Abstract: When sulfinating a carboxylic acid bromofluoroalkyl ester by using a sulfinating agent, an organic base is used, thereby obtaining a fluoroalkanesulfinic acid ammonium salt. This is oxidized to obtain a fluoroalkanesulfonic acid ammonium salt. This is used as the raw material and is converted to an onium salt or is converted to an onium salt by going through saponification and esterification, thereby obtaining a fluoroalkanesulfonic acid onium salt. This fluoroalkanesulfonic acid onium salt is useful as a photoacid generator used for chemically amplified resist materials, etc.

Abstract: In the present invention, a target alkoxycarbonylfluoroalkanesulfonic acid salt is obtained by using a halofluoroalkanoic acid ester as a starting raw material, sulfinating the halofluoroalkanoic acid ester in the presence of an amine (as a first step), and then, oxidizing the resulting sulfination product (as a second step). Further, an alkoxycarbonylfluoroalkanesulfinic acid onium salt, which is useful as a photoacid generator, is obtained by salt exchange reaction of the alkoxycarbonylfluoroalkanesulfonic acid salt.

Abstract: According to the present invention, there is provided a fluorine-containing sulfonate resin having a repeating unit of the following general formula (3). In order to prevent deficiency such as roughness after pattern formation or failure in pattern formation, the fluorine-containing sulfonate resin incorporates therein a photoacid generating function and serves as a resist resin in which “a moiety capable of changing its developer solubility by the action of an acid” and “a moiety having a photoacid generating function” are arranged with regularity.

Abstract: According to the present invention, a polymer is obtained by polycondensation of a fluorinated dicarboxylic acid derivative of the general formula (M-1) or an acid anhydride of the fluorinated dicarboxylic acid with a polyfunctional compound having two to four reactive groups corresponding in reactivity to carbonyl moieties of the fluorinated dicarboxylic acid derivative or acid anhydride. [Chem. 134] AOCF2C-Q-CF2COA???(M-1) In the above formula, Q represents a divalent organic group having a substituted or unsubstituted aromatic ring; and A and A? each independently represent an organic group. This polymer exhibits a sufficiently low dielectric constant for use as a semiconductor protection film and has the capability of forming a film at a relatively low temperature of 250° C. or lower.

Abstract: According to the present invention, there is provided a fluorine-containing sulfonate resin having a repeating unit of the following general formula (3). In order to prevent deficiency such as roughness after pattern formation or failure in pattern formation, the fluorine-containing sulfonate resin incorporates therein a photoacid generating function and serves as a resist resin in which “a moiety capable of changing its developer solubility by the action of an acid” and “a moiety having a photoacid generating function” are arranged with regularity.

Abstract: By using an organic base when a carboxylic acid bromodifluoroethyl ester is sulfinated by using a sulfinating agent, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt. By oxidizing the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt. By using the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt as a raw material and exchanging it into an onium salt directly or through saponification/esterification, there can be obtained a 2-alkylcarbonyloxy-1,1-difluoroethanesulfonic acid onium salt.

Abstract: A fluorine-containing polymer of the present invention contains a repeating unit (a) of the general formula (2) and has a mass-average molecular weight of 1,000 to 1,000,000. This polymer is suitably used in a resist composition for pattern formation by high energy ray radiation of 300 nm or less wavelength or electron beam radiation or a top coat composition for liquid immersion lithography and is characterized as having high water repellency, notably high receding contact angle. In the formula, R1 represents a polymerizable double bond-containing group; R2 represents a fluorine atom or a fluorine-containing alkyl group; R8 represents a substituted or unsubstituted alkyl group or the like; and W1 represents a single bond, a substituted or unsubstituted methylene group or the like.

Abstract: According to the present invention, there is provided a polymerizable fluorine-containing sulfonic acid onium salt of the following general formula (2) and a resin obtained by polymerization thereof. It is possible by the use of this sulfonate resin of the present invention to provide a resist composition with high resolution, board depth of focus tolerance (DOF), small line edge roughness (LER) and high sensitivity. In the formula, Z represents a substituted or unsubstituted C1-C6 straight or branched alkylene group, or a divalent moiety in which substituted or unsubstituted C1-C6 straight or branched alkylene groups are bonded in series to a divalent group obtained by elimination of two hydrogen atoms from an alicyclic or aromatic hydrocarbon; R represents a hydrogen atom, a halogen atom, or a C1-C3 alkyl or fluorine-containing alkyl group; and Q+ represents a sulfonium cation or an iodonium cation.

Abstract: Disclosed is a top coating composition formed on a resist film, for protecting the resist film, the top coating composition being a top coating composition for photoresist, characterized by containing a fluorine-containing polymer having a repeating unit represented by the following general formula (1). This composition is capable of controlling developing solution solubility and has a high water repellency. [In the formula, R1 represents a hydrogen atom, fluorine atom, methyl group or trifluoromethyl group, R2 represents a heat-labile protecting group, R3 represents a fluorine atom or fluorine-containing alkyl group, and W is a bivalent linking group.

Abstract: By using an organic base when a carboxylic acid bromodifluoroethyl ester is sulfinated by using a sulfinating agent, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt. By oxidizing the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt. By using the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt as a raw material and exchanging it into an onium salt directly or through saponification/esterification, there can be obtained a 2-alkylcarbonyloxy-1,1-difluoroethanesulfonic acid onium salt.

