, a halogen atom, a hetero atom, an alkyl group, or a group represented by R5 - 0 - [wherein R 5 is a monovalent aromatic organic group, a monovalent aliphatic hydrocarbon group or a hydroxyalkyl group]. The halogen atom 'alkyl group' is, for example, the same as the halogen atom or the alkyl group in the halogenated alkyl group in R 4 &quot;. The hetero atom 'e.g., an oxygen atom, a nitrogen atom, a sulfur atom or the like. The above R5 - 〇 - is represented by the base, ...! An aromatic hydrocarbon group such as a fluorene group having a hydrogen atom such as a ring of a base or a biphenyl group, a fluorenyl group, a naphthyl group, an anthra aCyl group or a phenanthryl group. a heteroaryl group obtained by substituting a part of a carbon atom of the ring of the above aryl group with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom; a lower group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthyl group Base, 1-naphthylethyl, 2-68-200923574 naphthylethyl and the like aralkyl. The carbon number of the alkyl chain in the above aralkyl group is preferably 1 to 4, more preferably 1 to 2, and most preferably 1 is used. The 'heteroaryl group or the aralkyl group in the above aryl group may have a substituent such as a group having a carbon number of 1 to 10, a halogenated compound group, a hospitaloxy group, a mesogenic group, or a halogen atom. The alkyl group or the bactericidal alkyl group in the substituent is preferably a carbon number of 1 to 8, and preferably a carbon number of 1 to 4. Moreover, the halogenated hospital base is preferably a fluoride hospital base. The halogen atom, for example, a fluorine atom, a chlorine atom, a moth atom, a bromine atom or the like, is preferably a fluorine atom. The monovalent aromatic organic group of R5 is preferably an aralkyl group, more preferably an arylmethyl group, and most preferably a naphthylmethyl group. a monovalent aliphatic hydrocarbon group of R5, for example, a linear, branched or cyclic monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a linear or branched chain having 2 to 5 carbon atoms; A valence aliphatic unsaturated hydrocarbon group or the like. A linear monovalent saturated hydrocarbon group, for example, 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 decyl group, a decyl group or the like. Branched monovalent saturated hydrocarbon group, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Butyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like. The cyclic monovalent saturated hydrocarbon group may be any of a polycyclic group or a monocyclic group, for example, a polycyclic ring such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. A group obtained by removing one hydrogen atom from an alkane. More specifically, for example, monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, -69-200923574 or Donkey Kong, Nori Institute, Heteroptera, Second Ring Hospital, Four A group obtained by removing one hydrogen atom from a polycyclic alkane such as a ring or a courtyard. A linear monovalent unsaturated hydrocarbon group, for example, a vinyl group, a propenyl group, a butenyl group or the like. A branched monovalent unsaturated hydrocarbon group, for example, a 1-methylpropenyl group, a 2-methylpropenyl group or the like. The carbon number of the monovalent aliphatic hydrocarbon group of R5 is preferably 2 to 4, and most preferably 3. The hydroxyalkyl group of R5 is one in which at least one hydrogen atom of a linear, branched or cyclic monovalent saturated hydrocarbon group is substituted with a hydroxyl group. Further, one or two hydrogen atoms of a linear or branched monovalent saturated hydrocarbon group are preferably substituted by a hydroxyl group. Specifically, for example, a hydroxymethyl group, a hydroxyethyl group, a monopropyl group, a 2-propyl group, a 3-propyl group, a 2,3-propyl group, and the like are used. The carbon number of the monovalent hydroxy group of R5 is preferably from 丨10 to 10, more preferably from 1 to 8, and most preferably from 1 to 6, and particularly preferably from 1 to 3. In the formula (b-2), R5&quot; and R6'' are each independently an aryl group or an alkyl group; at least one of R5" and R6&quot; is an aryl group, and both of R5&quot; and R6&quot; The base is the best. The aryl group of R5&quot; and R6&quot;, for example, is the same as the aryl group of R1" to R3". The alkyl group of R5&quot; and R6&quot; is, for example, the same as the alkyl group of R1'' to R3''. Among them, R5&quot; and r6&quot; both are the best. -70- 200923574 R4&quot; in the above formula (b-2) is the same as R4&quot; in (b-1). Specific examples of the sulfonium acid generator represented by the formulae (b-1) and (b-2), for example, diphenyliodide trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-tert) -butylphenyl) iodine gun trifluoromethanesulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate , tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl(4-hydroxynaphthyl)phosphonium trifluoromethanesulfonate Acid ester, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, triphenylmethanesulfonate of monophenyldimethylhydrazine, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl Trifluoromethanesulfonate of monomethyl vegetable, its heptafluoropropane sulfonate or its nonafluorobutanesulfonate, (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonic acid Ester, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate Acid ester, three (4 one Tert-butyl)phenyl hydrazine trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1-(4-methoxy)naphthyl) mirror Fluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, bis(1-naphthyl)phenyl fluorene trifluoromethane vinegar, its heptafluoropropane sulfonate or its nonafluorobutane Alkane sulfonate, trifluoromethanesulfonate of 1-phenyltetrahydrothiophene gun, heptafluoropropane extended acid ester or its nonafluorobutyrate extended acid ester, 1-(4-methylphenyl) tetrahydrothiophene gun Trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene gun-71 - 200923574 Fluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(4-methoxynaphthalene-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, and heptafluoropropane sulfonate An acid ester thereof or a nonafluorobutane sulfonate thereof, a trifluoromethanesulfonate of 1-(4-ethoxynaphthalene-1-yl)tetrahydrothiophene, a heptafluoropropane sulfonate thereof or a nonafluorobutane sulfonate thereof Acid ester, 1 (4-n-butoxynaphthalene-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, 1-phenyltetrahydrothiopyran Trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate thereof, trifluoromethanesulfonate of 1-(4-hydroxyphenyl)tetrahydrothiopyran gun, and heptafluoropropane sulfonate Or a nonafluorobutane sulfonate, a tris(3,5-dimethyl-4-iso-phenyl)tetrahydrothiopyran trifluoromethanesulfonate, a heptafluoropropane compound or Its nonafluorobutane sulfonate, 1-(4-methylphenyl)tetrahydrothiocarbamate trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate. Further, a gun salt in which the anion portion of the above gun salt is replaced by a methanesulfonate, η-propanesulfonate or η-butanesulfonate 'η-octanesulfonate can be used. Further, the key salt acid generator obtained by substituting an anion moiety with an anion moiety represented by the following formula (b-3) or (b-4) in the above formula (b-1) or (b-2) may also be used. (The cation moiety is the same as the above formula (b-1) or (b-2)). -72- 200923574 [Chem. 3 9]

X&quot;...(b-3) 02S—Y&quot;

(b_4) [wherein X" is an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom; Y '', Z" are each independently a carbon in which at least one hydrogen atom is replaced by a fluorine atom Number 1 to 1 〇 of the alkyl group]. X" is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is preferably from 2 to 6, more preferably from 3 to 5 carbon atoms, most preferably Carbon number 3. Y&quot;, Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is preferably from 1 to 10, more preferably carbon number. 1 to 7, the best carbon number is 1 to 3. When the carbon number of the alkyl group of X &quot; or the carbon number of the alkyl group of Y" and Z11 is in the above range, it is preferably as small as possible based on the excellent solubility to the photoresist solvent, etc. Further, X" In the alkyl group of the alkyl group or the Y", Z &quot;, the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the strength of the acid, and the higher the energy or electron line of 200 nm or less, It is preferred to increase the transparency. The proportion of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably from 70 to 100%, more preferably from 90 to 100%, and most preferably all hydrogen. A perfluoroalkylene group or a perfluoroalkyl group in which an atom is substituted by a fluorine atom. Further, a cation having a cation moiety represented by the following formula (b-5) or (b-6)-73-200923574 may also be used. Salt is used as an iron salt acid generator. [Chemical 4 0]

