# Patent

## Title
Photosensitive composition, compound for use in the photosensitive composition and pattern forming method using the photosensitive composition

## Abstract

A photosensitive composition comprising: (A) a compound capable of generating a compound having a specific structure upon irradiation with actinic rays or radiation, a pattern forming method using the photosensitive composition, and a compound capable of generating a compound having a specific structure upon irradiation with actinic rays or radiation.

## Background
This is a continuation of application Ser. No. 11/438,728 filed May 23, 2006. The entire disclosure of the prior application, application Ser. No. 11/438,728, is hereby incorporated by reference.
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a Continuation of application Ser. No. 11/438,728 filed May 23, 2006, which claims priority from Japanese Application No. 2005-149988 filed May 23, 2005. The entire disclosures of the prior applications are hereby incorporated by reference.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photosensitive composition capable of changing its properties by undergoing a reaction upon irradiation with actinic rays or radiation, a compound for use in the photosensitive composition, and a pattern forming method using the photosensitive composition. More specifically, the present invention relates to a photosensitive composition for use in the production process of a semiconductor such as IC, in the production of a circuit substrate of liquid crystal, thermal head or the like, in other photofabrication processes or in the lithographic printing plate or acid-curable composition, and also relates to a compound for use in the photosensitive composition and a pattern forming method using the photosensitive composition.
2. Description of the Related Art
The chemical amplification resist composition is a pattern forming material capable of forming a pattern on a substrate by producing an acid in the exposed area upon irradiation with radiation such as far ultraviolet light and through a reaction using this acid as the catalyst, changing the solubility in a developer between the area irradiated with actinic radiation and the non-irradiated area.
In the case of using a KrF excimer laser as the exposure light source, a resin having small absorption in the region of 248 nm and having a basic skeleton of poly(hydroxystyrene) is predominantly used as the main component, and this is an excellent system capable of forming a good pattern with high sensitivity and high resolution as compared with the conventional naphthoquinonediazide/novolak resin system.
In the case of using a light source of emitting light at a shorter wavelength, for example, in using an ArF excimer laser (193 nm) as the light source, a satisfactory pattern cannot be formed even by the above-described chemical amplification system because the compound having an aromatic group substantially has large absorption in the region of 193 nm.
In order to solve this problem, a resist containing a resin having an alicyclic hydrocarbon structure with high transparency has been developed for use with an ArF excimer laser. As for the alicyclic hydrocarbon structure, a norbornene or adamantane skeleton showing high transparency and high dry etching resistance is used as described in JP-A-2002-131897 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”)), JP-A-2003-149812, JP-T-11-501909 (the term (the term “JP-T” as used herein means a “published Japanese translation of a PCT patent application”), JP-A-2002-268223, JP-A-2003-246786 and JP-A-9-73173. However, the alicyclic structure generally has low polarity, and the reactivity for deprotection in the resin is greatly decreased as compared with that in poly(hydroxystyrene). Therefore, an acid having high acidity is necessary for the image formation and a specific fluoro-organic sulfonic acid is used, for example, in JP-A-2002-131897 and JP-A-2003-149812. Also, a composition containing an acid generator comprising an imide anion capable of generating a high-acidity imide upon irradiation with actinic rays or radiation is described in JP-T-11-501909, JP-A-2002-268223 and JP-A-2003-246786. Furthermore, in JP-A-6-242606, JP-A-11-160861, U.S. Patent Application 2004/0087690A1, a specific organic sulfonic acid is used.
In addition, as for the chemical amplification-type resist composition, a resist composition containing a specific amide compound is described in JP-A-5-181263, WO01-004706, pamphlet and JP-A-11-327145.
However, many points still remain unsatisfied, and improvement is demanded with respect to the pattern profile, line edge roughness and defocus latitude depended on line pitch.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a photosensitive composition improved in the pattern profile, line edge roughness and defocus latitude depended on line pitch and enhanced in the sensitivity and resolution at the exposure with EUV light, a compound for use in the photosensitive composition, and a pattern forming method using the photosensitive composition.
The present invention is as follows.
(1) A photosensitive composition comprising:
(A) a compound capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation:




wherein R1 and R2 each independently represents a monovalent organic group, provided that at least either one of R1 and R2 has a proton acceptor functional group, R1 and R2 may combine to form a ring and the ring formed may have a proton acceptor functional group; and
X1 and X2 each independently represents —CO— or —SO2—.
(2) The photosensitive composition as described in (1) above,
wherein the compound represented by formula (I) is represented by formula (II):




wherein R1 and R3 each independently represents a monovalent organic group, provided that at least either one of R1 and R3 has a proton acceptor functional group, R1 and R3 may combine to form a ring and the ring formed may have a proton acceptor functional group;
X1, X2 and X3 each independently represents —CO— or —SO2—;
A represents a divalent linking group;
B represents a single bond, an oxygen atom or —N(Rx)-;
Rx represents a hydrogen atom or a monovalent organic group;
when B is —N(Rx)-, R3 and Rx may combine to form a ring; and
n represents 0 or 1.
(3) The photosensitive composition as described in (1) or (2) above,
wherein the compound capable of generating a compound represented by formula (I) or (II) upon irradiation with actinic rays or radiation is a sulfonium salt compound of the compound represented by formula (I) or (II) or an iodonium salt compound of the compound represented by formula (I) or (II).
(4) A compound capable of generating a compound represented by formula (I) or (II) upon irradiation with actinic rays or radiation:




wherein R1 and R2 each independently represents a monovalent organic group, provided that at least either one of R1 and R2 has a proton acceptor functional group, R1 and R2 may combine to form a ring and the ring formed may have a proton acceptor functional group; and
X1 and X2 each independently represents —CO— or —SO2—;




wherein R1 and R3 each independently represents a monovalent organic group, provided that at least either one of R1 and R3 has a proton acceptor functional group, R1 and R3 may combine to form a ring and the ring formed may have a proton acceptor functional group;
X1, X2 and X3 each independently represents —CO— or —SO2—;
A represents a divalent linking group;
B represents a single bond, an oxygen atom or —N(Rx)-;
Rx represents a hydrogen atom or a monovalent organic group;
when B is —N(Rx)-, R3 and Rx may combine to form a ring; and
n represents 0 or 1.
(5) A pattern forming method comprising:
forming a photosensitive film from a photosensitive composition as described in any of (1) to (3) above; and
exposing and developing the photosensitive film.
Furthermore, the preferred embodiment includes the following constitutions.
(6) The photosensitive composition as described in any of (1) to (3) above, which further comprises (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation.
(7) The photosensitive composition as described in (6) above,
wherein the compound as the component (B) is a sulfonium salt of fluoro-substituted alkanesulfonic acid, fluorine-substituted benzenesulfonic acid or fluorine-substituted imide acid.
(8) The photosensitive composition as described in any of (1) to (3), (6) and (7) above, which is a positive photosensitive composition and further comprises (C) a resin capable of decomposing under an action of an acid to increase a solubility of the resin (C) in an alkali developer.
(9) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has a fluorine atom in a main or side chain.
(10) The photosensitive composition as described in (9) above,
wherein the resin as the component (C) has a hexafluoroisopropanol structure.
(11) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has a hydroxystyrene structural unit.
(12) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has at least one repeating unit selected from 2-alkyl-2-adamantyl (meth)acrylate and dialkyl(1-adamantyl)methyl (meth)acrylate.
(13) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has a monocyclic or polycyclic alicyclic hydrocarbon structure.
(14) The photosensitive composition as described in (13) above,
wherein the resin as the component (C) has at least one repeating unit selected from 2-alkyl-2-adamantyl (meth)acrylate and dialkyl(1-adamantyl)methyl (meth)acrylate, at least one repeating unit having a lactone structure and at least one repeating unit having a hydroxyl group.
(15) The photosensitive composition as described in (14) above,
wherein the resin as the component (C) further has a repeating unit having a carboxyl group.
(16) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has a silicon atom in a main or side chain.
(17) The photosensitive composition as described in (8) above,
wherein the resin as the component (C) has a repeating unit having a lactone structure.
(18) The photosensitive composition as described in any of (8) to (17) above, which further comprises (D) a dissolution inhibiting compound capable of decomposing under an action of an acid to increase a solubility of the compound (D) in an alkali developer and having a molecular weight of 3,000 or less.
(19) The photosensitive composition as described in any of (1) to (3), (6) and (7) above, which is a positive photosensitive composition and further comprises:
(E) a resin soluble in an alkali developer; and
(D) a dissolution inhibiting compound capable of decomposing under an action of an acid to increase a solubility of the compound (D) in an alkali developer and having a molecular weight of 3,000 or less.
(20) The photosensitive composition as described in any of (1) to (3), (6) and (7) above, which is a negative photosensitive composition and further comprises:
(E) a resin soluble in an alkali developer; and
(F) an acid crosslinking agent capable of crosslinking with the resin soluble in an alkali developer under an action of an acid.
(21) The photosensitive composition as described in any of (1) to (3) and (6) to (20) above, which further comprises at least one of (G) a basic compound and (H) at least one of a fluorine-containing surfactant and a silicon-containing surfactant.
(22) The photosensitive composition as described in (21) above,
wherein the basic compound (G) is a compound having a structure selected from an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure and a pyridine structure, an alkylamine derivative having at least one of a hydroxyl group and an ether bond or an aniline derivative having at least one of a hydroxyl group and an ether bond.



BRIEF DESCRIPTION OF THE DRAWINGS
The FIGURE is a schematic view of the two-beam interference exposure testing apparatus.



DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
In the present invention, when a group (atomic group) is denoted without specifying whether substituted or unsubstituted, the group includes both a group having no substituent and a group having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The positive photosensitive composition, preferably positive resist composition, of the present invention comprises (A) a compound capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (C) a compound capable of decomposing under the action of an acid to increase the solubility in an alkali developer, and, if desired, (D) a dissolution inhibiting compound capable of decomposing under the action of an acid to increase the solubility in an alkali developer and having a molecular weight of 3,000 or less, or comprises (A) a compound capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (E) a resin soluble in an alkali developer, and (D) a dissolution inhibiting compound capable of decomposing under the action of an acid to increase the solubility in an alkali developer and having a molecular weight of 3,000 or less.
The negative photosensitive composition, preferably negative resist composition, of the present invention comprises (A) a compound capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (E) a resin soluble in an alkali developer, and (F) an acid crosslinking agent capable of crosslinking with the alkali developer-soluble resin under the action of an acid.
[1] (A) Compound Capable of Generating a Compound Represented by Formula (I) Upon Irradiation with Actinic Rays or Radiation
The photosensitive composition of the present invention comprises a compound (hereinafter referred to as a “compound (A)”) capable of generating a compound represented by the following formula (I) upon irradiation with actinic rays or radiation.