Abstract: There is disclosed a fluorine-containing polymer compound comprising a repeating unit (a) of the following general formula (2) and having a weight-average molecular weight of 1000 to 1000000 where R1 represents a polymerizable double bond-containing group; R2 represents a fluorine atom or a fluorine-containing alkyl group; R3 represents a hydrogen atom, an acid labile group, a cross-linking site or the other monovalent organic group; and W1 represents a linking moiety. When the fluorine-containing polymer compound is used in a resist compound for pattern formation by high energy radiation of 300 nm or less wavelength or electron beam radiation, it is possible to form a resist pattern with a good rectangular profile.

Abstract: A polymerizable fluorine-containing compound represented by formula (1), wherein R1 represents a polymerizable double-bond containing group, R2 represents an acid-labile protecting group, R3 represents a fluorine atom or fluorine-containing alkyl group, and W represents a bivalent linking group. This compound can provide a fluorine-containing polymer compound that has a weight-average molecular weight of 1,000-1,000,000 and contains a repeating unit represented by formula (2), wherein R2, R3 and W are defined as above, each of R4, R5 and R6 independently represents a hydrogen atom, fluorine atom or monovalent organic group, at least two of R4, R5 and R6 may be combined to form a ring. This polymer compound can provide a resist composition capable of forming a pattern that is transparent to exposure light and superior in rectangularity.

Abstract: By using an organic base when a carboxylic acid bromodifluoroethyl ester is sulfinated by using a sulfinating agent, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt. By oxidizing the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfinic acid ammonium salt, there is obtained 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt. By using the 2-(alkylcarbonyloxy)-1,1-difluoroethanesulfonic acid ammonium salt as a raw material and exchanging it into an onium salt directly or through saponification/esterification, there can be obtained a 2-alkylcarbonyloxy-1,1-difluoroethanesulfonic acid onium salt.

Abstract: There is provided an acid having a fluorine-containing carbanion structure or a salt having a fluorine-containing carbanion structure, which is represented by the following general formula (1). By using a photoacid generator for chemically amplified resist materials that generates this acid, it is possible to provide a photoacid generator which has a high sensitivity to the ArF excimer laser light or the like, of which acid (photo generated acid) to be generated has a sufficiently high acidity, and which has a high dissolution in resist solvent and a superior compatibility with resin, and a resist material containing such a photoacid generator.

Abstract: A fluorine-containing unsaturated carboxylic acid represented by formula (1), wherein R1 represents a polymerizable double-bond containing group, R3 represents a fluorine atom or fluorine-containing alkyl group, and W represents a bivalent linking group. This compound can provide a fluorine-containing polymer compound that has a weight-average molecular weight of 1,000-1,000,000 and contains a repeating unit represented by formula (2), wherein R3 and W are defined as above, each of R4, R5 and R6 independently represents a hydrogen atom, fluorine atom or monovalent organic group, at least two of R4, R5 and R6 may be combined to form a ring. This polymer compound can provide a chemically amplified resist composition that is transparent to KrF or ArF excimer laser light and has a high resolution and is capable of forming a pattern having a rectangular section with no swelling.

Abstract: A resist composition according to the present invention includes at least a base resin, a photoacid generator and a solvent, wherein the photoacid generator comprises a fluorine-containing sulfonic acid salt of the following general formula (4). In the formula, X independently represents a hydrogen atom or a fluorine atom; n represents an integer of 1 to 6; R1 represents a hydrogen atom, or an alkyl, alkenyl, oxoalkyl, aryl or aralkyl group; any of hydrogen atoms on carbons in R1 may be substituted with a substituent; R2 represents RAO or RBRCN; and A represents a divalent group. This fluorine-containing sulfonic acid salt can serve as a photoacid generator having high solubility in a resist solvent and thus can suitably be used for a resist composition such that the resist composition shows high resolution, wide DOF, small LER and high sensitivity to form a good pattern shape in lithographic processes.

Abstract: According to the present invention, there is provided a sulfonate resin having a repeating unit of the following general formula (3): where X each independently represents a hydrogen atom or a fluorine atom; n represents an integer of 1 to 10; R1 represents a hydrogen atom, a halogen atom, a C1-C3 alkyl group or a C1-C3 fluorine-containing alkyl group; R2 represents either RAO or RBRCN; and M+ represents a monovalent cation. The sulfonate resin has an onium sulfonate incorporated in a side chain thereof with an anion moiety of the sulfonate salt fixed to the resin and can suitably be used as a resist resin having a high solubility in propylene glycol monomethyl ether acetate.

Abstract: A sulfonic acid onium salt represented by the following formula (1) can be used as a superior radiosensitive acid generator for resist compositions. It is possible to form a good pattern by using a resist composition containing this sulfonic acid onium salt. In formula (1), R1 represents a monovalent organic group, and Q+ represents a sulfonium cation or iodonium cation.

Abstract: According to the present invention, there is provided a fluorine-containing sulfonate resin having a repeating unit of the following general formula (3). In order to prevent deficiency such as roughness after pattern formation or failure in pattern formation, the fluorine-containing sulfonate resin incorporates therein a photoacid generating function and serves as a resist resin in which “a moiety capable of changing its developer solubility by the action of an acid” and “a moiety having a photoacid generating function” are arranged with regularity.

Abstract: According to the present invention, there are provided a fluorine-containing sulfonate salt resin or fluorine-containing sulfonate ester resin having a structure of the following general formula (A) and a fluorine-containing N-sulfonyloxyimide resin having a repeating unit of the general formula (17). It is possible obtain a resist composition using the above resin such that the resist composition can attain high resolution, wide DOF, small LER and high sensitivity and form a good pattern shape.