Wherein R41 to R46 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; ηι to η5 are each an integer of 0 to 3, and n6 is an integer of 0 to 2; ]. In R46, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, and a η group. - Butyl, or tert - butyl is particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group. The hydroxyalkyl group is preferably a group in which one or a plurality of hydrogen atoms of the above alkyl group are substituted with a group, for example, a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. When the symbols ～ to n6 to be added to R41 to R46 are integers of 2 or more, the respective R41 to R40 of the plural number may be the same or different. m is preferably 0 to 2, more preferably 0 or 1, most preferably 〇. 112 and n3, preferably each independently 0 or 1, more preferably 〇°

Du is preferably 〇~2, more preferably 0 or 1. -74- 200923574 n5 is preferably 0 or 1, more preferably 0. Η6 is preferably 0 or 1, more preferably 1. The anion portion having a sulfonium salt of the cation portion represented by the formula (b-5) or (b-6) is not particularly limited, and it can be used in the same manner as the anion portion currently proposed as a gun salt acid generator. Anion part. The anion moiety is, for example, a fluorinated alkylsulfonate ion such as an anion moiety (R4__S03-) of the phosphonium salt generator represented by the above formula (b-1) or (b-2); 3) or an anion moiety represented by (b-4). In the present specification, the oxime sulfonate-based acid generator has, for example, a compound having at least one group represented by the following formula (B-1), which has a property of generating an acid by radiation irradiation. The above-mentioned oxime sulfonate-based acid generator is generally used for a chemically amplified positive-type photoresist composition, and the present invention can be optionally used. [Chemical 4 1] —C=N—0—S〇2—R31 R32 · · (B-i) [In the formula (B-1), R31 and R32 are each independently an organic group]. The organic group of R31 and R32 is a group containing a carbon atom, but it may contain an atom other than a carbon atom (e.g., a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)). The organic group of R31 is preferably a linear, branched or cyclic alkyl or aryl group. The aforementioned alkyl group or aryl group may have a substituent. The substituent is not particularly limited and may, for example, be a fluorine atom, a linear one having a carbon number of 1 to 6, a branched or a cyclic alkyl group or the like. Here, the "having a substituent" means that at least one of the -75 to 200923574 hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent. The alkyl group preferably has a carbon number of from 1 to 20, preferably from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, most preferably from 1 to 6 carbon atoms, and particularly preferably from 1 to 4 carbon atoms. . Among them, the alkyl group is particularly preferably an alkyl group (hereinafter, also referred to as a halogenated alkyl group) obtained by partial or complete halogenation. Further, the "partially halogenated alkyl group" means an alkyl group in which a part of a hydrogen atom is substituted by a halogen atom, and a completely halogenated alkyl group means an alkyl group in which all hydrogen atoms are replaced by a circle atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like is particularly preferably a fluorine atom. That is, the halogenated yard base is preferably a fluorinated yard base. The aryl group is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 10. The aryl group is particularly preferably an aryl group obtained by partially or completely halogenating. Further, a partially halogenated aryl group means an aryl group in which one of hydrogen atoms is partially substituted by a halogen atom, and an aryl group which is completely halogenated means an aryl group in which a hydrogen atom is entirely substituted by a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms which has no substituent. The organic group of R32 is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The fluorenyl group and the aryl group of R3 2 are, for example, the same as those of the alkyl group and the aryl group exemplified in the above R 3 1 . R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (B-2) or (B-3). -76- 200923574 R4-C=N—Ο—S02—R35 R33 . (B-2) [In the formula (B_2), R3 3 is a cyano group, an alkyl group having no substituent or halogenated Mercapto·R34 is an aryl group. 'R35 is a hospital group or a halogenated alkyl group having no substituent. [化4 3] R37--C=N-Ο-SO, a R38

I R36 n„ t [In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or an alkyl halide; R37 is a 2- or trivalent aromatic hydrocarbon group; and r38 is an alkane having no substituent. Or a halogenated alkyl group, P&quot; is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated compound having no substituent of R33 is preferably a carbon number of 1 to 1 Å. 1 to 8 is more preferable, and the carbon number is preferably 1 to 6. R33 is preferably a halogenated alkyl group and more preferably a fluorinated alkyl group. The fluorinated alkyl group in R3 3 is a hydrogen atom in the alkyl group. It is preferred that more than 50% is fluorinated, more preferably 70% or more, and more preferably 90% or more of fluorinated. R34 aryl, such as phenyl or biphenyl (biPhenyl), fluorenyl A ring of an aromatic hydrocarbon such as a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthryl group, and a part of a carbon atom which removes one hydrogen atom and a part of a carbon atom constituting the ring of the aforementioned group are oxygen atoms and sulfur atoms. a hetero atom such as a nitrogen atom is substituted by -77-200923574 to obtain a heteroaryl group, etc., wherein a fluorenyl group is more preferred. The aryl group of R34 may have an alkyl group having a carbon number of 1 to 1 fluorene, an alkyl halide group, or a a substituent such as an oxy group The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8 and more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group having a substituent or the alkyl group having a halogenated group is preferably a carbon number of from 10 to 10, more preferably a carbon number of from 1 to 8, and most preferably a carbon number of from 1 to 6. R 3 5 is preferably a halogenated alkyl group. More preferably, the fluorinated alkyl group is a fluorinated alkyl group in R35, wherein the hydrogen atom of the alkyl group is preferably fluorinated by 50% or more, more preferably 70% or more, and fluorinated by more than 9% by weight. In the case of the above formula (B-3), R3 6 has no substituent. The alkyl group or the halogenated alkyl group is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R33. The 2 or 3 valent aromatic hydrocarbon group of R37 is, for example, an aryl group of the above r34. A group obtained by removing 1 or 2 hydrogen atoms, etc. The alkyl group or the halogenated alkyl group having no substituent of R38 is, for example, the same as the alkyl group or halogenated alkyl group having no substituent represented by the above R35. 〇 p " is preferably 2. Specific examples of an oxime sulfonate-based acid generator such as α _( p-toluenesulfonyloxyimino)-benzyl cyanide (cyanide), 〇: — (ρ-chlorophenylsulfonyloxyimino) )~Benzyl cyanide, α-(4-nitrophenylsulfonyl-78-200923574 oxyimino), a cyanide, α-(4-nitro-2-difluoromethylbenzenesulfonate) Imino)-benzyl cyanide, α-(phenylsulfonyloxyimino)-tetrachlorobenzyl benzyl cyanide, a-(phenylsulfonyloxyimino)- 2,4-dichloro Benzyl cyanide, α-(phenylsulfonyloxyimido)-2,6-dichlorobenzyl cyanide, -(phenylsulfonyloxyimino)-4-methoxybenzyl cyanide, Α-(2-Chlorobenzenesulfonyloxyimino)-tetramethyloxycyanide, α-(phenylsulfonyloxyimino)-thiazol-2-ylacetonitrile, α - (4 Dodecylbenzenesulfonyloxyimido)-benzyl cyanide, hydrazine: —[(ρ-toluenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α — 〔(十Dialkylbenzenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α- (pair Phenylsulfonyloxyimido)-4-ylthiocyanate, α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino) 1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimido)-1,4-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1 monocyclooctenylacetonitrile, - ( Trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino) Monoethyl acetonitrile, α-(propylsulfonyloxyimido)-propyl acetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimine a) cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α - ( Isopropylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimino)-1,4-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimine Base) Acetonitrile-79-200923574, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, (methyl extended oxyimino)-phenylacetonitrile, α-(methylsulfonyloxy-yenyl)-ρ-methoxyphenylacetonitrile, hydrazine:-(trifluoromethylsulfonate Amino)-phenylacetonitrile, -(trifluoromethylsulfonyloxyimino)-ρ-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-ρ~methoxybenzene Acetonitrile, 0: - (propylsulfonyloxyimido)-ρ~methylphenylacetonitrile, α-(methylsulfonyloxyimido)_Ρ-bromophenylacetonitrile, etc. - 20 8 5 5 No. 4 (paragraphs [0012] to [ 〇〇1 4] [Chem. 18] to [Chem. 1 9]), which are not disclosed in the Θ 扩 扩 扩 扩 扩 ,, W02004/ The sulfonate-based acid generator disclosed in 074242A2 (Examples 1 to 40 on pages 65 to 85) may also be used in combination. Further, for example, a compound shown below or the like is suitable. [4 4]