In formula (I), R1 and R2 each independently represents a monovalent organic group, provided that at least either one of R1 and R2 has a proton acceptor functional group. R1 and R2 may combine to form a ring and the ring formed may have a proton acceptor functional group.
X1 and X2 each independently represents —CO— or —SO2—.
The monovalent organic group as R1 and R2 in formula (I) is preferably a monovalent organic group having a carbon number of 1 to 40, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group.
The alkyl group as R1 and R2, which may have a substituent, is preferably a linear or branched alkyl group having a carbon number of 1 to 30 and may contain an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof include a linear alkyl group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group and n-octadecyl group; and a branched alkyl group such as isopropyl group, isobutyl group, tert-butyl group, neopentyl group and 2-ethylhexyl group.
The cycloalkyl group as R1 and R2, which may have a substituent, is preferably a cycloalkyl group having a carbon number of 3 to 20 and may contain an oxygen atom or a nitrogen atom in the ring. Specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
The aryl group as R1 and R2, which may have a substituent, is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group and a naphthyl group.
The aralkyl group as R1 and R2, which may have a substituent, is preferably an aralkyl group having a carbon number of 7 to 20, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and a naphthylethyl group.
The alkenyl group as R1 and R2, which may have a substituent, includes a group having a double bond at an arbitrary position of the alkyl group described above.
Examples of the substituent which the above-described groups each may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), an aryl group (preferably having a carbon number of 6 to 14), an alkoxy group (preferably having a carbon number of 1 to 10), an acyl group (preferably having a carbon number of 2 to 20), an acyloxy group (preferably having a carbon number of 2 to 10), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20) and an aminoacyl group (preferably having a carbon number of 2 to 10). As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). Examples of the alkyl group having a substituent include a perfluoroalkyl group such as perfluoromethyl group, perfluoroethyl group, perfluoropropyl group and perfluorobutyl group.
Either one monovalent organic group of R1 and R2 has a proton acceptor functional group. The proton acceptor functional group is a group capable of electrostatically interacting with a proton or a functional group having a lone pair of electrons, and examples thereof include a functional group having a microcyclic structure such as cyclic polyether, and a functional group containing a nitrogen atom having a lone pair of electrons less contributing to π-conjugation. Examples of the nitrogen atom having a lone pair of electrons less contributing to π-conjugation include a nitrogen atom having a partial structure represented by either one of the following formulae:




Preferred examples of the partial structure of the proton acceptor functional group include a crown ether structure, an aza-crown ether structure, a tertiary amine structure, a secondary amine structure, a primary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and an aniline structure. The carbon number thereof is preferably from 4 to 30. Examples of the group containing such a structure include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. The alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group are the same as those described above.
Examples of the substituent which the above-described groups each may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having a carbon number of 3 to 10), an aryl group (preferably having a carbon number of 6 to 14), an alkoxy group (preferably having a carbon number of 1 to 10), an acyl group (preferably having a carbon number of 2 to 20), an acyloxy group (preferably having a carbon number of 2 to 10), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20) and an aminoacyl group (preferably having a carbon number of 2 to 20). As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20).
The proton acceptor functional group may be substituted by an organic group having a bond which is breakable by an acid. Examples of the organic group having a bond breakable by an acid include an amide group, an ester group (preferably tertiary alkyloxycarbonyl group), an acetal group (preferably 1-alkyloxy-alkyloxy group), a carbamoyl group and a carbonate group.
When R1 and R2 combine to form a ring and the ring formed has a proton acceptor functional group, examples of the structure therefor include a structure where the organic groups of R1 and R2 are further bonded through an alkylene group, an oxy group or an imino group.
In formula (I), at least either one of X1 and X2 is preferably —SO2—.
The compound represented by formula (I) is preferably represented by the following formula (II):




In formula (II), R1 and R3 each independently represents a monovalent organic group, provided that at least either one of R1 and R3 has a proton acceptor functional group. R1 and R3 may combine to form a ring and the ring formed may have a proton acceptor functional group.
X1, X2 and X3 each independently represents —CO— or —SO2—.
A represents a divalent linking group.
B represents a single bond, an oxygen atom or —N(Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
when B is —N(Rx)-, R3 and Rx may combine to form a ring.
n represents 0 or 1.
R1 has the same meaning as R1 in formula (I).
Examples of the organic group of R3 are the same as those of the organic group of R1 and R2 in formula (I).
The divalent linking group as A is preferably a divalent organic group having a carbon number of 1 to 8 and containing a fluorine atom, and examples thereof include an alkylene group having a carbon number of 1 to 8 and containing a fluorine atom, and a phenylene group having a fluorine atom. The divalent linking group is more preferably an alkylene group having a fluorine atom, and the carbon number thereof is preferably from 2 to 6, more preferably from 2 to 4. The alkylene group may contain a linking group such as oxygen atom and sulfur atom, in the alkylene chain. The alkylene group is preferably an alkylene group where from 30 to 100% by number of the hydrogen atom is replaced by a fluorine atom, more preferably a perfluoroakylene group, still more preferably a perfluoroethylene group, a perfluoropropylene group or a perfluorobutylene group.
The monovalent organic group as Rx is preferably a monovalent organic group having a carbon number of 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group are the same as those described above.
In formula (II), X1, X2 and X3 each is preferably —SO2—.
Specific examples of the compounds represented by formulae (I) and (II) are set forth below, but the present invention is not limited thereto.













The compound capable of generating a compound represented by formula (I) or (II) upon irradiation with actinic rays or radiation is preferably a sulfonium salt compound of the compound represented by formula (I) or (II), or an iodonium salt compound of the compound represented by formula (I) or (II).
The compound capable of generating a compound represented by formula (I) or (II) upon irradiation with actinic rays or radiation is more preferably a compound represented by the following formula (A1) or (A2):




In formula (A1), R201, R202 and R203 each independently represents an organic group.
X− represents an anion of the compound represented by formula (I) or (II).
The carbon number of the organic group as R201, R202 and R203 is generally from 1 to 30, preferably from 1 to 20.
Two members out of R201 to R203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two members out of R201 to R203 include an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R201, R202 and R203 include the corresponding groups in the compounds (A1a), (A1b) and (A1c) described later.
The compound may be a compound having a plurality of structures represented by formula (A1). For example, the compound may be a compound having a structure that at least one of R201 to R203 in the compound represented by formula (A1) is bonded to at least one of R201 to R203 in another compound represented by formula (A1).
The component (A1) is more preferably a compound (A1a), (A1b) or (A1c) described below.
The compound (A1a) is an arylsulfonium compound where at least one of R201 to R203 in formula (A1) is an aryl group, that is, a compound having arylsulfonium as the cation.
In the arylsulfonium compound, R201 to R203 all may be an aryl group or a part of R201 to R203 may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, a diarylcycloalkylsulfonium compound, an aryldialkyl-sulfonium compound, an aryldicycloalkylsulfonium compound and an arylalkylcycloalkylsulfonium compound.
The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by removing one hydrogen atom from a pyrrole), a furan residue (a group formed by removing one hydrogen atom from a furan), a thiophene residue (a group formed by removing one hydrogen atom from a thiophene), an indole residue (a group formed by removing one hydrogen atom from an indole), a benzofuran residue (a group formed by removing one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by removing one hydrogen atom from a benzothiophene). In the case where the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be the same of different.
The alkyl group which is present, if desired, in the arylsulfonium compound is preferably a linear or branched alkyl group having a carbon number of 1 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.
The cycloalkyl group which is present, if desired, in the arylsulfonium compound is preferably a cycloalkyl group having a carbon number of 3 to 15, such as cyclopropyl group, cyclobutyl group and cyclohexyl group.
The aryl group, alkyl group and cycloalkyl group of R201 to R203 each may have, as the substituent, an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 14), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group. The substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 12, a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic alkoxy group having a carbon number of 1 to 12, and most preferably an alkyl group having a carbon number of 1 to 4, or an alkoxy group having a carbon number of 1 to 4. The substituent may be substituted to any one of three members R201 to R203 or may be substituted to all of these three members. In the case where R201 to R203 are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.
The compound (A1b) is described below.
The compound (A1b) is a compound when R201 to R203 in formula (A1) each independently represents an organic group having no aromatic ring. The aromatic ring as used herein includes an aromatic ring having a heteroatom.
The organic group as R201 to R203 having no aromatic ring has a carbon number of generally from 1 to 30, preferably from 1 to 20.
R201 to R203 each independently represents preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, still more preferably a linear or branched 2-oxoalkyl group.
The alkyl group as R201 to R203 may be either linear or branched and is preferably a linear or branched alkyl group having a carbon number of 1 to 20 (e.g., methyl, ethyl, propyl, butyl, pentyl), more preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
The cycloalkyl group as R201 to R203 is preferably a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl), more preferably a 2-oxocycloalkyl group.
The linear or branched 2-oxoalkyl group as R201 to R203 may have a double bond in the chain, and preferred examples thereof include a group having >C═O at the 2-position of the above-described alkyl group.
The 2-oxocycloalkyl group as R201 to R203 may have a double bond in the chain, and preferred examples thereof include a group having >C═O at the 2-position of the above-described cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R201 to R203 is preferably an alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy).
R201 to R203 each may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 5), an alkoxycarbonyl group (for example, an alkoxycarbonyl group having a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.
The compound (A1c) is a compound represented by the following formula (A1c), and this is a compound having an arylacylsulfonium salt structure.




In formula (A1c), R213 represents an aryl group which may have a substituent, and is preferably a phenyl group or a naphthyl group.
Preferred examples of the substituent on R213 include an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group and a carboxy group.
R214 and R215 each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Y201 and Y202 each independently represents an alkyl group, a cycloalkyl group, an aryl group or a vinyl group.
X− represents an anion of the compound represented by formula (I) or (II).
R213 and R214 may combine with each other to form a ring structure, R214 and R215 may combine with each other to form a ring structure, and Y201 and Y202 may combine with each other to form a ring structure. The ring structure formed may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond. Examples of the group formed by combining each pair of R213 and R214, R214 and R215, or Y201 and Y202 include a butylene group and a pentylene group.
The alkyl group as R214, R215, Y201 and Y202 is preferably a linear or branched alkyl group having a carbon number of 1 to 20. The alkyl group as Y201 and Y202 is more preferably a 2-oxoalkyl group having >C═O at the 2-position of the alkyl group, an alkoxycarbonylalkyl group (preferably with the alkoxy group having a carbon number of 2 to 20), or a carboxyalkyl group.
The cycloalkyl group as R214, R215, Y201 and Y202 is preferably a cycloalkyl group having a carbon number of 3 to 20.
The aryl group as Y201 and Y202 is preferably a phenyl group or a naphthyl group.
Y201 and Y202 each is preferably an alkyl group having a carbon number of 4 or more, more preferably from 4 to 6, still more preferably from 4 to 12.
At least either one of R214 and R215 is preferably an alkyl group, and more preferably, R214 and R215 both are an alkyl group.
In formula (A2), R204 and R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
X− represents an anion of the compound represented by formula (I) or (II).
The aryl group of R204 and R205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R204 and R205 may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by removing one hydrogen atom from a pyrrole), a furan residue (a group formed by removing one hydrogen atom from a furan), a thiophene residue (a group formed by removing one hydrogen atom from a thiophene), an indole residue (a group formed by removing one hydrogen atom from an indole), a benzofuran residue (a group formed by removing one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by removing one hydrogen atom from a benzothiophene).
The alkyl group as R204 and R205 may be either linear or branched and is preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl).
The cycloalkyl group as R204 and R205 is preferably a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).
R204 and R205 each may have a substituent, and examples of the substituent which R204 and R205 each may have include an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 15), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group and a phenylthio group.
The compound (A) is preferably a compound represented by formula (A1), more preferably a compound represented by any one of formulae (A1a) to (A1e).
Specific examples of the compound (A) are set forth below, but the present invention is not limited thereto.


































The content of the compound (A) in the photosensitive composition of the present invention is preferably from 0.1 to 20 mass %, more preferably from 0.1 to 10 mass %, based on the solid content of the composition. (In this specification, mass ratio is equal to weight ratio.)
The compound (A) is a novel compound.
The compound (A) can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, this compound may be obtained by a method of selectively reacting one sulfonyl halide moiety of a bis-sulfonyl halide compound with an amine, alcohol or the like containing a partial structure represented by formula (I) to form a sulfonamide bond or a sulfonic acid ester bond, and then hydrolyzing the other sulfonyl halide moiety, or a method of ring-opening a cyclic sulfonic anhydride with an amine or alcohol containing a partial structure represented by formula (I). The amine or alcohol containing a partial structure represented by formula (I) can be synthesized by reacting an amine or alcohol with an anhydride (e.g., (R′O2C)2O, R′O2CCl) or an acid chloride compound under basic condition.
[2] (B) Compound Capable of Generating an Acid Upon Irradiation with Actinic Rays or Radiation
The photosensitive composition of the present invention preferably comprises a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter sometimes referred to as an “acid generator”).
The acid generator which can be used may be appropriately selected from a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photo-decoloring agent for coloring matters, a photo-discoloring agent, a known compound capable of generating an acid upon irradiation with actinic rays or radiation, which is used for microresist and the like, and a mixture thereof.
Examples thereof include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imidosulfonate, oxime sulfonate, diazodisulfone, disulfone and o-nitrobenzyl sulfonate.
Also, a compound where the above-described group or compound capable of generating an acid upon irradiation with actinic rays or radiation is introduced into the polymer main or side chain, such as compounds described in U.S. Pat. No. 3,849,137, German Patent 3,914,407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853 and JP-A-63-146029, may be used.
Furthermore, a compound capable of generating an acid by the effect of light described, for example, in U.S. Pat. No. 3,779,778 and European Patent 126,712 may also be used.
Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, preferred are the compounds represented by the following formulae (ZI), (ZII) and (ZIII):