C4H9-O2S—〇—N=C—C=N—〇—S02—C4He CN CN H3C--C=N-OS〇2-(CH2)3CH3 H3C*—C^=N—OSO2-(CH2)$ CH3

C*==N-0-S〇2-C4F9 (CF2)6-H

In the 0-S〇2-C4F9 (cF2)4-H diazomethane acid generator, specific examples of the dialkyl or m-sulfonyldiazomethane, such as bis(isopropylsulfonyl) Diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(I,1 methylethylsulfonyl-80-200923574) diazotamine, bis(cyclohexylsulfonyl)diazide Institute, bis(2,4-dimethylphenylsulfonyl) diazomethane, etc. Further, a diazomethane-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 11-035551, No. Hei 11-035552, and No. Hei 11-035573. Further, 'poly(disulfonyl) diazomethane, such as 1,3 - bis(phenylsulfonyldiazomethylmethyl)propane disclosed in JP-A No. 1 322707, 1,4 a pair of (phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, M〇-double (phenylsulfonate) Base heavy nitrogen methylsulfonyl) decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane' 1,3 -bis(cyclohexylsulfonyldiazomethylsulfonate Mercapto) propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,1 〇 bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. . (B) The component may be used alone or in combination of two or more. In the present invention, the component (B) is preferably a key salt-based acid generator using a fluorinated alkylsulfonic acid ion which may have a substituent as an anion moiety. The content of the component (B) in the resist composition for immersion exposure of the present invention is preferably from 1 to 10 parts by mass based on 100 parts by mass of the component (A). In the above range, the pattern can be sufficiently formed. Further, a homogeneous solution can be obtained, and it is preferably -81 - 200923574 &lt; (C) component &gt; (C) component, which is the above-mentioned fluorine-containing compound (c) of the present invention. (c) The components may be used singly or in combination of two or more. In the resist composition for immersion exposure of the present invention, the content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the component (A). It is preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass. When it is at least the lower limit of the above range, the hydrophobicity of the photoresist film formed by using the resist composition for immersion exposure can be improved, and it is a substance having hydrophobicity suitable for immersion exposure, and when it is below the upper limit ,, The lithography etching characteristics can be improved. &lt;arbitrary component&gt; The exposure exposure of the latent image formed by the pattern — wise exposure of the resist layer In addition, a nitrogen-containing organic compound (D) (hereinafter also referred to as (D) component) of any component may be further added. As the component (D), proposals have been made for various compounds, and any of the known components may be used, and among them, an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine is preferred. Wherein, the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group is preferably a fatty amine having a carbon number of 1 to 12, for example, at least one hydrogen atom of ammonia N Η 3 is Carbon number - 82 - 200923574 The alkyl group or hydroxyalkyl group below 1 2 is substituted with the obtained amine (alkylamine or polyalcoholamine) or cyclic amine. Specific examples of the alkylamine and the alkanolamine such as η-hexylamine, η-heptylamine, η-羊amine, η-decylamine, η-decylamine, etc.; a dialkylamine such as η-propylamine, di-n-heptylamine, di-n-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tris-n-propylamine , bis-butylamine, tri-n-hexylamine, tri-n-pentylamine, di-n-heptylamine, tri-n-octylamine, tri-n-decylamine, trin a trialkylamine such as η_mercaptoamine, tris-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-η-octanolamine, and triammine An alkanolamine such as an octanolamine. Among them, the second amine of the carbon number of 5 to 10 is preferred, and the second η-pentylamine is preferred. The cyclic amine ' contains, for example, a heterocyclic compound as a nitrogen atom of a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). The aliphatic monocyclic amine, specifically, for example, piperidine, piperazine or the like, an aliphatic polycyclic amine, preferably having a carbon number of 6 to 10, specifically, for example, I, 5 - 2 Azabicyclo[4.3_0]-5-nonene, ι,8-diazabicyclo[5_4_0]-7-undecene, hexamethylenetetramine, ι,4 diazabicyclo [2.2.2] Octane and the like. They may be used alone or in combination of two or more. (D) The component (A) component is usually used in an amount of 0.01 to 5.0 parts by mass, based on 100 parts by mass of the component (A). -83- 200923574 The photoresist composition for immersion exposure of the present invention, in order to prevent deterioration of sensitivity, or to improve the shape of the photoresist pattern, post expo sure stability of the latent image formed by the p At least one compound (E) selected from the group consisting of an organic carboxylic acid or a phosphorus oxyacid or a derivative thereof, which may further contain an optional component, at least tern — wi se exposure of the resist layer Also known as (E) component). An organic carboxylic acid such as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. Phosphorus oxyacids and derivatives thereof, such as phosphoric acid, Phosphonic acid, Phosphinic acid, etc., of which phosphonic acid is preferred. The oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the oxo acid with a hydrocarbon group, or the like, the hydrocarbon group, for example, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms. The phosphoric acid derivative is, for example, a phosphoric acid ester such as di-n-butyl phosphate or diphenyl phosphate. Phosphonic acid derivatives such as dimethyl phosphonate, di-n-butyl phosphinate, phenylphosphonic acid, diphenyl phosphonate, diphenyl phosphonate, and the like. A phosphinic acid (P h 〇 s p h i n i c a c id ) derivative such as a phosphinate such as 'phenylphosphinic acid. (E) The components may be used singly or in combination of two or more. -84- 200923574 (E) The component is usually used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A). The photoresist composition for immersion exposure of the present invention can be further blended with an additive which is suitable for mixing, for example, an additive resin which can improve the properties of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, and a plasticizer. Agents, stabilizers, colorants, halo inhibitors, dyes, and the like. &lt;Organic solvent (S) &gt; The photoresist composition for immersion exposure of the present invention can be produced by dissolving a material in an organic solvent (S) (hereinafter also referred to as (S) component). The component (S) can be used as long as it can dissolve the components to be used in a uniform manner. For example, one or two or more kinds of the above-mentioned conventional solvents can be used as a chemically amplified resist solvent. For example, lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl η-pentanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, Polyols such as ethylene glycol, propylene glycol, and dipropylene glycol; ester-bonded compounds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate a compound having an ether bond such as a monoalkyl ether or a monophenyl ether such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether; or a compound having an ester-bonded compound; a derivative of a polyol such as propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME); a cyclic ether such as dioxane; or methyl lactate Ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxy-85-200923574 methyl propyl propionate, ethyl ethoxy propionate, etc. Esters; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylphenyl ether, ethylbenzene, two An aromatic organic solvent such as ethylbenzene, pentylbenzene, cumene, toluene, xylene, cumene or trimethylbenzene. The above organic solvent may be used singly or in the form of a mixed solvent of two or more kinds. Further, among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL) are preferably used. Further, a mixed solvent obtained by mixing P G Μ E A with a polar solvent can also be used. The addition ratio (mass ratio) may be appropriately determined depending on the compatibility of P 〇 M E A with a polar solvent, etc., preferably from 1:9 to 9:1', more preferably from 2:8 to 8:2. More specifically, when the polar solvent is ethyl lactate (E L ), the mass of PGMEA: EL is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2. When the polar solvent is PGME, the mass of PGMEA: PGME is preferably from 1:9 to 9:1', more preferably from 2:8 to 8:2, most preferably from 3:7 to 7:3. Further, among the components (S), for example, a mixed solvent of at least one selected from PGMEA and EL and r-butyrolactone is preferably used. In this case, in the mixing ratio, the mass of the former and the latter is preferably 70: 3 0 to 9 5 : 5 The amount of the 〇 (S) component is not particularly limited, and generally can be applied to a concentration such as a substrate. The film thickness and the like are appropriately selected and set, and generally -86 to 200923574 can be used in the range of 2 to 20% by mass, preferably 5 to 15% by mass, based on the solid content of the photoresist composition. For the dissolution of the material (S) component, for example, the above components may be mixed and stirred only by a usual method, and if necessary, a high-speed stirrer, a homomixer, a 3-roller honing machine, or the like may be used. The disperser is dispersed and mixed. Further, after mixing, it is also possible to use a sieve, a membrane filter or the like for filtration. The positive-type photoresist composition for immersion exposure of the present invention has the characteristics sought for the photoresist composition used for immersion exposure, and has good lithographic etching characteristics and is suitable for use as an immersion exposure. Hydrophobic (hydrophilic), it is very suitable for use as an immersion exposure. Namely, the photoresist film formed by using the resist composition for immersion exposure of the present invention contains the component (C) (i.e., the fluorine-containing compound (C) of the present invention). The component (C) has a property of increasing hydrophilicity under alkaline conditions, in addition to having a high hydrophobicity due to a fluorine atom and having a bond to the base of Q-CO-R2. It should be the result of dissociating -CO - R2 based on the action of a base to form a hydrophilic group (a QH). Therefore, a photoresist film formed by the photoresist composition for immersion exposure of the present invention which is simultaneously blended with the component (C) and the component (A) and the component (B) is used before the contact with the alkali developer (for example, immersion) At the time of exposure, it has high hydrophobicity and can also improve hydrophilicity upon contact with water. In this way, since the hydrophobicity in the immersion exposure is higher, the photoresist film formed by using the photoresist composition for immersion exposure of the present invention has a scan described in Non-Patent Document 1 which is excellent in the range of -87 to 200923574. The immersion exposure machine performs the water followability sought by the immersion exposure. Further, since the alkali-developing photoresist composition has high hydrophilicity, the immersion-type photoresist composition for exposure of the present invention can effectively reduce defects during immersion exposure. That is, when the resist film is subjected to the immersion exposure in the "wetting exposure", the solubility of the alkali developing solution in the exposed portion can be changed. For example, in the case of a positive type, the solubility in the alkali developing solution of the exposed portion is high, and in the case of a negative type, the solubility in the alkali developing solution in the exposed portion is low. Therefore, in the case of performing alkali development, in the case of a positive type, the exposed portion can be removed in the case of a negative type, and the unexposed portion can be removed to form a photoresist pattern. At this time, in the immersion exposure of the photoresist film, on the surface of the portion where the radiation is not irradiated (for example, the unexposed portion in the case of a positive type), after development, it is likely to be affected by the immersion medium such as water. The resulting defect (water stain, etc.), but the photoresist film formed by using the photoresist composition for immersion exposure of the present invention has high hydrophilicity during development, so that occurrence of defects can be reduced. Further, when the resist composition for immersion type exposure of the present invention is used, it is possible to suppress elution of the substance from the photoresist film during the immersion exposure. That is, in the immersion type exposure, as described above, in the conventional exposure, a portion between a lens filled with an inert gas such as air or nitrogen and a photoresist film on the wafer is filled with a refractive index higher than that of air. A method of performing a step of exposure (immersion exposure) in the state of a large solvent (immersion medium). In the immersion exposure, the material in the photoresist film ((B) component, (D) component, etc.) is eluted by contacting the photoresist film with the infiltrating solvent (the substance is dissolved in the infiltrating solvent). The phenomenon. The dissolution of the substance often causes deterioration of the photoresist layer and changes in the refractive index of the immersion solvent, and deteriorates the lithography characteristics. The amount of the substance eluted is affected by the surface characteristics of the photoresist film (e.g., hydrophilicity, hydrophobicity, etc.). Therefore, it is presumed that, for example, the hydrophobicity of the surface of the photoresist film can be improved to reduce the elution of the substance. The photoresist film formed by using the photoresist composition for immersion exposure of the present invention contains (C) component having a fluorine atom, and is exposed and developed when compared with the case where the component (C) is not contained. The former is more hydrophobic. Therefore, when the photoresist composition for immersion exposure of the present invention is used, the elution of the substance during the immersion exposure can be suppressed. When the elution-type photoresist composition of the present invention is used, the deterioration of the photoresist film or the change in the refractive index of the infiltrating solvent can be suppressed in the immersion exposure. A photoresist pattern having a good shape or the like can be formed by suppressing fluctuations in the refractive index of the immersion solvent or the like. Further, since the contamination of the lens of the exposure device can be reduced, it is not necessary to protect it, and thus it contributes greatly to the simplification of the process or the exposure device. Further, the photoresist film formed by the photoresist composition for immersion exposure of the present invention is swelled by water, so that a fine photoresist pattern can be formed extremely accurately. In addition, the photoresist composition for immersion exposure of the present invention also has good lithography characteristics such as sensitivity, resolution, and etching resistance, and can be used as a photoresist in immersion exposure. A photoresist pattern is formed under the practical problem. For example, when the photoresist for immersion exposure of the present invention is used in the composition of -89 to 200923574, a fine photoresist pattern having a size of 1 2 Onm or less can be formed. The hydrophobicity of the photoresist film is to determine the contact angle with respect to water, such as the static contact angle (the angle formed by the surface of the water droplet on the photoresist film in the horizontal state and the surface of the photoresist film), the dynamic contact angle (the tilt of the photoresist film) At the time of contact, the contact angle (rolling angle) at which the water droplet starts to roll off, the contact angle (forward angle) of the front end of the water droplet in the rolling direction, and the contact angle (reverse angle) of the rear end point in the rolling direction, etc.) Ways to evaluate. For example, the higher the hydrophobicity of the photoresist film, the larger the static contact angle, the advancing angle, and the receding angle, and the more the roll angle is /J. Wherein, the advancing angle is as shown in FIG. 1, and when the plane 2 on which the droplet 1 is placed is sequentially inclined, when the droplet 1 starts to move (rolls off) from the plane 2, the droplet 1 The surface of the droplet at the lower end 1 a and the angle formed as the plane 2 are 0 !. Further, at this time (when the droplet 1 starts to move (fall) from the plane 2), the surface of the droplet at the upper end lb of the droplet 1 and the angle 0 2 formed by the plane 2 are receding angles, and the plane 2 The tilt angle 0 3 is the roll angle. In the present specification, the advancing angle, the receding angle, and the roll angle are measured in the following manner. First, a photoresist composition was spin-coated on a substrate, and then heated at a temperature of 110 ° C for 6 seconds to form a photoresist film. Next, for the above-mentioned photoresist film, DROP M ASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.), AUTO SLIDING ANGLE: SA-30DM (product name, Kyowa Interface Science Co., Ltd.), AUTO DISPENSER: AD-31 ( Product name, manufactured by Kyowa Interface Science Co., Ltd.) -90-200923574 and other commercially available measuring devices. In the immersion exposure photoresist composition of the present invention, the measurement of the back angle before and after exposure and development of the photoresist film obtained by using the photoresist composition is preferably 5 〇 or more, and 50 to 15 0 degree is better, with 50 to 1 30 degrees being particularly good, and 53 to 100 degrees is the best. When the receding angle is equal to or greater than the lower limit, the effect of suppressing the elution of the substance during the immersion exposure can be enhanced. This reason is still unclear, and the main reason is that it should be related to the hydrophobicity of the photoresist film. That is, when an aqueous medium such as water is used, the immersion medium is highly hydrophobic, and it is presumed that when the immersion medium is removed after immersion exposure, it is possible to quickly remove the immersed medium from the surface of the photoresist film. Further, when the relief angle is equal to or less than the upper limit ,, good lithographic etching characteristics and the like can be obtained. For the same reason, in the photoresist composition for immersion exposure of the present invention, the static contact angle before exposure and development of the photoresist film obtained by using the photoresist composition is preferably 60 degrees or more, and is preferably 6 3 to 9 5 degrees is better, and 6 5 to 9 5 degrees is particularly good. Further, in the photoresist composition for immersion exposure of the present invention, the measurement of the roll angle before exposure and development of the photoresist film obtained by using the photoresist composition is preferably 36 degrees or less, and is preferably 10 to 36 degrees. For better, 7 to 30 degrees is especially good for '1 to 2 to 7 degrees. When the roll angle is below the upper limit ,, the effect of suppressing the dissolution of the substance during the immersion exposure can be improved. Further, when the roll angle is equal to or lower than the lower limit, good lithographic etching characteristics and the like can be obtained. The above various angles (dynamic contact (advance angle, receding angle, roll angle, etc.), static contact angle) can adjust the composition content of the photoresist composition for immersion exposure, for example, the type or amount of (C) component , (-91 - 200923574 A) The type of ingredients is adjusted. For example, when the content of the component (C) is increased, the hydrophobicity of the resulting photoresist composition can be increased, and the advancing angle, the receding angle, and the static contact angle can be increased to reduce the roll angle. As described above, the photoresist composition for immersion exposure of the present invention is highly suitable for use as an immersion exposure because it sufficiently satisfies various characteristics sought for by the photoresist material during immersion exposure. <<Method for Forming Photoresist Patterns>> The method for forming a photoresist pattern of the present invention comprises the step of forming a photoresist film on a support by using the above-described resist composition for immersion exposure of the present invention, and the photoresist film is formed. The step of performing the immersion exposure and the step of forming the photoresist pattern by alkali development of the photoresist film. Preferred examples of the method for forming the photoresist pattern of the present invention are as follows. First, the photoresist composition for immersion exposure of the present invention is applied onto a support by a spin coater or the like, and then subjected to post-bake (PAB) treatment to form a photoresist film. The support is not particularly limited, and conventionally known articles such as a substrate for an electronic component or an article on which a specific circuit pattern is formed may be used. More specifically, for example, a metal wafer such as a sand wafer, copper, chromium, iron, or the like, or a glass substrate. For the material of the circuit pattern, for example, copper, aluminum, nickel, gold, or the like can be used. Further, for the support, for example, an inorganic or/or organic film may be provided on the substrate. An inorganic film such as an inorganic antireflection film (Inorganic-92-200923574 BARC). Organic film, such as organic anti-reflective film (organic B ARC ) or underlying organic film in multilayer photoresist method. Wherein, the multilayer photoresist method refers to an organic film (lower organic film) provided on the substrate, and at least one photoresist film (upper photoresist film), and the photoresist pattern formed on the upper photoresist film is used as The mask is patterned by drawing the underlying organic film to form a pattern having a high aspect ratio. That is, according to the multilayer photoresist method, since the thickness of the lower organic film can be ensured, the photoresist film can be thinned, and a fine pattern having a high aspect ratio can be formed. The multilayer photoresist method is basically a method of dividing into a two-layer structure having an upper photoresist film and a lower organic film (two-layer photoresist method), and one or more layers between the upper photoresist film and the lower organic film. A method of three-layer or more multilayer structure of an intermediate layer (metal thin film or the like) (three-layer photoresist method). After the formation of the photoresist film, an organic antireflection film may be further provided on the photoresist film to form a three-layer laminate formed of the support and the photoresist film and the antireflection film. The antireflection film provided on the photoresist film is preferably one which is soluble in an alkali developer. A well-known method can be used for the steps so far. The operating conditions and the like can be appropriately set in accordance with the composition or characteristics of the positive-type resist composition for the immersion exposure to be used. Next, the photoresist film obtained as described above is subjected to selective immersion exposure (Liquid Immersion Lithography) through a desired mask. At this time, a solvent having a refractive index higher than that of air (immersion medium) is filled between the photoresist film and the lens at the lowest position of the exposure device, and exposure (immersion exposure) is performed in this state. The wavelength used for exposure is not particularly limited, and it can be used -93- 200923574