In formula (ZI), R201, R202 and R203 each independently represents an organic group.
The number of carbons in the organic group as R201, R202 and R203 is generally from 1 to 30, preferably from 1 to 20.
Two members out of R201 to R203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two members out of R201 to R203 include an alkylene group (e.g., butylene, pentylene).
Z− represents a non-nucleophilic anion.
Examples of the non-nucleophilic anion as Z− include sulfonate anion, carboxylate anion, sulfonylimide anion, bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methyl anion.
The non-nucleophilic anion is an anion having an extremely low ability of causing a nucleophilic reaction and this anion can suppress the decomposition in aging due to intramolecular nucleophilic reaction. By this anion, the aging stability of the resist is enhanced.
Examples of the sulfonate anion include aliphatic sulfonate anion, aromatic sulfonate anion and camphorsulfonate anion.
Examples of the carboxylate anion include aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion.
The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group but is preferably an alkyl group having a carbon number of 1 to 30 or a cycloalkyl group having a carbon number of 3 to 30, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group and a boronyl group.
The aromatic group in the aromatic sulfonate anion is preferably an aryl group having a carbon number of 6 to 14, and examples thereof include a phenyl group, a tolyl group and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion each may have a substituent. Examples of the substituent for the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include a nitro group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 5), a cycloalkyl group (preferably having a carbon number of 3 to 15), an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), an acyl group (preferably having a carbon number of 2 to 12) and an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 7). As for the aryl group or ring structure in each group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.
Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.
The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having a carbon number of 6 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylmethyl group.
The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion each may have a substituent. Examples of the substituent for the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group and alkylthio group as in the aromatic sulfonate anion.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methyl anion is preferably an alkyl group having a carbon number of 1 to 5, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group and a neopentyl group. Examples of the substituent for such an alkyl group include a halogen atom, a halogen atom-substituted alkyl group, an alkoxy group and an alkylthio group. Among these, an alkyl group substituted by a fluorine atom is preferred.
Other examples of the non-nucleophilic anion include fluorinated phosphorus, fluorinated boron and fluorinated antimony.
The non-nucleophilic anion of Z− is preferably an aliphatic sulfonate anion with the α-position of sulfonic acid being substituted by a fluorine atom, an aromatic sulfonate anion substituted by a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion with the alkyl group being substituted by a fluorine atom, or a tris(alkylsulfonyl)methide anion with the alkyl group being substituted by a fluorine atom, more preferably a perfluoroaliphatic sulfonate anion having a carbon number of 4 to 8 or a benzenesulfonate anion having a fluorine atom, still more preferably nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, pentafluorobenzene-sulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.
Examples of the organic group as R201, R202 and R203 include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) which are described later.
The compound may be a compound having a plurality of structures represented by formula (Z1), for example, may be a compound having a structure that at least one of R201 to R203 in the compound represented by formula (Z1) is bonded to at least one of R201 to R203 in another compound represented by formula (Z1).
The component (Z1) is more preferably a compound (ZI-1), (ZI-2) or (ZI-3) described below.
The compound (ZI-1) is an arylsulfonium compound where at least one of R201 to R203 in formula (Z1) is an aryl group, that is, a compound having an arylsulfonium as the cation.
In the arylsulfonium compound, R201 to R203 all may be an aryl group or a part of R201 to R203 may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkyl-sulfonium compound and an aryldicycloalkylsulfonium compound.
The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by removing one hydrogen atom from a pyrrole), a furan residue (a group formed by removing one hydrogen atom from a furan), a thiophene residue (a group formed by removing one hydrogen atom from a thiophene), an indole residue (a group formed by removing one hydrogen atom from an indole), a benzofuran residue (a group formed by removing one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by removing one hydrogen atom from a benzothiophene). In the case where the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be the same of different.
The alkyl group or cycloalkyl group which is present, if desired, in the arylsulfonium compound is preferably a linear or branched alkyl group having a carbon number of 1 to 15 or a cycloalkyl group having a carbon number of 3 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.
The aryl group, alkyl group and cycloalkyl group of R201 to R203 each may have, as the substituent, an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 14), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group. The substituent is preferably a linear or branched alkyl group having a carbon number of 1 to 12, a cycloalkyl group having a carbon number of 3 to 12, or a linear, branched or cyclic alkoxy group having a carbon number of 1 to 12, more preferably an alkyl group having a carbon number of 1 to 4, or an alkoxy group having a carbon number of 1 to 4. The substituent may be substituted to any one of three members R201 to R203 or may be substituted to all of these three members. In the case where R201 to R203 are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.
The compound (ZI-2) is described below.
The compound (ZI-2) is a compound where R201 to R203 in formula (ZI) each independently represents an organic group having no aromatic ring. The aromatic ring as used herein includes an aromatic ring containing a heteroatom.
The organic group as R201 to R203 having no aromatic ring has a carbon number of generally 1 to 30, preferably from 1 to 20.
R201 to R203 each independently represents preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, still preferably a linear or branched 2-oxoalkyl group.
The alkyl group and cycloalkyl group of R201 to R203 are preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl). The alkyl group is more preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group. The cycloalkyl group is more preferably a 2-oxocycloalkyl group.
The 2-oxoalkyl group may be either linear or branched and is preferably a group having >C═O at the 2-position of the above-described alkyl group.
The 2-oxocycloalkyl group is preferably a group having >C═O at the 2-position of the above-described cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkyl group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy).
R201 to R203 each may be further substituted by a halogen atom, an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.
The compound (ZI-3) is a compound represented by the following formula (ZI-3), and this is a compound having a phenacylsulfonium salt structure.




In formula (ZI-3), R1c to R5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R6c and R7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Any two or more members out of R1c to R5c or each pair of R6c and R7c, or Rx and Ry may combine with each other to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond. Examples of the group formed by combining any two or more members out of R1c to R5c or combining each pair of R6c and R7c, or Rx and Ry include a butylene group and a pentylene group.
Zc− represents a non-nucleophilic anion, and examples thereof are the same as those of the non-nucleophilic anion of Z− in formula (ZI).
The alkyl group as R1c to R7c may be either linear or branched and this is, for example, an alkyl group having a carbon number of 1 to 20, preferably a linear or branched alkyl group having a carbon number of 1 to 12 (e.g., methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl). The cycloalkyl group is, for example, a cycloalkyl group having a carbon number of 3 to 8 (e.g., cyclopentyl, cyclohexyl).
The alkoxy group as R1c to R5c may be linear, branched or cyclic and this is, for example, an alkoxy group having a carbon number of 1 to 10, preferably a linear or branched alkoxy group having a carbon number of 1 to 5 (e.g., methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy) or a cyclic alkoxy group having a carbon number of 3 to 8 (e.g., cyclopentyloxy, cyclohexyloxy).
A compound where any one of R1c to R5c is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group is preferred, and a compound where the sum of carbon numbers of R1c to R5c is from 2 to 15 is more preferred. In this case, the solubility in a solvent is more enhanced and the generation of particles during storage can be suppressed.
Examples of the alkyl group and cycloalkyl group as Rx and Ry include the same alkyl group and cycloalkyl group as in R1c to R7c. Among these, a 2-oxoalkyl group, a 2-oxocycloalkyl group and an alkoxycarbonylmethyl group are preferred.
Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having >C═O at the 2-position of the alkyl group or cycloalkyl group as R1c to R7c.
Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy group as in R1c to R5c.
Rx and Ry each is preferably an alkyl or cycloalkyl group having a carbon number of 4 or more, more preferably 6 or more, still more preferably 8 or more.
In formulae (ZII) and (ZIII), R204 to R207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group of R204 to R207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R204 and R207 may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by removing one hydrogen atom from a pyrrole), a furan residue (a group formed by removing one hydrogen atom from a furan), a thiophene residue (a group formed by removing one hydrogen atom from a thiophene), an indole residue (a group formed by removing one hydrogen atom from an indole), a benzofuran residue (a group formed by removing one hydrogen atom from a benzofuran) and a benzothiophene residue (a group formed by removing one hydrogen atom from a benzothiophene).
The alkyl group and cycloalkyl group in R204 to R207 are preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) and a cycloalkyl group having a carbon number of 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).
The aryl group, alkyl group and cycloalkyl group of R204 to R207 each may have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R204 to R207 each may have include an alkyl group (for example, an alkyl group having a carbon number of 1 to 15), a cycloalkyl group (for example, a cycloalkyl group having a carbon number of 3 to 15), an aryl group (for example, an aryl group having a carbon number of 6 to 15), an alkoxy group (for example, an alkoxy group having a carbon number of 1 to 15), a halogen atom, a hydroxyl group and a phenylthio group.
Z− represents a non-nucleophilic anion, and examples thereof are the same as those of the non-nucleophilic anion of Z− in formula (ZI).
Other examples of the compound capable of generating an acid upon irradiation with actinic rays or radiation, which can be used, include the compounds represented by the following formulae (ZIV), (ZV) and (ZVI):




In formulae (ZIV) to (ZVI), Ar3 and Ar4 each independently represents an aryl group.
R206, R207 and R208 each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, more preferred are the compounds represented by formulae (ZI) to (ZIII).
The compound capable of generating an acid upon irradiation with actinic rays or radiation is preferably a compound capable of generating an acid having one sulfonic acid group or imide group, more preferably a compound capable of generating a monovalent perfluoroalkanesulfonic acid, a compound capable of generating a monovalent aromatic sulfonic acid substituted by a fluorine atom or a fluorine atom-containing group, or a compound capable of generating a monovalent imide acid substituted by a fluorine atom or a fluorine atom-containing group. In particular, the usable acid generator preferably generates a fluoro-substituted alkanesulfonic acid, a fluoro-substituted benzenesulfonic acid or a fluoro-substituted imide acid, each having a pKa of −1 or less, and in this case, the sensitivity can be enhanced.
Among the compounds capable of generating an acid upon irradiation with actinic rays or radiation, particularly preferred compounds are set forth below.
















One acid generator may be used alone or two or more kinds of acid generators may be used in combination.
The content of the acid generator in the photosensitive composition is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, still more preferably from 1 to 7 mass %, based on the entire solid content of the photosensitive composition.
[3] (C) Resin Capable of Decomposing Under the Action of an Acid to Increase the Solubility in an Alkali Developer (Hereinafter Sometimes Referred to as a “Component (C)”)
The resin capable of decomposing under the action of an acid to increase the solubility in an alkali developer, which is used in the positive photosensitive composition of the present invention, is a resin having a group capable of decomposing under the action of an acid (hereinafter sometimes referred to as an “acid-decomposable group”), in ether one or both of the main chain and the side chain thereof. Of these, a resin having an acid-decomposable group in the side chain is preferred.
The group capable of decomposing under the action of an acid is preferably a group resulting from replacement of the hydrogen atom of a —COOH or —OH group by a group which splits off by the effect of an acid.
In the present invention, the acid-decomposable group is preferably an acetal group or a tertiary ester group.
In the case where the group capable of decomposing under the action of an acid is bonded as a side chain, the mother resin is an alkali-soluble resin having an —OH or —COOH group in the side chain. Examples thereof include an alkali-soluble resin described later.
The alkali dissolution rate of such an alkali-soluble resin is preferably 170 A/sec or more, more preferably 330 A/sec or more (A is angstrom), as measured (at 23° C.) in 0.261N tetramethylammonium hydroxide (TMAH).
From this standpoint, the alkali-soluble resin is preferably an alkali-soluble resin having a hydroxystyrene structural unit, such as o-, m- or p-poly(hydroxystyrene) or a copolymer thereof, hydrogenated poly(hydroxystyrene), halogen- or alkyl-substituted poly(hydroxystyrene), partially O-alkylated or O-acylated poly(hydroxystyrene), styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin; or an alkali-soluble resin containing a repeating unit having a carboxyl group, such as (meth)acrylic acid and norbornene carboxylic acid.
Preferred examples of the repeating unit having an acid-decomposable group for use in the present invention include tert-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene and tertiary alkyl (meth)acrylate. Among these, 2-alkyl-2-adamantyl (meth)acrylate and dialkyl(1-adamantyl)methyl (meth)acrylate are more preferred.
The component (C) for use in the present invention can be obtained by reacting an acid-decomposable group precursor with an alkali-soluble resin or copolymerizing an acid-decomposable group-bonded alkali-soluble resin monomer with various monomers, and this is disclosed in European Patent 254853, JP-A-2-25850, JP-A-3-223860 and JP-A-4-251259.
In the case of irradiating the positive photosensitive composition of the present invention with KrF excimer laser light, electron beam, X-ray or high-energy light at a wavelength of 50 nm or less (e.g., EUV), the resin as the component (C) preferably has a hydroxystyrene repeating unit, and the resin is more preferably a copolymer of hydroxystyrene/hydroxystyrene protected by an acid-decomposable group, or hydroxystyrene/tertiary alkyl methacrylate.
Specific examples of the component (C) for use in the present invention are set forth below, but the present invention is not limited thereto.
















In these specific examples, “tBu” indicates a tert-butyl group.
The content of the group capable of decomposing under the action of an acid is expressed by B/(B+S) using the number (B) of acid-decomposable groups in the resin and the number (S) of alkali-soluble groups not protected by a group which splits off by the effect of an acid. The content is preferably from 0.01 to 0.7, more preferably from 0.05 to 0.50, still more preferably from 0.05 to 0.40.
In the case of irradiating the positive photosensitive composition of the present invention with ArF excimer laser light, the resin as the component (C) is preferably a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and undergoing decomposition by the effect of an acid to increase the solubility in an alkali developer.
The resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and undergoing decomposition by the effect of an acid to increase the solubility in an alkali developer (hereinafter sometimes referred to as an “alicyclic hydrocarbon-based acid-decomposable resin”) is preferably a resin containing at least one repeating unit selected from the group consisting of a repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of the following formulae (pI) to (pV), and a repeating unit represented by the following formula (II-AB):




In formulae (pI) to (pV), R11 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group. Z represents an atomic group necessary for forming a cycloalkyl group together with the carbon atom.
R12 to R16 each independently represents a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R12 to R14 or either one of R15 and R16 represents a cycloalkyl group.
R17 to R21 each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R17 to R21 represents a cycloalkyl group and that either one of R19 and R21 represents a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group.
R22 to R25 each independently represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or a cycloalkyl group, provided that at least one of R22 to R25 represents a cycloalkyl group. R23 and R24 may combine with each other to form a ring.




In formula (II-AB), R11′ and R12′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z′ represents an atomic group for forming an alicyclic structure, containing two bonded carbon atoms (C—C).
Formula (II-AB) is preferably the following formula (II-AB1) or (II-AB2).




In formulae (II-AB1) and (II-AB2), R13′ to R16′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —COOH, —COOR5, a group capable of decomposing under the action of an acid, —C(═O)—X-A′—R17′, an alkyl group or a cycloalkyl group, and at least two members out of R13′ to R16′ may combine to form a ring.
R5 represents an alkyl group, a cycloalkyl group or a group having a lactone structure.
X represents an oxygen atom, a sulfur atom, —NH—, —NHSO2— or —NHSO2NH—.
A′ represents a single bond or a divalent linking group.
R17′ represents —COOH, —COOR5, —CN, a hydroxyl group, an alkoxy group, —CO—NH—R6, —CO—NH—SO2—R6 or a group having a lactone structure.
R6 represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.
In formulae (pI) to (pV), the alkyl group of R12 to R25 is a linear or branched alkyl group having from 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.
The cycloalkyl group of R11 to R25 and the cycloalkyl group formed by Z together with the carbon atom may be monocyclic or polycyclic. Specific examples thereof include a group having a monocyclo, bicyclo, tricyclo or tetracyclo structure or the like with a carbon number of 5 or more. The carbon number thereof is preferably from 6 to 30, more preferably from 7 to 25. These cycloalkyl groups each may have a substituent.
Preferred examples of the cycloalkyl group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group. Among these, more preferred are an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group and a tricyclodecanyl group.
These alkyl group and cycloalkyl group each may further have a substituent. Examples of the substituent which the alkyl group and cycloalkyl group may further have include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group and an alkoxycarbonyl group (having a carbon number of 2 to 6). These alkyl group, alkoxy group, alkoxycarbonyl group and the like each may further have a substituent. Examples of the substituent which the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom and an alkoxy group.
The structures represented by formulae (pI) to (pV) each can be used for the protection of an alkali-soluble group in the resin. Examples of the alkali-soluble group include various groups known in this technical field.
Specific examples thereof include a structure where the hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group or a thiol group is replaced by the structure represented by any one of formulae (pI) to (pV). Among these, preferred is a structure where the hydrogen atom of a carboxylic acid group or a sulfonic acid group is replaced by the structure represented by any one of formulae (pI) to (pV).
The repeating unit having an alkali-soluble group protected by the structure represented by any one of formulae (pI) to (pV) is preferably a repeating unit represented by the following formula (pA):




In formula (pA), R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having a carbon number of 1 to 4, and a plurality of R's may be the same or different.
A represents a single bond, or sole group or a combination of two or more groups, selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group and a urea group. A is preferably a single bond.
Rp1 represents any one group of formulae (pI) to (pV).
The repeating unit represented by formula (pA) is most preferably a repeating unit comprising a 2-alkyl-2-adamantyl (meth)acrylate or a dialkyl(1-adamantyl)methyl (meth)acrylate.
Specific examples of the repeating unit represented by formula (pA) are set forth below.










In the formulae above, Rx represents H, CH3, CF3 or CH2OH, and Rxa and Rxb each independently represents an alkyl group having a carbon number of 1 to 4.
Examples of the halogen atom of R11′ and R12′ in formula (II-AB) include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.
The alkyl group of R11′ and R12′ is preferably a linear or branched alkyl group having a carbon number of 1 to 10, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a linear or branched butyl, pentyl, hexyl or heptyl group.
The atomic group of Z′ for forming an alicyclic structure is an atomic group of forming, in the resin, an alicyclic hydrocarbon repeating unit which may have a substituent, and in particular, an atomic group of forming a crosslinked alicyclic structure to form a crosslinked alicyclic hydrocarbon repeating unit is preferred.
Examples of the skeleton of the alicyclic hydrocarbon formed are the same as those of the cycloalkyl group of R12 to R25 in formulae (pI) to (pVI).
The alicyclic hydrocarbon skeleton may have a substituent, and examples of the substituent include R13′ to R16′ in formulae (II-AB1) and (II-AB2).
In the alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention, the group capable of decomposing under the action of an acid may be contained in at least one repeating unit out of the repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pV), the repeating unit represented by formula (II-AB), and the repeating unit comprising a copolymerization component described later.
Various substituents R13′ to R16′ in formulae (II-AB1) and (II-AB2) may work out to a substituent of an atomic group for forming an alicyclic structure in formula (II-AB) or an atomic group Z for forming a crosslinked alicyclic structure.
Specific examples of the repeating units represented by formulae (II-AB1) and (II-AB2) are set forth below, but the present invention is not limited thereto.
















The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention preferably has a repeating unit having a lactone group. As for the lactone group, any group may be used as long as it has a lactone structure, but a group having a 5-, 6- or 7-membered ring lactone structure is preferred. The 5-, 6- or 7-membered ring lactone structure is preferably condensed with another ring structure in the form of forming a bicyclo or spiro structure. The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention more preferably has a repeating unit containing a group having a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-16). The group having a lactone structure may be bonded directly to the main chain. Among these lactone structures, (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13) and (LC1-14) are preferred. By virtue of using a specific lactone structure, the line edge roughness and the development defect are improved.







The lactone structure moiety may or may not have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having a carbon number of 1 to 8, a cycloalkyl group having a carbon number of 4 to 7, an alkoxy group having a carbon number of 1 to 8, an alkoxycarbonyl group having a carbon number of 1 to 8, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is an integer of 2 or more, the plurality of Rb2's may be the same or different and also, Rb2's may combine with each other to form a ring.
Examples of the repeating unit containing a group having a lactone structure represented by any one of formulae (LC1-1) to (LC1-16) include a repeating unit where at least one of R13′ to R16′ in formula (II-AB1) or (II-AB2) has a group represented by any one of formulae (LC1-1) to (LC1-16) (for example, R5 of —COOR5 is a group represented by any one of formulae (LC1-1) to (LC1-16)), and a repeating unit represented by the following formula (AI):




In formula (AI), Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having a carbon number of 1 to 4.
Examples of the alkyl group of Rb0 include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. The alkyl group of Rb0 may have a substituent. Preferred examples of the substituent which the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.
Ab represents an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group comprising a combination thereof, preferably a single bond or a linking group represented by -Ab1-CO2—.
Ab1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl residue, an adamantyl residue or a norbornyl residue.
V represents a group represented by any one of formulae (LC1-1) to (LC1-16).
The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone or a mixture of a plurality of optical isomers may be used. In the case of mainly using one optical isomer, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
Specific examples of the repeating unit containing a group having a lactone structure are set forth below, but the present invention is not limited thereto.
(In formulae, Rx is H, CH3, CH2OH or CF3.)







(In formulae, Rx is H, CH3, CH2OH or CF3.)










(In formulae, Rx is H, CH3, CH2OH or CF3.)







The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention preferably contains a repeating unit having an alicyclic hydrocarbon structure substituted by a polar group. By virtue of this repeating unit, the adhesion to substrate and the affinity for developer are enhanced. The polar group is preferably a hydroxyl group or a cyano group.
Examples of the alicyclic hydrocarbon structure substituted by a polar group include a structure represented by the following formula (VIIa) or (VIIb):




In formula (VIIa), R2c to R4c each independently represents a hydrogen atom, a hydroxyl group or a cyano group, provided that at least one of R2c to R4c represents a hydroxyl group or a cyano group. A structure where one or two member out of R2c to R4c is a hydroxyl group with the remaining being a hydrogen atom is preferred, and a structure where two members out of R2c to R4c are a hydroxyl group with the remaining being a hydrogen atom is more preferred.
The group represented by formula (VIIa) is preferably a dihydroxy form or a monohydroxy form, more preferably a dihydroxy form.
Examples of the repeating unit having a group represented by formula (VIIa) or (VIIb) include a repeating unit where at least one of R13′ to R16′ in formula (II-AB1) or (II-AB2) has a group represented by formula (VIIa) or (VIIb) (for example, R5 of —COOR5 is a group represented by formula (VIIa) or (VIIb)), and a repeating unit represented by the following formula (AIIa) or (AIIb):




In formulae (AIIa) and (AIIb), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R2c to R4c have the same meanings as R2 to R4c in formula (VIIa).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure substituted by a polar group, represented by formula (AIIa) or (AIIb), are set forth below, but the present invention is not limited thereto.




The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention may contain a repeating unit represented by the following formula (VIII):




In formula (VIII), Z2 represents —O— or —N(R41)—. R41 represents a hydrogen atom, a hydroxyl group, an alkyl group or —OSO2—R42. R42 represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R41 and R42 may be substituted by a halogen atom (preferably fluorine atom) or the like.
Specific examples of the repeating unit represented by formula (VIII) are set forth below, but the present invention is not limited thereto.




The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention preferably contains a repeating unit having an alkali-soluble group, more preferably a repeating unit having a carboxyl group. By virtue of containing such a repeating unit, the resolution increases in usage of forming contact holes. As for the repeating unit having a carboxyl group, a repeating unit where a carboxyl group is directly bonded to the resin main chain, such as repeating unit by an acrylic acid or a methacrylic acid, and a repeating unit where a carboxyl group is bonded to the resin main chain through a linking group, both are preferred. The linking group may have a monocyclic or polycyclic hydrocarbon structure. An acrylic acid and a methacrylic acid are most preferred.
The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention may contain a repeating unit having from 1 to 3 groups represented by the following formula (F1). By virtue of this repeating unit, the line edge roughness performance is enhanced.




In formula (F1), R50 to R55 each independently represents a hydrogen atom, a fluorine atom or an alkyl group, provided that at least one of R50 to R55 is a fluorine atom or an alkyl group with at least one hydrogen atom being substituted by a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protective group, an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group).
The alkyl group of R50 to R55 may be substituted by a halogen atom (e.g., fluorine), a cyano group or the like, and is preferably an alkyl group having a carbon number of 1 to 3, such as methyl group and trifluoromethyl group.
It is preferred that R50 to R55 all are a fluorine atom.
The organic group represented by Rx is preferably an acid-decomposable group or an alkyl, cycloalkyl, acyl, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylmethyl, alkoxymethyl or 1-alkoxyethyl group which may have a substituent.
The repeating unit having a group represented by formula (F1) is preferably a repeating unit represented by the following formula (F2):




In formula (F2), Rx represents a hydrogen atom, a halogen atom or an alkyl group having a carbon number of 1 to 4. Preferred examples of the substituent which the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group, preferably a single bond.
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group, preferably a single bond or a methylene group.
F1 represents a group represented by formula (F1).
p1 represents a number of 1 to 3.
The cyclic hydrocarbon group in Fb is preferably a cyclopentyl group, a cyclohexyl group or a norbornyl group.
Specific examples of the repeating unit having a structure of formula (F1) are set forth below.