KrF excimer laser, ArF excimer laser, F2 excimer laser and other radiation. Among them, the photoresist composition of the present invention is effective for KrF excimer laser and ArF excimer laser, and is particularly effective for ArF excimer laser. The immersion medium preferably has a refractive index larger than that of air, and is preferably a solvent having a refractive index smaller than that of the photoresist film formed by using the positive-type photoresist composition for immersion exposure of the present invention. The refractive index of the solvent is not particularly limited as long as it is within the above range. A solvent having a refractive index greater than that of air and smaller than the refractive index of the photoresist film, for example, water, a fluorine-based inert liquid, an oxime-based solvent, a hydrocarbon-based solvent, or the like. Specific examples of the fluorine-based inert liquid include a liquid such as C 3 HC 12 F 5 , C 4 F 9 〇C Η 3, C4F9OC2H5, and c5h3f7, and the like, and a boiling point of 70 to 180 C is preferably 80. It is better to 160 〇C. In the fluorine-based inert liquid, when the boiling point is in the above range, the medium used for the wetting type can be removed simply after the end of the exposure, and it is preferred that the fluorine-containing inert liquid 'in particular, the hydrogen in the alkyl group. A perfluoroalkyl compound obtained by substituting all of the atoms with a fluorine atom is preferred. A perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further 'more specifically' the above perfluoroalkyl ether compound, such as perfluoro(2-butyl-tetrahydrofuran) (boiling point 102t:), the aforementioned perfluoroalkyl compound, such as perfluorotributylamine (boiling point) 1 7 4 °C) and so on. The positive-type resist composition for immersion exposure of the present invention is particularly susceptible to the adverse effects of water, and excellent sensitivity, light-94-200923574 resistance pattern appearance, etc. The dip in the invention is most suitable for use. In addition, water is also better in terms of cost, safety, and general use. Next, post exposure bake (PEB) is performed after the immersion exposure step is completed. Next, the alkali developing solution formed by the liquid is preferably washed with pure water, for example, a substrate surface developing solution which can be sprayed or sprayed in a rotating state, and an immersion type exposure which is dissolved in the developing solution. Further, by performing a drying treatment, a photoresist pattern obtained by patterning a photoresist pattern can be obtained by using a coating film of a photoresist composition for a photoresist film. [Embodiment] [Embodiment] Next, the present invention will be described in more detail by way of examples without limitation. [Example 1] Under a nitrogen atmosphere, 〇 ° C, dissolved in 2,3, monophenylbenzene 5g (26mmol), triethylamine 5.: tetraammine (THF) gluten solution In i5 ml, 6 ml of a 3.8 g (31-2 mmol) solution of THF in three portions was added dropwise. The temperature of the reaction solution was returned to room temperature, and it was mixed for 1 hour. After confirming the disappearance of the raw materials by the analytical method (TLC), the reaction medium is heated with water environment problems and after extensive exposure (washing with alkaline water, washing, and forming a photoresist composition on the substrate (immersion exposure pattern) Type drawing (illustration, but this is 5,6 - four gas - 4 3 g ( 5 2 mm ο 1 ) After the chlorination of methyl ethyl hydrazine, the thin layer of color layer will be used to cool to 〇 °c, -95- 200923574 After the addition of water, the reaction was stopped. After the addition of water and t-ester acetate for 3 times, the obtained organic layer was washed once with saturated aqueous ammonium chloride solution, water and saturated brine, and anhydrous sulfuric acid was added thereto. The sodium is dried. After the solvent is distilled off under reduced pressure, the obtained product is re-slurried with hexane-acetic acid, and b'servant 2,3,5,6-tetraki- 4-trimethylacetoxybenzene B. (hereinafter referred to as compound (1)) colorless solid 5.9 g (yield 8 2 %) 〇 [化 4 5]

The obtained compound (1) was measured by 1 Η - N M R. The results are as follows: ^ Η NMR (solvent: CDC13, 400MHz): (5 (ppm) = 6.6 ( dd, 1 Η (Hb)), 6 _ 1 (d, 1 Η ( Ηa ) ), 5_7 ( d, 1 Η ( Ha ) ) , 1 · 4 ( s, 9 Η ( Hc )). From the above results, it was confirmed that the compound (1) has the following structure -96-200923574 [Chem. 4 6]