The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention may contain, in addition to the above-described repeating units, various repeating structural units for the purpose of controlling the dry etching resistance, suitability for standard developer, adhesion to substrate, resist profile and properties generally required of the resist, such as resolving power, heat resistance and sensitivity.
Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the monomers described below.
By virtue of such a repeating structural unit, the performance required of the alicyclic hydrocarbon-based acid-decomposable resin, particularly,
(1) solubility in the coating solvent,
(2) film-forming property (glass transition point),
(3) alkali developability,
(4) film loss (selection of hydrophilic, hydrophobic or alkali-soluble group),
(5) adhesion of unexposed area to substrate,
(6) dry etching resistance
and the like, can be subtly controlled.
Examples of such a monomer include a compound having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers and vinyl esters.
Other than these, an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the above-described various repeating structural units may be copolymerized.
In the alicyclic hydrocarbon-based acid-decomposable resin, the molar ratio of respective repeating structural units contained is appropriately determined to control the dry etching resistance of resist, suitability for standard developer, adhesion to substrate, resist profile and performances generally required of the resist, such as resolving power, heat resistance and sensitivity.
The preferred embodiment of the alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention includes the followings:
(1) a resin containing a repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pV) (side chain type), preferably containing a repeating unit by a (meth)acrylate having a structure represented by any one of formulae (pI) to (pV), and
(2) a resin containing a repeating unit represented by formula (II-AB) (main chain type).
The embodiment of (2) further includes:
(3) a resin having a repeating unit represented by formula (II-AB), a maleic anhydride derivative structure and a (meth)acrylate structure (hybrid type).
In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably from 10 to 60 mol %, more preferably from 20 to 50 mol %, still more preferably from 25 to 40 mol %, based on all repeating structural units.
In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pV) is preferably from 25 to 70 mol %, more preferably from 35 to 65 mol %, still more preferably from 40 to 60 mol %, based on all repeating structural units.
In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by formula (II-AB) is preferably from 10 to 60 mol %, more preferably from 15 to 55 mol %, still more preferably from 20 to 50 mol %, based on all repeating structural units.
In the resin, the content of the repeating structural unit based on the monomer as the further copolymerization component can also be appropriately selected according to the desired resist performance, but the content thereof is preferably 99 mol % or less, more preferably 90 mol % or less, still more preferably 80 mol % or less, based on the total molar number of the repeating structural unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pV) and the repeating unit represented by formula (II-AB).
When the composition of the present invention is used for exposure with ArF, the resin preferably has no aromatic group in view of transparency to ArF light.
The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention is preferably a resin where all repeating units comprise a (meth)acrylate repeating unit. In this case, the repeating units may be all a methacrylate, all an acrylate, or a mixture of methacrylate/acrylate, but the content of the acrylate repeating unit is preferably 50 mol % or less based on all repeating units.
The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention is more preferably a ternary copolymerization polymer comprising from 25 to 50% of the repeating unit having an alicyclic hydrocarbon-containing partial structure represented by any one of formulae (pI) to (pV), from 25 to 50% of the repeating unit having a lactone structure and from 5 to 30% of the repeating unit having an alicyclic hydrocarbon structure substituted by a polar group, or a quaternary copolymerization polymer additionally comprising from 5 to 20% of the repeating unit having a carboxyl group or a structure represented by formula (F1).
The alicyclic hydrocarbon-based acid-decomposable resin for use in the present invention can be synthesized by an ordinary method (for example, radical polymerization). Examples of the synthesis method in general include a batch polymerization method of dissolving the monomer species and an initiator in a solvent and heating the solution, thereby effecting the polymerization, and a dropping polymerization method of adding dropwise a solution containing monomer species and an initiator to a heated solvent over 1 to 10 hours. A dropping polymerization method is preferred. Examples of the reaction solvent include tetrahydrofuran, 1,4-dioxane, ethers (e.g., diisopropyl ether), ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone), an ester solvent (e.g., ethyl acetate), an amide solvent (e.g., dimethylformamide, diethylacetamide), and a solvent capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and cyclohexanone which are described later. The polymerization is preferably performed by using the same solvent as the solvent used in the photosensitive composition of the present invention. By the use of this solvent, generation of particles during storage can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen and argon. The polymerization is started by using a commercially available radical initiator (e.g., azo-based initiator, peroxide). The radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl 2,2′-azobis(2-methyl-propionate). The initiator is added additionally or in parts, if desired. After the completion of reaction, the reactant is charged into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is from 5 to 50 mass %, preferably from 10 to 30 mass %, and the reaction temperature is usually from 10 to 150° C., preferably from 30 to 120° C., more preferably from 50 to 100° C.
In the case of using the composition of the present invention for the upper resist of a multilayer resist, the resin of the component (C) preferably has a silicon atom.
As for the resin having a silicon atom and capable of decomposing under the action of an acid to increase the solubility in an alkali developer, a resin having a silicon atom at least in either the main chain or the side chain can be used. Examples of the resin having a siloxane structure in the side chain of the resin include a copolymer of an olefin-based monomer having a silicon atom in the side chain and a (meth)acrylic acid-based monomer having a maleic anhydride and an acid-decomposable group in the side chain.
The resin having a silicon atom is preferably a resin having a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure, more preferably a resin containing a repeating unit having a structure represented by any one of the following formulae (SS-1) to (SS-4), still more preferably a resin containing a (meth)acrylic acid ester-based, vinyl-based or acryl-based repeating unit having a structure represented by any one of formulae (SS-1) to (SS-4).




In formulae (SS-1) to (SS-4), Rs represents an alkyl group having a carbon number of 1 to 5, preferably a methyl group or an ethyl group.
The resin having a silicon atom is preferably a resin containing two or more different repeating units having a silicon atom, more preferably a resin containing both (Sa) a repeating unit having from 1 to 4 silicon atoms and (Sb) a repeating unit having from 5 to 10 silicon atoms, still more preferably a resin containing at least one repeating unit having a structure represented by any one of formulae (SS-1) to (SS-3) and a repeating unit having a structure represented by formula (SS-4).
In the case of irradiating the positive photosensitive composition of the present invention with F2 excimer laser light, the resin of the component (C) is preferably a resin having a structure that a fluorine atom is substituted to the main chain and/or the side chain of the polymer skeleton, and being capable of decomposing under the action of an acid to increase the solubility in an alkali developer (hereinafter sometimes referred to as a “fluorine-based acid-decomposable resin”), more preferably a resin containing a hydroxyl group with the 1-position being substituted by a fluorine atom or a fluoroalkyl group or containing a group where the hydroxyl group with the 1-position being substituted by a fluorine atom or a fluoroalkyl group is protected by an acid-decomposable group, and still more preferably a resin having a hexafluoro-2-propanol structure or a structure that the hydroxyl group of hexafluoro-2-propanol is protected by an acid-decomposable group. By virtue of introducing a fluorine atom, the transparency to far ultraviolet light, particularly F2 (157 nm) light, can be enhanced.
Preferred examples of the fluorine-based acid-decomposable resin include a resin having at least one repeating unit represented by the following formulae (FA) to (FG):




In these formulae, R100 to R103 each represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R104 and R106 each is a hydrogen atom, a fluorine atom or an alkyl group, and at least either one of R104 and R106 is a fluorine atom or a fluoroalkyl group. R104 and R106 are preferably both a trifluoromethyl group.
R105 is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or a group capable of decomposing under the action of an acid.
A1 is a single bond, a divalent linking group such as alkylene group, cycloalkylene group, alkenylene group, arylene group, —COO—, —COO— and —CON(R24)—, or a linking group comprising a plurality of members out of these groups. R24 is a hydrogen atom or an alkyl group.
R107 and R108 each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a group capable of decomposing under the action of an acid.
R109 is a hydrogen atom, an alkyl group, a cycloalkyl group or a group capable of decomposing under the action of an acid.
b is 0, 1 or 2.
In formulae (FA) and (FC), R100 and R101 may form a ring through an alkylene group (having a carbon number of 1 to 5) which may be substituted by fluorine.
The repeating units represented by formulae (FA) to (FG) each contains at least one fluorine atom, preferably 3 or more fluorine atoms, per one repeating unit.
In formulae (FA) to (FG), the alkyl group is, for example, an alkyl group having a carbon number of 1 to 8, and specific preferred examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group and an octyl group.
The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type is a cycloalkyl group having a carbon number of 3 to 8, and preferred examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The polycyclic type is a cycloalkyl group having a carbon number of 6 to 20, and preferred examples thereof include an adamantyl group, a norbornyl group, an isoboronyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group and an androstanyl group. In these monocyclic or polycyclic cycloalkyl groups, the carbon atom may be substituted by a heteroatom such as oxygen atom.
The fluoroalkyl group is, for example, a fluoroalkyl group having a carbon number of 1 to 12, and specific preferred examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group and a perfluorododecyl group.
The aryl group is, for example, an aryl group having a carbon number of 6 to 15, and specific preferred examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, an anthryl group and a 9,10-dimethoxyanthryl group.
The alkoxy group is, for example, an alkoxy group having a carbon number of 1 to 8, and specific preferred examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group and an octoxy group.
The acyl group is, for example, an acyl group having a carbon number of 1 to 10, and specific preferred examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group and a benzoyl group.
The alkoxycarbonyl group is preferably a secondary alkoxycarbonyl group, more preferably a tertiary alkoxycarbonyl group, such as i-propoxycarbonyl group, tert-butoxycarbonyl group, tert-amyloxycarbonyl group and 1-methyl-1-cyclohexyloxycarbonyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkylene group is preferably an alkylene group having a carbon number of 1 to 8, such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
The alkenylene group is preferably an alkenylene group having a carbon number of 2 to 6, such as ethenylene group, propenylene group and butenylene group.
The cycloalkylene group is preferably a cycloalkylene group having a carbon number of 5 to 8, such as cyclopentylene group and cyclohexylene group.
The arylene group is preferably an arylene group having a carbon number of 6 to 15, such as phenylene group, tolylene group and naphthylene group.
These groups each may have a substituent, and examples of the substituent include those having an active hydrogen, such as alkyl group, cycloalkyl group, aryl group, amino group, amido group, ureido group, urethane group, hydroxyl group and carboxyl group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine), an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy), a thioether group, an acyl group (e.g., acetyl, propanoyl, benzoyl), an acyloxy group (e.g., acetoxy, propanoyloxy, benzoyloxy), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl), a cyano group and a nitro group.
Here, the alkyl group, cycloalkyl group and aryl group include those described above, and the alkyl group may be further substituted by a fluorine atom or a cycloalkyl group.
Examples of the group capable of decomposing under the action of an acid to show alkali solubility, which is contained in the fluorine-based acid-decomposable resin of the present invention, include —O—C(R36)(R37)(R38), —O—C(R36)(R37)(OR39), —O—COO—C(R36)(R37)(R38), —O—C(R01)(R02)COO—C(R36)(R37)(R38), —COO—C(R36)(R37)(R38) and —COO—C(R36)(R37)(OR39).
R36 to R39 each represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and R01 and R02 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group (e.g., vinyl, allyl, butenyl, cyclohexenyl), an aralkyl group (e.g., benzyl, phenethyl, naphthylmethyl) or an aryl group.
Specific preferred examples include an ether or ester group of a tertiary alkyl group, such as tert-butyl group, tert-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group and 2-(4-methylcyclohexyl)-2-propyl group; an acetal or acetal ester group such as 1-alkoxy-1-ethoxy group and tetrahydropyranyl group; a tert-alkylcarbonate group; and a tert-alkylcarbonylmethoxy group.
Specific examples of the repeating structural units represented by formulae (FA) to (FG) are set forth below, but the present invention is not limited thereto.































The total content of the repeating units represented by formulae (FA) to (FG) is generally from 10 to 80 mol %, preferably from 30 to 70 mol %, more preferably from 35 to 65 mol %, based on all repeating units constituting the resin.
In the fluorine-based acid-decomposable resin, in addition to these repeating structural units, other polymerizable monomers may be copolymerized for the purpose of enhancing the performance of the resist of the present invention.
Examples of the copolymerization monomer which can be used include a compound having one addition-polymerizable unsaturated bond selected from acrylic acid esters other than those described above, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and crotonic acid esters.
From the standpoint of enhancing the dry etching resistance, controlling the alkali solubility and increasing the adhesion to substrate, the fluorine-based acid-decomposable resin preferably contains another repeating unit as a copolymerization component in addition to the above-described fluorine atom-containing repeating unit. Preferred examples of the another repeating unit include:
1) a repeating unit having an alicyclic hydrocarbon structure represented by any one of formulae (pI) to (pVI) and formula (II-AB), specifically, repeating units 1 to 23 and repeating units [II-1] to [II-32], preferably repeating units 1 to 23 where Rx is CF3;
2) a repeating unit having a lactone structure represented by formula (Lc) or by any one of formulae (V-1) to (V-5), specifically, repeating units shown above, particularly, repeating units having a group represented by any one of formulae (Lc) and (V-1) to (V-4); and
3) a repeating unit derived from a maleic anhydride, a vinyl ether or a vinyl compound having a cyano group, represented by the following formula (XV), (XVI) or (XVII), specifically, repeating units (C-1) to (C-15). These repeating units each may or may not contain a fluorine atom.