CHc3 - CHC; bHc3 The obtained compound (1) was subjected to the following evaluation. [Reaction under the test conditions] To 20 mg of the compound (1), a mixed solution of THF / 2.38 mass% aqueous solution of tetramethylammonium hydroxide = 1 / 1 (mass ratio) 〇 · 5 m 1 ' and vibrated for 10 seconds was added. bell. Thereafter, the removed organic layer and the deprotected body were developed with T.sub.2 (Heptane:ethyl acetate = 8:2) as a predetermined 2,3,5,6-tetrafluoro-4-hydroxystyrene. As a result, it was confirmed that a part of the compound (1) was deprotected (dissociation of trimethylethenyl (a CO-C(CH3)3)) to form a deprotector (2, 3, 5, 6 - 4) Fluor-4-tetrahydroxystyrene) (deprotection is the same as Rf値 of 2,3,5,6-tetrafluoro-4-hydroxystyrene, compound (1) is 値:0_77, Rf of deprotector値: 0.42). [Example 2] The compound (1) of 1. 〇〇g ( 3.62 mmol) synthesized in Example 1 was dissolved in toluene of . 〇 g. To the solution, a polymerization initiator V-6 0 1 (manufactured by Wako Pure Chemical Industries, Ltd.) 〇 · 5 4 m m ο 1 was added to dissolve it. After the solution of the solution -97-200923574 was subjected to polymerization at 80 ° C for 2 hours in a nitrogen atmosphere, the reaction solution was cooled to room temperature. Thereafter, the polymer was repeatedly subjected to two precipitation operations in the reaction methanol solution. The polymer obtained in the above manner was reduced in a powder of 66 g (yield 60%) at room temperature. This is referred to as a fluorine-containing ί. The mass average molecular weight converted from the (C)-1' GP C measurement is 9,900, and the degree of dispersion is [Chem. 4 7]. The reaction junction is flooded into a large amount. Press dry, white: compound (C) a standard polystyrene L29.

7.9 g of ethyl-3-th-heptanol, Comparative Synthesis Example 1] 7,7,7-trifluoro-yl-pyridinium. 2 g, diethylamine 7.lg was added to a mixer equipped with a stirrer, a thermometer, and a dropping funnel. 1 〇g of acetonitrile, 6.7 g of methacrylic acid chloride was dissolved in about 75 t, 3 Torr, and stirred at the same temperature for 2 hours. While warming, it was washed once with a mixture of 8-8 g of potassium carbonate and 1 ml of water mixed with 1% of a saline solution. The mixture was dried over anhydrous magnesium sulfate in a -98- 4-neck flask, and 4-dimethylamine was stirred and dissolved. The solution was dropped into the chamber and cooled to the chamber for 1 time, and the pressure was reduced to 200923574. The concentrate was purified by ruthenium gel permeation chromatography to give 5.7 g of 7,7,7-trifluoro-3-ethyl-3-heptyl methacrylate. The 1 Η - N M R data of 7,7,7-trifluoro-3-ethyl- 3 -heptyl methacrylate obtained is shown below. 'Η - NMR ( CDC13 ) &lt;5: 〇.82~〇.87(tr,6H,-CH3), 1.46~1.58(m'2H, -CH2—), 1.78~1.97 (m, 9H' = C - CH3 &gt; - C - CH2 - ), 1-98 to 2.16 (m, 2H,

CF3CH2 - ), 5.49 (s' 1H' C = CH2), 6.01 (s, 1H, C = CH2 ) Based on the above results, it was confirmed that the structure has the following formula. [化4 8]

Next, 'in a four-necked flask equipped with a nitrogen gas injection tube, a refluxing device, a dropping funnel, and a thermometer, 27 g of tetrahydrofuran, and the above-obtained 7,7,7-trifluoro-3-ethyl-3-hexyl methacrylate were added. 11.98 g, after nitrogen substitution, was warmed to 67 °C. While maintaining this temperature, a solution obtained by dissolving 3 g of 2,2,-azobis(2,4-dimethylvaleronitrile) 30.30 g of tetrahydrofuran was dropped over 1 Torr. After the completion of the dropwise addition, the mixture was continuously stirred for 6 hours while maintaining the temperature, and then cooled to room temperature. The obtained polymerization reaction is dropped into a large amount of a mixed solution of methanol/water. The precipitated resin is filtered, washed, and dried to obtain a fluorine-containing compound of the following chemical formula (C)-2 as a white solid. . (C) Quality of standard polystyrene converted to 2 200923574 The average molecular weight (Mw) is 65 Å and the degree of dispersion (Mw/Mn) is 1.4. [化4 9]

[Example 3] 8 g (42 mmol) of 2,3,5,6-tetrafluoro-4-tetrahydroxystyrene was added to 3 g of 3,3,3-trifluoropropionic acid at 0 ° C under a nitrogen atmosphere ( 62 mmol ), ethyl diisopropylaminocarbonyl ruthenium diimide hydrochloride (EE > C1 ) 14 g (75 mmol ), dimethylaminopyridine (DMAP) 0.5 g (4 mmol) in 40 ml of THF solution, replied Stir for 3 hours to room temperature. After confirming the disappearance of the raw material by thin layer chromatography (TLC), the reaction liquid was cooled to 〇7, and water was added to stop the reaction. Thereafter, ethyl acetate was added to the reaction liquid for extraction three times. The obtained organic layer was washed twice with water. Thereafter, the bath was removed under reduced pressure. The obtained product was purified by hydrazine gel chromatography (ethyl acetate to ethyl acetate) to give the compound (3) of the following colorless oily substance (3). 9 g (yield 72%). -100- 200923574 【化5 0】

The obtained compound (3) was measured by 1 Η-NMR. The results are shown below. 'H-NMR (solvent: CDC13, 400MHz): δ (ppm) = 6.6 ( dd &gt; 1 Η (Hb ) ) , 6.1 (d, lH(Ha)) , 5_7(d, 1 H ( Ha ) ) , 3 .5 ( m, 2H ( Hc )). From the above results, it was confirmed that the compound (3) had the structure shown below. 【化5 1】

[Example 4] 2.50 g (8.28 mmol) of the compound (3) synthesized in Example 3 was dissolved in 5.3 g of toluene. To the solution, 0.41 mmol of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Let it dissolve. This solution was subjected to polymerization at 9 CTC for 3 hours under a nitrogen atmosphere. After the reaction was completed -101 - 200923574, the reaction solution was cooled to room temperature. Thereafter, the reaction was dropped into a large amount of a methanol solution, and the operation of precipitating the polymer was repeated twice. The polymer obtained in this manner was dried under reduced pressure at room temperature to give white powder (yield: 58%). This is called a fluorine-containing compound (C)-3. For this (C)-3, the mass average molecular weight in terms of standard polystyrene determined by GPC measurement is a dispersion of 1.67. [化5 2]

CF3 (C) - 3 [Example 5] 3 § (equivalent to 25 mmo1) of polyhydroxystyrene (product name: VP8000, manufactured by Nippon Soda Co., Ltd.) was added to 3, 3 under a nitrogen atmosphere at 0 °C. , 3-trifluoropropionic acid 4g (30mmol), ethyl diisopropylaminopyrrolidine hydrochloride (EDC1) 6.2g (33mmo1), dimethylaminopyridine (DMAP) 0_5g (4mmo1) The THF solution was returned to room temperature in 60 ml and stirred for 3 hours. Thereafter, the reaction liquid was cooled to 0 ° C, and water was added to stop the reaction. The obtained organic layer was washed three times with water, and the solvent was evaporated under reduced pressure. The THF solution of the obtained product was dropped into heptane to carry out a reprecipitation-102-200923574 operation to obtain a fluorine-containing compound (C) - 4 4 - 3 g represented by the following formula (4) as a colorless solid (yield 7 5 %) ). The obtained fluorine-containing compound (C)-4 was measured for 13 C - N M R . As a result, it was confirmed that -C(=0)-CH2-CF3 (introduction rate 74_1 mol%) was introduced in 74.1 mol% of the hydroxyl group of the polyhydroxystyrene of the raw material. Therefore, m in the following formula (C)-4: η is 74.1: 25.9 (mole ratio) ° Further, in (C)-4, the mass average of the standard polystyrene conversion obtained by GPC measurement is used. The molecular weight was 14,000 and the degree of dispersion was 1.08. 【化5 3】

Ο

(C) - 4 [Examples 6 to 9, Comparative Examples 1 to 2] The components shown in the following Table 1 were mixed and dissolved to prepare a photoresist composition -103 - 200923574 [Table 1] (Α) component (8) (C) Ingredient (D) Ingredient (S) Ingredient Example 6 (Α) —1 [1〇〇] (8)—1 [8.0] (C) -1 (1.0) (D) -1 [1.2] (S) -1 [1500] Example 7 (A) -1 [100] (Β) -1 [8.0] (C) -1 [5.0] (D) - 1 [1.2] (8) -1 [1500] Comparative Example 1 ( A) -1 〔1〇〇〕 (Β) -1 〔8.0〕 (C) -1 [1.0] (D) -1 [1.2] (S) -1 [ 1500] Comparative Example 2 (Α) -1 〔 100] (Β) -1 [8.0] — (D) -1 C1.2] (8) -1 [1500] Example 8 (Α) - 1 [100] (Β) -1 [8.0] (C) —3 [1.0] (D) [1.2] (8) -1 [1500] Example 9 (A) -1 [1〇〇] (Β) -1 [8.0] (C) A 4 [1.0] (D) - 1 ( 1.2) (8)—1 [1500] The abbreviations in Table 1 are as follows. (A) - 1: a copolymer represented by the following chemical formula (A)-1. In the formula, the number on the lower right side of () is the ratio of each structural unit (% by mole) 〇(B) — 1: (4-methylphenyl)diphenylphosphonium hexafluoro- η-butane sulfonate . (C) A: The fluorine-containing compound (C) synthesized in Example 2 - 1 〇 (C) - 2 : Comparative fluorine-containing compound (C)-2 synthesized in Synthesis Example 1. (c) a 3: a fluorine-containing compound (C) synthesized in Example 4 - 3 〇 (C) - 4 : a fluorine-containing compound (C) synthesized in Example 5 - 4 - 104 - 200923574 (D) -1 : Tri-n-pentylamine. (S) — l: Mixed solvent of PGMEA/PGME=6/4 (mass ratio). 【化5 4】

[Mw is 7 000 and M w/Mn is 1 · 8]. Next, 'the photoresist composition having the composition shown in Table 1 was coated on a 8-inch wafer using a spin coater, and then pre-baked at π 0 ° C for 60 seconds on a hot platen. After drying, a photoresist film having a film thickness of 2 〇 nm is formed. The surface of the photoresist film (photoresist film before exposure) was dropped, and the contact angle (static contact angle) was measured using DROP MASTER-700 (product name, Kyowa Interface Science Co., Ltd.) (measurement of contact angle: Water 2 // L ). This measurement is referred to as "contact angle (°) after Coat". The wafer after the contact angle was measured was subjected to development treatment at 2.3% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution at 60 ° C for 60 seconds, followed by 15 seconds of pure water. After washing with water, the contact angle was measured in the same manner as above. The measured enthalpy was taken as "contact angle after development (.) -105 - 200923574". Further, the difference between the contact angle after the Coat and the contact angle after development is represented by Δ (.). The results are shown in Table 2. 〔Table 2〕

Contact angle after Coat (.) Contact color Q_ △ (.) after development Example 6 85.6 75.9 .. -9.7 Example 7 95.0 90.6 -4.4 Comparative Example 88.3 89.7___ 1.4 Comparative Example 2 68.2 59.4 -8.8 Example 8 83.3 60.0 _ -23.3 Example 9 78.8 55.4 - 23.4 From the above results, Examples 6 to 9 using the fluorine-containing compound of the present invention, and Comparative Example 1 containing the fluorine-containing compound (C)-2, either or both When compared with Comparative Example 2 in which no fluorine-containing compound was added, the contact angle after Coat was high. In Examples 6 to 9 in which the fluorine-containing compound of the present invention was used, the contact angle after development was low, and in particular, in Examples 8 to 9, it was lower than that of Comparative Example 2 in which no fluorine-containing compound was added. . Therefore, it was confirmed that it had hydrophobic properties when it was subjected to immersion exposure, and it was hydrophilic when developed. Further, in Comparative Example 1, the developing solution failed to dissociate the protective group, and the contact angle was not lowered. [Example 1 0] Under a nitrogen atmosphere, 15 g (84 mmol) of P-phenylphenyl methacrylate-106-200923574 ester was added to llg (84 mmol) of 3,3,3-trifluoropropanoic acid under a nitrogen atmosphere. Ethyl diisopropylaminocarbonyl ruthenium diamine hydrochloride (EDC1) 19g (1 01 mmol), dimethylaminopyridine (DMAP) 0.5g (4mmol) in 150ml of THF solution, returned to the room Warm and stir for 3 hours. After confirming the disappearance of the raw material by thin layer chromatography (TLC), the reaction solution was cooled to 〇 ° C, and water was added to stop the reaction. Thereafter, ethyl acetate was added to the reaction mixture, and extraction was performed three times, and the obtained organic layer was washed twice with water. Then, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by heptane-ethyl acetate to give the compound (5) 22 g (yield of the formula (5). 91%). [5 5]

The obtained compound (5) was measured for 1 Η-NMR. The results are shown below.

iH-NMR (solvent: DMSO-6d): 7.2 - 7.1 (m, 4H (Hc)), 6.35 (s, lH(Hb)), 5.78 (s, lH(Hb)), 3.46 (m, 2H (Hd) ) ) , 2_08(s, 3H(Ha)). 200923574 From the above results, it was confirmed that the compound (5) has the structure shown below.

With respect to the obtained compound (5), except for the developing solution of TLC, a part of the compound (5) was produced in the same manner as in Example 1 except that a solution of heptane: ethyl acetate = 7:3 was used. Protection (dissociation of (a CO-CH2 - CF3)) confirms the formation of a deprotector. [Example 1 1] In a three-necked flask equipped with a thermometer and a reflux tube, the compound (5) synthesized in Example 10 was placed in an amount of 2-27 g (11.57 mmol), and the compound (6) 5.00 g (1 7.36 mmol) and THF. 41.20g, stirred and dissolved. To the solution, 1.74 mmol of a polymerization initiator V-601 (manufactured by Wako Pharmaceutical Co., Ltd.) was added and dissolved. This solution was heated and stirred under a nitrogen atmosphere at 8 Torr for 6 hours to carry out a polymerization reaction, and then the reaction liquid was cooled to room temperature. Thereafter, 'concentrating the polymerization reaction solution under reduced pressure, dropping a large amount of π-Gengyuan' to precipitate the polymer, and filtering, washing and drying the immersed polymer to obtain the desired fluorine-containing compound. (C) a 5 4.5 0 g °

The obtained fluorine-containing compound (C)-5 was measured using 13C-NMR 200923574 600 MHz, and it was found that 1 of the following formula (C)-5: m was 68.7:31.3 (mole ratio). Further, in the above (C)-5, the mass average molecular weight in terms of standard polystyrene determined by GPC measurement was 18,600, and the degree of dispersion was 1.84. [化5 7]

[Example 1 2] Each component shown in the following Table 3 was mixed and dissolved to prepare a photoresist composition.