In these formulae, R41 represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, and the alkyl group of R41 may be substituted by an aryl group.
R42 represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
A5 represents a single bond, a divalent alkylene, alkenylene, cycloalkylene or arylene group, —O—CO—R22, —OO—O—R23— or —CO—N(R24)—R25—.
R22, R23 and R25, which may be the same or different, each represents a single bond or a divalent alkylene, alkenylene, cycloalkylene or arylene group which may have an ether group, an ester group, an amide group, a urethane group or a ureido group.
R24 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
Examples of each substituent are the same as those described above for the substituents of formulae (FA) to (FG).
Specific examples of the repeating structural units represented by formulae (XV) to (XVII) are set forth below, but the present invention is not limited thereto.







The total amount of the repeating unit represented by any one of formulae (XV) to (XVII) and the another repeating unit is generally from 0 to 70 mol %, preferably from 10 to 60 mol %, more preferably from 20 to 50 mol %, based on all repeating units constituting the resin.
The fluorine-based acid-decomposable resin may contain an acid-decomposable group in any repeating unit.
The content of the repeating unit having an acid-decomposable group is preferably from 10 to 70 mol %, more preferably from 20 to 60 mol %, still more preferably from 30 to 60 mol %, based on all repeating units.
The fluorine-based acid-decomposable resin can be synthesized by radical polymerization almost in the same manner as the alicyclic hydrocarbon-based acid-decomposable resin.
The weight average molecular weight of the resin as the component (C) is preferably from 2,000 to 200,000 in terms of polystyrene by the GPC method. When the weight average molecular weight is 2,000 or more, heat resistance and dry etching resistance can be elevated and when the weight average molecular weight is 200,000 or less, developability can be enhanced and at the same time, by virtue of reduction in the viscosity, the film-forming property can be enhanced. The molecular weight is more preferably from 5,000 to 50,000, still more preferably from 7,000 to 30,000. By adjusting the molecular weight, the composition can be satisfied with all of heat resistance, resolving power, development defect and the like. The dispersity (Mw/Mn) of the resin as the component (C) is preferably from 1.0 to 3.0, more preferably from 1.2 to 2.5, still more preferably from 1.2 to 1.6. By adjusting the dispersity to an appropriate range, the line edge roughness performance can be enhanced.
In the positive photosensitive composition of the present invention, the amount of the resin as the component (C) blended in the entire composition is preferably from 40 to 99.99 mass %, more preferably from 50 to 99 mass %, still more preferably from 80 to 96 mass %, based on the entire solid content.
[4] (D) Dissolution Inhibiting Compound Capable of Decomposing Under the Action of an Acid to Increase the Solubility in an Alkali Developer and Having a Molecular Weight of 3,000 or Less (Hereinafter Sometimes Referred to as a “Component (D)” or “Dissolution Inhibiting Compound”)
In order to prevent reduction in the transparency to light at 220 nm or less, the dissolution inhibiting compound (D) capable of decomposing under the action of an acid to increase the solubility in an alkali developer and having a molecular weight of 3,000 or less is preferably an alicyclic or aliphatic compound containing an acid-decomposable group, such as acid-decomposable group-containing cholic acid derivative described in Proceeding of SPIE, 2724, 355 (1996). Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.
In the case where the photosensitive composition of the present invention is exposed with a KrF excimer laser or irradiated with electron beams, the dissolution inhibiting compound preferably contains a structure in which the phenolic hydroxyl group of a phenol compound is replaced by an acid-decomposable group. The phenol compound is preferably a phenol compound containing from 1 to 9 phenol skeletons, more preferably from 2 to 6 phenol skeletons.
The molecular weight of the dissolution inhibiting compound for use in the present invention is 3,000 or less, preferably from 300 to 3,000, more preferably from 500 to 2,500.
The amount of the dissolution inhibiting compound added is preferably from 3 to 50 mass %, more preferably from 5 to 40 mass %, based on the solid content of the photosensitive composition.
Specific examples of the dissolution inhibiting compound are set forth below, but the present invention is not limited thereto.




[5] (E) Resin Soluble in an Alkali Developer (Hereinafter Sometimes Referred to as a “Component (E)” or “Alkali-Soluble Resin”)

The alkali dissolution rate of the alkali-soluble resin is preferably 20 Å/sec or more, more preferably 200 Å/sec or more (Å is angstrom), as measured (at 23° C.) in 0.261N tetramethylammonium hydroxide (TMAH).
Examples of the alkali-soluble resin for use in the present invention include, but are not limited to, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, a hydroxystyrene-N-substituted maleimide copolymer, an o/p- or m/p-hydroxystyrene copolymer, polyhydroxystyrene with the hydroxyl group being partially O-alkylated (for example, 5 to 30 mol % being O-methylated, O-(1-methoxy)ethylated, O-(1-ethoxy)ethylated, O-2-tetrahydropyranylated or O-(tert-butoxycarbonyl)methylated) or O-acylated (for example, 5 to 30 mol % being o-acylated or O-(tert-butoxy)carbonylated), a styrene-maleic anhydride copolymer, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, a carboxyl group-containing methacrylic resin including a derivative thereof, and a polyvinyl alcohol derivative.
Among these alkali-soluble resins, preferred are novolak resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, a copolymer thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxystyrene, a styrene-hydroxystyrene copolymer, and an α-methylstyrene-hydroxystyrene copolymer.
The novolak resin can be obtained by subjecting a predetermined monomer as the main component to addition condensation with aldehydes in the presence of an acidic catalyst.
The weight average molecular weight of the alkali-soluble resin is 2,000 or more, preferably from 5,000 to 200,000, more preferably from 5,000 to 100,000.
The weight average molecular weight used herein is defined as a polystyrene-reduced value measured by gel permeation chromatography.
In the present invention, two or more kinds of these alkali-soluble resins (E) may be used in combination.
The amount of the alkali-soluble resin used is from 40 to 97 mass %, preferably from 60 to 90 mass %, based on the entire solid content of the photosensitive composition.
[6] (F) Acid Crosslinking Agent Capable of Crosslinking with the Alkali-Soluble Resin Under the Action of an Acid (Hereinafter Sometimes Referred to as a “Component (F)” or “Crosslinking Agent”)
In the negative photosensitive composition of the present invention, a crosslinking agent is used.
The crosslinking agent may be any compound as long as it causes crosslinking of the resin soluble in an alkali developer under the action of an acid, but the following compounds (1) to (3) are preferred:
(1) a hydroxymethyl, alkoxymethyl or acyloxymethyl form of a phenol derivative,
(2) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, and
(3) a compound having an epoxy group.
The alkoxymethyl group is preferably an alkoxymethyl group having a carbon number of 6 or less, and the acyloxymethyl group is preferably an acyloxymethyl group having a carbon number of 6 or less.
Among these crosslinking agents, the followings are particularly preferred.







In these formulae, L1 to L8, which may be the same or different, each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group or an alkyl group having a carbon number of 1 to 6.
The crosslinking agent is usually added in an amount of 3 to 70 mass %, preferably from 5 to 50 mass %, based on the solid content of the photosensitive composition.
<Other Components>
[7] (G) Basic Compound
The photosensitive composition of the present invention preferably contains (G) a basic compound so as to reduce the change of performance in aging from exposure to heating.
Preferred structures of the basic compound include structures represented by the following formulae (A) to (E).




In these formulae, R250, R251 and R252 each independently represents a hydrogen atom, an alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 20, or an aryl group having a carbon number of 6 to 20, and R250 and R251 may combine with each other to form a ring. These groups each may have a substituent. The alkyl or cycloalkyl group having a substituent is preferably an aminoalkyl group having a carbon number of 1 to 20, an aminocycloalkyl group having a carbon number of 3 to 20, a hydroxyalkyl group having a carbon number of 1 to 20, or a hydroxycycloalkyl group having a carbon number of 3 to 20.
These groups each may contain an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.
R253, R254, R255 and R256 each independently represents an alkyl group having a carbon number of 1 to 6 or a cycloalkyl group having a carbon number of 3 to 6.
Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine, and these compound each may have a substituent. The compound is more preferably, for example, a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure; an alkylamine derivative having a hydroxyl group and/or an ether bond; or an aniline derivative having a hydroxyl group and/or an ether bond.
Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of the compound having an onium hydroxide structure include a triarylsulfonium hydroxide, a phenacylsulfonium hydroxide and a sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound where the anion moiety of the compound having an onium hydroxide structure is converted into a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate and perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline and N,N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine and tris-(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.
One of these basic compounds may be used alone, or two or more thereof may be used in combination. However, when the amount of the component (B) used is 0.05 mass % or more, the basic substance may or may not be used. In the case of using the basic compound, the amount used thereof is usually from 0.001 to 10 mass %, preferably from 0.01 to 5 mass %, based on the solid content of the photosensitive composition. The amount used is preferably 0.001 mass % or more for obtaining a sufficiently high addition effect and preferably 10 mass % or less in view of sensitivity and developability of unexposed area.
[8] (H) Fluorine- and/or Silicon-Containing Surfactant
The photosensitive composition of the present invention preferably further contains any one fluorine- and/or silicon-containing surfactant (a fluorine-containing surfactant, a silicon-containing surfactant or a surfactant containing both a fluorine atom and a silicon atom), or two or more thereof.
When the photosensitive composition of the present invention contains a fluorine- and/or silicon-containing surfactant, a resist pattern with good sensitivity, resolution and adhesion and less development defects can be obtained at the time of using an exposure light source of 250 nm or less, particularly 220 nm or less.
Examples of the fluorine- and/or silicon-containing surfactant include surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2002-277862 and U.S. Pat. Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451. The following commercially available surfactants each may also be used as it is.
Examples of the commercially available surfactant which can be used include a fluorine-containing surfactant and a silicon-containing surfactant, such as EFtop EF301 and EF303 (produced by Shin-Akita Kasei K.K.), Florad FC430 and 431 (produced by Sumitomo 3M Inc.), Megafac F171, F173, F176, F189 and R08 (produced by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (produced by Asahi Glass Co., Ltd.), and Troysol S-366 (produced by Troy Chemical). In addition, polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-containing surfactant.
Other than these known surfactants, a surfactant using a polymer having a fluoro-aliphatic group, which is derived from a fluoro-aliphatic compound produced by telomerization process (also called telomer process) or oligomerization process (also called oligomer process), may be used. The fluoro-aliphatic compound can be synthesized by the method described in JP-A-2002-90991.
The polymer having a fluoro-aliphatic group is preferably a copolymer of a fluoro-aliphatic group-containing monomer with (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene)) methacrylate, and the polymer may have an irregular distribution or may be a block copolymer. Examples of the poly(oxyalkylene) group include a poly(oxy-ethylene) group, a poly(oxypropylene) group and a poly(oxybutylene group). This group may also be a unit having alkylenes differing in the chain length within the same chain, such as block-linked poly(oxyethylene, oxypropylene and oxyethylene) and block-linked poly(oxyethylene and oxypropylene). Furthermore, the copolymer of a fluoro-aliphatic group-containing monomer and a (poly(oxyalkylene)) acrylate (or methacrylate) may be not only a binary copolymer but also a ternary or greater copolymer obtained by simultaneously copolymerizing two or more different fluoro-aliphatic group-containing monomers or two or more different (poly(oxyalkylene)) acrylates (or methacrylates).
Examples thereof include commercially available surfactants such as Megafac F178, F-470, F-473, F-475, F-476 and F-472 (produced by Dainippon Ink & Chemicals, Inc.). Other examples include a copolymer of an acrylate (or methacrylate) having a C6F13 group with a (poly(oxyalkylene)) acrylate (or methacrylate), a copolymer of an acrylate (or methacrylate) having a C6F13 group with a (poly(oxyethylene)) acrylate (or methacrylate) and a (poly(oxypropylene)) acrylate (or methacrylate), a copolymer of an acrylate (or methacrylate) having a C8F17 group with a (poly(oxyalkylene)) acrylate (or methacrylate), and a copolymer of an acrylate (or methacrylate) having a C8F17 group with a (poly(oxyethylene)) acrylate (or methacrylate) and a (poly(oxypropylene)) acrylate (or methacrylate).
The amount of the fluorine- and/or silicon-containing surfactant used is preferably from 0.0001 to 2 mass %, more preferably from 0.001 to 1 mass %, based on the entire amount of the photosensitive composition (excluding the solvent).
[9] (I) Organic Solvent
The photosensitive composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent.
Examples of the organic solvent which can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and tetrahydrofuran.
(Ia) Ketone-Based Solvent
The solvent for use in the present invention is preferably a solvent having at least one ketone structure.
The solvent having a ketone structure includes a chain ketone solvent and a cyclic ketone solvent. A compound having a total carbon number of 5 to 8 is preferred in view of good coatability.
Examples of the chain ketone solvent include 2-heptanone, methyl ethyl ketone and methyl isobutyl ketone, with 2-heptanone being preferred.
Examples of the cyclic ketone solvent include cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, cyclo-heptanone, cyclooctanone and isophorone, with cyclohexanone and cycloheptanone being preferred.
The solvent is preferably used as sole solvent having a ketone structure or as a mixed solvent with another solvent. Examples of the solvent mixed (solvent used in combination) include a propylene glycol monoalkyl ether carboxylate, an alkyl lactate, a propylene glycol monoalkyl ether, an alkyl alkoxypropionate and a lactone compound.
Examples of the propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate.
Examples of the alkyl lactate include methyl lactate and ethyl lactate.
Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Examples of the alkyl alkoxypropionate include methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate and ethyl ethoxypropionate.
Examples of the lactone compound include γ-butyrolactone.
The solvent used in combination is preferably a propylene glycol monoalkyl ether carboxylate, an alkyl lactate or a propylene glycol monoalkyl ether, more preferably propylene glycol monomethyl ether acetate.
By virtue of mixing the ketone-based solvent and the solvent used in combination, adhesion to substrate, developability, DOF and the like are improved.
The ratio (by mass) of the ketone-based solvent and the solvent used in combination is preferably from 10/90 to 95/5, more preferably from 20/80 to 80/20, still more preferably from 30/70 to 70/30.
From the standpoint of enhancing the film thickness uniformity or development defect performance, a high boiling point solvent having a boiling point of 200° C. or more, such as ethylene carbonate and propylene carbonate, may be mixed.
The amount of the high boiling point solvent added is usually from 0.1 to 15 mass %, preferably from 0.5 to 10 mass %, more preferably from 1 to 5 mass %, based on the entire solvent.
In the present invention, a photosensitive composition having a solid content concentration of usually from 3 to 25 mass %, preferably from 5 to 22 mass %, more preferably from 5 to 15 mass %, is prepared by using a solvent alone, preferably by using two or more kinds of solvents.
<Other Additives>
If desired, the photosensitive composition of the present invention may further contain, for example, a dye, a plasticizer, a surfactant other than the component (H), a photosensitizer, and a compound capable of accelerating the solubility in a developer.
The compound capable of accelerating the dissolution in a developer, which can be used in the present invention, is a low molecular compound containing two or more phenolic OH groups or one or more carboxy group and having a molecular weight of 1,000 or less. In the case of containing a carboxyl group, an alicyclic or aliphatic compound is preferred.
The amount of the dissolution accelerating compound added is preferably from 2 to 50 mass %, more preferably from 5 to 30 mass %, based on the resin of component (C) or the resin of component (E). The amount added is preferably 50 mass % or less from the standpoint of suppressing the development residue or preventing the deformation of pattern at the development.
The phenol compound having a molecular weight of 1,000 or less can be easily synthesized by one skilled in the art by referring to the method described, for example, in JP-A-4-122938, JP-A-2-28531, U.S. Pat. No. 4,916,210 and European Patent 219294.
Specific examples of the alicyclic or aliphatic compound having a carboxy group include, but are not limited to, a carboxylic acid derivative having a steroid structure, such as cholic acid, deoxycholic acid and lithocholic acid, an adamantane carboxylic acid derivative, an adamantane dicarboxylic acid, a cyclohexanecarboxylic acid and a cyclohexanedicarboxylic acid.
In the present invention, a surfactant other than the fluorine- and/or silicon-containing surfactant (H) can also be added. Specific examples thereof include a nonionic surfactant such as polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, polyoxyethylene.polyoxypropylene block copolymers, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
One of these surfactants may be used alone or some of these surfactants may be used in combination.
(Pattern Forming Method)
The photosensitive composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent, preferably a mixed solvent described above, and coating the obtained solution on a predetermined support as follows.
For example, the photosensitive composition is coated on a substrate (e.g., silicon/silicon dioxide-coated substrate) as used in the production of a precision integrated circuit device, by an appropriate coating method such as spinner or coater, and dried to form a photosensitive film.
This photosensitive film is irradiated with actinic rays or radiation through a predetermined mask, preferably subjected to baking (heating), and then developed, whereby a good pattern can be obtained.
At the irradiation with actinic rays or radiation, the exposure may be performed by filling a liquid having a refractive index higher than that of air between the photosensitive film and the lens (immersion exposure). By this exposure, resolution can be elevated.
Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray and electron beam. Among these, preferred is far ultraviolet light at a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), an X-ray, an electron beam and the like are used. An ArF excimer laser, an F2 excimer laser, EUV (13 nm) and an electron beam are preferred.
In the development step, an alkali developer is used as follows. The alkali developer usable for the resist composition is an alkaline aqueous solution of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, a quaternary ammonium salt such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, or cyclic amines such as pyrrole and piperidine.
In the alkali developer, alcohols and a surfactant may also be added in an appropriate amount.
The alkali concentration of the alkali developer is usually from 0.1 to 20 mass %. The pH of the alkali developer is usually from 10.0 to 15.0.
EXAMPLES
The present invention is described in greater detail below by referring to Examples, but the present invention should not be construed as being limited thereto.
Synthesis Example of Compound (A)
Synthesis Example 1
Synthesis of Compound (A-1)
In a 1,000 mL-volume three-neck flask equipped with a 100-mL dropping funnel and a nitrogen inlet tube, 34.4 g (200 mmol) of sulfanylamide was charged and then dissolved in 200 mL of 10% NaOH, and the resulting solution was stirred under ice cooling. Subsequently, 55.3 g (200 mmol) of 1-octanesulfonyl chloride was added dropwise through the dropping funnel over 1 hour. After the dropwise addition, the mixed solution was stirred under ice cooling for 1 hour and after removing the ice bath, further stirred at room temperature for 3 hours. Thereafter, concentrated hydrochloric acid was added dropwise to the reaction solution, thereby effecting neutralization, and the precipitated white solid was filtered. This solid was then recrystallized from water/methanol to obtain 45.1 g of the following compound as a plate-like crystal.




Separately, 16.1 g (46.9 mmol) of triphenylsulfonium bromide and 12.4 g (53.5 mmol) of silver oxide were added to 150 mL of methanol, and the resulting mixture was stirred at room temperature for 2 hours. After removing the silver salt by filtration, 16.34 g (46.9 mmol) of the compound prepared above was added to the filtrate, and this solution was further stirred for 1 hour. Subsequently, the solvent was removed and after adding 200 mL of chloroform to the residue, the organic layer was washed with water. Furthermore, the solvent was removed, and the residue was dried to obtain 20.9 g of Compound (A-1) as a white solid.
1H-NMR (400 MHz, CD3OD):
δ 0.93 (t, 3H), 1.34-1.46 (m, 10H), 1.81 (quin, 2H), 3.24 (t, 2H), 6.78 (d, 2H), 7.66-7.78 (m, 17H).
Synthesis Example 2
Synthesis of Compound (A-6)
Triphenylsulfonium bromide (8.01 g (23.34 mmol)) and 5.68 g (24.51 mmol) were added to 100 mL of methanol, and the resulting mixture was stirred at room temperature for 2 hours. After removing the silver salt by filtration, 5.0 g (23.34 mmol) sulfacetamide was added to the filtrate, and this solution was further stirred for 1 hour. Thereafter, the solvent was removed, and the residue was dried to obtain 10.0 g of Compound (A-6) as a white solid.
1H-NMR (400 MHz, CD3OD):
δ 1.84 (s, 3H), 6.63 (d, 2H), 7.63 (d, 2H), 7.78-7.87 (m, 15H).
Synthesis Example 3
Synthesis of Compound (A-8)
In a nitrogen stream, a mixture containing 5.0 g (15.8 mmol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride and 50 mL of THF was ice-cooled and thereto, a mixed solution containing 1.66 g (16.6 mmol) of 1-methylpiperazine, 10 mL of triethylamine and 50 mL of THF was added dropwise over 60 minutes. The resulting solution was stirred under ice cooling for 1 hour and further stirred at room temperature for 1 hour. Thereafter, the organic layer was washed with water, an aqueous saturated ammonium chloride solution and water in this order and then dried over sodium sulfate. After concentrating the solvent, 2.36 g (15.8 mmol) of trifluoromethanesulfonamide and 10 mL of triethylamine were added to the residue, and this mixture was transferred to a pressure-resistant glass tube and stirred at 100° C. for 20 hours in the sealed tube. Subsequently, 100 mL of chloroform was added, and the organic layer was washed with water and then dried over sodium sulfate to obtain a brown oil. This oil was then rendered neutral by adding thereto 25 mL of methanol and 60 mL of 1.5N—HCl, and the precipitated white solid was filtered to obtain 5.65 g of the following compound.




The compound (4.0 g) obtained above was dissolved in a mixed solvent containing 100 ml of methanol and 40 ml of 1M-NaOH and after adding 2.61 g (7.61 mmol) of triphenylsulfonium bromide, the resulting solution was stirred at room temperature for 3 hours. Subsequently, 200 mL of chloroform was added, the organic layer was washed with water, the solvent was removed, and the residue was purified by column chromatography (SiO2, chloroform/methanol=10/1) to obtain the objective Compound (A-8) (4.56 g) as a white solid.
1H-NMR (400 MHz, CDCl3):
δ 2.32 (s, 3H), 2.50 (m, 4H), 3.55 (m, 4H), 7.65-7.80 (m, 15H).
19F-NMR (400 MHz, CDCl3):
δ-118.5 (m, 2F), −112.3 (m, 2F), −111.1 (m, 2F), −78.6 (m, 3F).
Other compounds (A) were synthesized in the same manner.
<Resin (C)>
The structure, molecular weight and dispersity of the resin (C) used in Examples are shown below.




























Examples 1 to 17 and Comparative Examples 1 to 3
Preparation of Resist
The components shown in Table 1 below were dissolved in a solvent to prepare a solution having a solid content concentration of 12 mass %, and this solution was filtered through a 0.1-μm polytetrafluoroethylene filter or polyethylene filter to prepare a positive resist solution. The positive resist solution prepared was evaluated by the following methods. The results obtained are shown in Table 1.
<Evaluation of Resist>
An antireflection film DUV-42 produced by Brewer Science Co., Ltd. was uniformly coated on a silicon substrate treated with hexamethyldisilazane by a spin coater to a thickness of 600 Å, dried on a hot plate at 100° C. for 90 seconds and then dried under heating at 190° C. for 240 seconds. Thereafter, each positive resist solution was coated by a spin coater and dried at 120° C. for 90 seconds to form a resist film of 0.25 μm.
The formed resist film was exposed by an ArF excimer laser stepper (manufactured by ISI, NA=0.6) through a mask and immediately after the exposure, heated on a hot plate at 120° C. for 90 seconds. Furthermore, the resist film was developed with an aqueous 2.38 mass % tetramethylammonium hydroxide solution at 23° C. for 60 seconds, rinsed with pure water for 30 seconds and dried to obtain a line pattern.
Defocus Latitude Depended on Line Pitch:
The line width of an isolated pattern (line/space=1/10) at the exposure amount for reproducing a mask pattern of a 130-nm dense pattern (line/space=1/1) was evaluated and expressed by the difference (nm) from 130 nm. As the value is smaller, the difference in performance between the dense pattern and the isolated pattern is smaller and the defocus latitude depended on line pitch is better.
Line Edge Roughness:
In the measurement of line edge roughness, a 90-nm pattern was observed by using a length-measuring scanning electron microscope (SEM). With respect to the region where the edge in the longitudinal direction of the line pattern was 5 μm, the distance from a reference line where the edge should be present was measured at 50 points by a length-measuring SEM (S-8840, manufactured by Hitachi, Ltd.) and after determining the standard deviation, 3σ was calculated. As the value is smaller, the performance is better.
Pattern Profile:
Assuming that the exposure amount for reproducing a line-and-space mask pattern with a line width of 90 nm is an optimal exposure amount, the profile at the optimal exposure amount was observed by a scanning electron microscope (SEM).