Further, in Table 3, (A)-1, (B)-1, (D)-1, (S)1, and 1 are the same as Table 1. Further, in the table (C)-5, the fluorine-containing compound (C)-5 synthesized in Example 11 was used. [Table 3] (A) Component (8) Component (C) Component (9) Component (S) Component Example 12 (A) -1 [100] (B) -1 (8.0) (C) -5 [1.0] (D) —1 [1.2] (S) -1 [ 1500 ] -109 - 200923574 Next, the photoresist composition of Example 1 2 was applied to a 8 吋 sand wafer using a spin coater, and then to a hot plate. The film was pre-baked at 1 〇 ° c for 90 seconds, and dried to form a photoresist film having a film thickness of 1 2 Onm. The surface of the photoresist film (photoresist film before exposure) was dropped, and the contact angle (static contact angle) was measured using DROP MASTER-70.00 (product name, Kyowa Interface Science Co., Ltd.) (Measurement of contact angle) : Water 2 # L ). This measurement is referred to as "contact angle (°) after "C 〇 at". The wafer after the contact angle was measured was subjected to development treatment at 23 ° C for 30 seconds or 60 seconds with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), and then for 15 seconds. After washing with pure water, the contact angle was measured in the same manner as above. The measurement was carried out as "contact angle (°) after development for 3 seconds" and "contact angle (.) after development for 60 seconds). Further, the difference between the contact angle after the Coat and the contact angle after development is represented by Δ (.). The results are shown in Table 4. 〔Table 4〕

Contact angle after Coat (.) Contact angle after development for 30 seconds (.) △ (.) Contact angle after development for 60 seconds (.) △ (.) Example 12 78.9 61.1 - 17.8 60.5 -18.4 From the above results, it was found that 'addition In the embodiment 12 of the fluorine-containing compound (C)-5 of the present invention, the contact angle after development is small as compared with the post-Coat contact angle. Therefore, it was confirmed that it was hydrophobic at the time of immersion exposure and formed a hydrophilic property upon development. -110- 200923574 [Simple description of the drawing] [Fig. 1] A diagram showing the advancing angle (0 1 ), the receding angle (0 2 ), and the roll-off angle (6* 3 ). [Description of main component symbols] 1 : Droplet 1 a : lower end 1 b : upper end 2 : plane 0 1 : advancing angle Θ 2 : receding angle 0 3 : rolling angle -111 -

Claims (1)

200923574 X. Patent Application No. 1 · A photoresist composition for immersion exposure characterized in that a substrate component (A) containing a change in solubility of an alkali developer via an action of an acid is generated and formed by exposure Acid acid generator component (B), and fluorine-containing compound (C) having a group represented by the following formula (c) and containing at least one fluorine atom; [Chemical Formula 1] Q-Ο C-R1 ... (C) [wherein Q is a group in which one hydrophilic group removes one hydrogen atom, and R1 is a hydrocarbon group having two or more carbon atoms which may have a fluorine atom]. The immersion exposure photoresist composition according to the first aspect of the invention, wherein the fluorine-containing compound (C) is a compound represented by the following formula (C-1), and is a compound represented by the following formula (C-1). 3 R 2 —Q—C—R 3 (( c — 1) [wherein Q is a monovalent hydrophilic group which removes one hydrogen atom, and R 2 is an organic group containing an aromatic ring group which may have a fluorine atom, R3 is a hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom, and at least one of R2 and R3 has a fluorine atom. 3. The photoresist composition for immersion exposure according to claim 2, wherein the fluorine-containing compound (C) is a compound of the following formula (c-1 - 1) - 112 - 200923574 - (C-1) 4) a compound represented by a formula selected from the group, [Chemical 3] ...(C — 1 — 1 ) R63 ...(C-1 - 2) (C-1 - 3) (C - 1 - 4 ) wherein R51 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R52 to R55 are each independently a hydrogen atom or a fluorine atom, and at least one of R52 to R5 5 is a fluorine atom. R56 is a hydrocarbon group having a carbon number of 2 or more and having a fluorine atom of -113 to 200923574; R61 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R62 to R65 are each independently a hydrogen atom or a fluorine atom, and R66 is a fluorine atom. a hydrocarbon group having 2 or more carbon atoms]. 4. The photoresist composition for immersion exposure according to the first aspect of the invention, wherein the fluorine-containing compound (C) has a formula (cl-:i-1)~(cl-11-4) a polymer compound selected from the group of structural units represented by the formula, -114 - 200923574 [Chemical 4] (cl-1 1 - 1 R61 R55^\^\r53 R62 R5VV-' cr , '〇64 01c—o R56 *&quot; (cl — 1 — 3) 0Ic=o R66 “·(cl — 1 — 4) [wherein R51 is a hydrogen atom a lower alkyl group or a halogenated lower alkyl group, R52 to R55 are each independently a hydrogen atom or a fluorine atom, at least one of R52 to R55 is a fluorine atom, and R.sup.6 is a hydrocarbon group having a fluorine atom of 2 or more; R61 Is a hydrogen atom 'lower alkyl or halogenated lower alkyl, R62 to R05 are each independently a hydrogen atom or a fluorine atom, and R66 is a hydrocarbon group having a fluorine atom of from 2 to 115 to 200923574. The immersion exposure photoresist composition of the first aspect, wherein the substrate component (A) is a substrate component which increases the solubility to an alkali developer via the action of an acid. The immersion exposure photoresist composition, wherein the aforementioned substrate component (A) is a resin component (A 1 ) containing a solubility enhancing effect on an alkali developer via an action of an acid, the resin component (A 1 ) It is a structural unit (a 1 ) derived from an acrylate having an acid-dissociable dissolution inhibiting group. The immersion exposure photoresist composition of claim 6, wherein the resin component (A1) has a structural unit (a2) derived from an acrylate containing a lactone-containing cyclic group. The immersion exposure photoresist composition of claim 6, wherein the resin component (A 1 ) 尙 has a structural unit (a3 ) derived from an acrylate containing a polar group-containing aliphatic hydrocarbon group. The photoresist composition for immersion exposure according to the first aspect of the invention, which comprises a nitrogen-containing organic compound (D). 10. A method for forming a photoresist pattern, characterized by comprising, using the patent application range 1~ The step of forming a photoresist film on the support by the photoresist composition for immersion exposure according to any one of the steps of the present invention, the step of performing the immersion exposure of the photoresist film, and subjecting the photoresist film to alkali development to form light Step of resisting pattern 11. A fluorine-containing compound having a group represented by the following formula (c) and containing at least one fluorine atom, -116-200923574 [Chemical 5] R1 I OHNC IQ [where, Q The base 'R1 obtained by removing one hydrogen atom of the monovalent hydrophilic group is a hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom. 1 2 _ The fluorine-containing compound of the first aspect of the patent application is the following A compound represented by the formula (C-1), [Chem. 6] 〇R2—Q—q_R3 ((--) (wherein Q is a monovalent hydrophilic group which removes one hydrogen atom group, and R2 contains a An organic group having an aromatic cyclic group of a fluorine atom, R 3 is a hydrocarbon group having 2 or more carbon atoms which may have a fluorine atom, and at least one of R 2 and R 3 has a fluorine atom. 13. A fluorine-containing compound according to claim 12, which is a compound represented by a formula selected from the group consisting of the following formula (C-1_1)) to (C-1-4-) , -117- 200923574 [ί匕7] -3) 1-4) a lower alkyl group, at least 2 or more hydrocarbon groups of 5 2 to R 5 5 , and R 62 to R 65 are carbon atoms of the atom 2 (wherein R 51 is a hydrogen atom, a lower alkyl group or a halogen R 52 ) ～R55 is a hydrogen atom or a fluorine atom which is independent of each other, R 1 is a fluorine atom, R 56 is a carbon number which may have a fluorine atom; and R 61 is a hydrogen atom or a fluorine atom independently a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R06 is a hydrocarbon group having a fluorine-118-200923574 or higher]. 1 4 - a fluorine-containing compound as claimed in claim 11 which is represented by a formula selected from the group consisting of the following formula (c 1 -1 (c 1 -1 - 4 )) Structural unit of polymer compound [Chemical 8] 院-119- 200923574 R~R are independent hydrogen atoms or fluorine atoms, at least one of R52 to R55 is a fluorine atom, and R56 is a hydrocarbon group having a carbon number of 2 or more. 'R 6 1 is hydrogen An atom, a lower-grade or a halogenated lower-grade compound, R 6 2 to R 6 5 are each independently a hydrogen atom or a fluorine atom 'R66 is a hydrocarbon group having a fluorine atom of 2 or more. -120-