TABLE 1





ArF, Positive
























Compound






Surfactant



(A)
(g)
Acid Generator
(g)
Resin (10 g)
Basic Compound
(g)
(0.03 g)





Example


 1
A-1
(0.2)
z38
(0.3)
RA-1
PEA/TPA
(0.01/0.02)
W-4


 2
A-6
(0.2)
z60
(0.4)
RA-20
PEA/DIA
(0.01/0.02)
W-4





z38
(0.5)


 3
A-3
(0.2)
z63
(0.4)
RA-22
PEA
(0.02)
W-4


 4
A-14
(0.3)
z58
(0.4)
RA-21
PEA/DIA
(0.01/0.02)
W-4


 5
A-5
(0.3)
z57
(0.3)
RA-19
PEA
(0.02)
W-4


 6
A-8
(0.2)
z61
(0.4)
RA-21
PEA/DIA
(0.02/0.02)
W-1


 7
A-7
(0.2)
z50
(0.4)
RA-24
DIA
(0.02)
W-2


 8
A-8
(0.2)
z58
(0.3)
RA-7
PEA
(0.02)
W-4


 9
A-11
(0.2)
z38
(0.5)
RA-8
PEA
(0.02)
W-2


10
A-20
(0.3)
z59
(0.3)
RA-20
DIA
(0.02)
W-4


11
A-8
(0.2)
z58
(0.4)
RA-22
PEA
(0.02)
W-4





z60
(0.3)


12
A-33
(0.1)
z60
(0.4)
RA-21
PEA
(0.03)
W-2


13
A-38
(0.2)
z61
(0.5)
RA-20
PEA
(0.03)
W-4


14
A-42
 (0.18)
z63
(0.3)
RA-8
PEA/DIA
(0.01/0.01)
W-4


15
A-44
(0.2)
z38
(0.3)
RA-25
PEA
(0.03)
W-4


16
A-2
(0.1)
z58
(0.3)
RA-4
TMEA
(0.02)
W-4


17
A-28
(0.3)
z38
(0.5)
RA-23
DIA
(0.02)
W-1


Comparative


Example


 1
none
(—)
z38
(0.4)
RA-6
DIA
(0.02)
W-4


 2
none
(—)
z38
(0.4)
RA-20
PEA/DIA
(0.01/0.02)
W-4


 3
none
(—)
z38
(0.3)
RA-7
TMEA
(0.03)
W-4




















Defocus Latitude







Dissolution Inhibiting
Depended on Line Pitch
Line Edge Roughness



Solvent
(ratio by mass)
Compound (g)
(nm)
(nm)
Pattern Profile





Example


 1
A1/B1
(60/40)

21.0
4.2
slightly tapered


 2
A1/B1
(70/30)

23.7
3.6
slightly tapered


 3
A1/A3
(60/40)
LCB (0.2)
20.6
4.1
slightly tapered


 4
A1/A3
(60/40)

21.0
4.6
rectangular


 5
A1/B1
(80/20)

21.3
3.3
slightly tapered


 6
A1/B1
(80/20)

25.3
3.9
slightly tapered


 7
A1/B1
(60/40)

18.9
3.7
slightly tapered


 8
A1/A3
(80/20)

21.1
4.0
slightly tapered


 9
A1/B1
(60/40)

21.9
3.5
rectangular


10
A1/A4
(60/40)

20.6
3.9
slightly tapered


11
A1/B1
(60/40)
LCB (0.5)
23.1
3.5
slightly tapered


12
A1/B2
(60/40)

21.1
4.0
rectangular


13
A1/B1
(80/20)

26.9
3.5
slightly tapered


14
A1/B1
(80/20)

21.6
3.1
slightly tapered


15
A1/A4
(80/20)

22.0
3.8
slightly tapered


16
A1/B1
(70/30)

21.0
4.1
slightly tapered


17
A1/B1
(60/40)

22.1
4.0
slightly tapered


Comparative


Example


 1
A1/B1
(60/40)

35.2
9.6
tapered


 2
A1/B1
(70/30)

40.2
8.3
tapered


 3
A1/B1
(60/40)

41.2
10.6
tapered









Abbreviations common in respective Tables are shown together below.
[Basic Compound]
TPI: 2,4,5-triphenylimidazole
TPSA: triphenylsulfonium acetate
HEP: N-hydroxyethylpiperidine
DIA: 2,6-diisopropylaniline
DCMA: dicyclohexylmethylamine
TPA: tripentylamine
HAP: hydroxyantipyrine
TBAH: tetrabutylammonium hydroxide
TMEA: tris(methoxyethoxyethyl)amine
PEA: N-phenyldiethanolamine
TOA: trioctylamine
DBN: 1,5-diazabicyclo[4.3.0]non-5-ene
[Surfactant]


    W-1: Megafac F176 (produced by Dainippon Ink & Chemicals, Inc.) (fluorine-containing)
    W-2: Megafac R08 (produced by Dainippon Ink & Chemicals, Inc.) (fluorine- and silicon-containing)
    W-3: polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) (silicon-containing)
    W-4: Troysol S-366 (produced by Troy Chemical)

[Solvent]

A1: propylene glycol monomethyl ether acetate

A2: 2-heptanone

A3: cyclohexanone

A4: γ-butyrolactone

B1: propylene glycol monomethyl ether

B2: ethyl lactate

[Dissolution Inhibiting Compound]

LCB: tert-butyl lithocholate



As apparent from the results in Table 1, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile at the ArF exposure.
[Evaluation of Immersion Exposure]
<Preparation of Resist>
The components of each of Examples 1 to 17 shown in Table 1 were dissolved in a solvent to prepare a solution having a solid content concentration of 8 mass %, and this solution was filtered through a 0.1-μm polyethylene filter to prepare a positive resist solution. The prepared positive resist solutions were evaluated by the following methods.
<Evaluation of Resolution>
An organic antireflection film ARC29A (produced by Nissan Chemical Industries, Ltd.) was coated on a silicon wafer and baked at 205° C. for 60 seconds to form a 78-nm antireflection film. On this film, the resist composition prepared was coated and baked at 120° C. for 60 seconds to form a 150-nm resist film. The thus-obtained wafer was subjected to two-beam interference exposure (wet exposure) by using pure water as the immersion liquid. In the two-beam interference exposure (wet exposure), as shown in the FIGURE, the wafer 10 with an antireflection film and a resist film was exposed through a prism 8 and an immersion liquid (pure water) 9 by using a laser 1, a diaphragm 2, a shutter 3, three reflecting mirrors 4, 5 and 6, and a condenser lens 7. The wavelength of the laser 1 used was 193 nm, and a prism of forming a 65-nm line-and-space pattern 8 was used. Immediately after the exposure, the resist film was heated at 120° C. for 60 seconds, then developed with an aqueous tetramethylammonium hydroxide solution (2.38%) for 60 seconds and after rinsing with pure water, spin-dried. The obtained resist pattern was observed by a scanning electron microscope (S-9260, manufactured by Hitachi Ltd.), as a result, a 65-nm line-and-space pattern was resolved.
The compositions of Examples 1 to 17 were found to exhibit good image-forming capability also in the exposure through an immersion liquid.
Examples 18 to 23 and Comparative Examples 4 to 6
(1) Formation of Lower Resist Layer
FHi-028DD Resist (resist for i-line, produced by Fujifilm Olin Co., Ltd.) was coated on a 6-inch silicon wafer by using a spin coater, Mark 8, manufactured by Tokyo Electron Ltd. and then baked at 90° C. for 90 seconds to obtain a uniform film having a thickness of 0.55 μm.
This film was further heated at 200° C. for 3 minutes to form a lower resist layer having a thickness of 0.40 μm.
(2) Formation of Upper Resist Layer
The components shown in Table 2 below were dissolved in a solvent to prepare a solution having a solid content concentration of 11 mass %, and this solution was microfiltered through a membrane filter having a pore size of 0.1 μm to prepare an upper resist composition.
This upper resist composition was coated on the lower resist layer in the same manner and heated at 130° C. for 90 seconds to form an upper resist layer having a thickness of 0.20 μm.
Resins (SI-1) to (SI-5) in Table 2 are shown below.














Molecular




Weight







(SI-1)




15000










 


(SI-2)




14500










 


(SI-3)




 9600










 


(SI-4)




 8900


















 


(SI-5)




10800
























(3) Evaluation of Resist
The wafer obtained above was exposed by an ArF excimer stepper 9300 (manufactured by ISI) having mounted thereon a resolving power mask, while changing the exposure amount.
Subsequently, the wafer was heated at 120° C. for 90 seconds, developed with a tetrahydroammonium hydroxide developer (2.38 mass %) for 60 seconds, rinsed with distilled water and dried to form an upper layer pattern. The defocus latitude depended on line pitch, the line edge roughness and the pattern profile were evaluated in the same manner as in Example 1.
The results obtained are shown in Table 2.







TABLE 2





Silicon-Containing Positive
























Compound






Surfactant



(A)
(g)
Acid Generator
(g)
Resin (10 g)
Basic Compound
(g)
(0.03 g)





Example


18
A-1
(0.2)
z38
(0.4)
SI-1
PEA
(0.02)
W-2


19
A-33
(0.1)
z38
(0.4)
SI-2
TPA
 (0.025)
W-4


20
A-6
(0.1)
z14
(0.4)
SI-1
DIA
(0.02)
W-3


21
A-8
(0.3)
z59
(0.4)
SI-3
TMEA
 (0.015)
W-4


22
A-11
(0.2)
z38
(0.4)
SI-4
DIA
(0.02)
W-4


23
A-3
 (0.25)
z60
(0.4)
SI-5
PEA
(0.02)
W-1


Comparative


Example


 4
none
(—)
z38
(0.4)
SI-1
PEA
(0.02)
W-1


 5
none
(—)
z38
(0.3)
SI-1
PEA/DIA
(0.01/0.01)
W-4


 6
none
(—)
z58
(0.4)
SI-4
TPA
(0.02)
W-4



















Line Edge Roughness




Solvent
(ratio by mass)
Defocus Latitude Depended on Line Pitch (nm)
(nm)
Pattern Profile





Example


18
A1/A3
(80/20)
22.8
3.6
slightly tapered


19
A1
(100)
26.0
4.2
rectangular


20
A1/A3
(60/40)
23.5
3.7
slightly tapered


21
A1
(100)
25.5
4.1
rectangular


22
A1/A3
(80/20)
24.4
3.9
slightly tapered


23
A1/A3
(80/20)
24.7
4.0
slightly tapered


Comparative


Example


 4
A1/A3
(80/20)
45.5
10.6
tapered


 5
A1
(100)
31.5
8.9
tapered


 6
A1/A3
(60/40)
42.3
9.1
tapered









As apparent from the results in Table 2, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile also when used as a two-layer resist.
Examples 24 to 29 and Comparative Examples 7 to 9
Preparation of Resist
The components shown in Table 3 below were dissolved in a solvent, and the resulting solution was filtered through a 0.1-μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 14 mass %.
<Evaluation of Resist>
The prepared positive resist solution was uniformly coated by a spin coater on a silicon substrate treated with hexamethyldisilazane, and dried under heating on a hot plate at 120° C. for 90 seconds to form a resist film having a thickness of 0.4 μm.
This resist film was exposed through a mask for a line-and-space pattern by using a KrF excimer laser stepper (NA=0.63) and immediately after the exposure, heated on a hot plate at 110° C. for 90 seconds. Thereafter, the resist film was developed with an aqueous 2.38 mass % tetramethylammonium hydroxide solution at 23° C. for 60 seconds, rinsed with pure water for 30 seconds and then dried to form a line pattern. The defocus latitude depended on line pitch, the line edge roughness and the pattern profile were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.







TABLE 3





KrF, Positive
























Compound






Surfactant



(A)
(g)
Acid Generator
(g)
Resin (10 g)
Basic Compound
(g)
(0.03 g)





Example


24
A-1
(0.1)
z38
(0.4)
R-1
PEA
(0.02)
W-4


25
A-14
(0.1)
z38
(0.4)
R-2
PEA/DIA
(0.01/0.02)
W-1


26
A-6
(0.1)
z38
(0.4)
R-1
TMEA
(0.02)
W-4


27
A-8
(0.3)
z38
(0.4)
R-2
PEA
(0.04)
W-4


28
A-11
(0.1)
z59
(0.3)
R-5
DIA
(0.02)
W-4


29
A-3
 (0.33)
z61
(0.4)
R-2
PEA/TPA
(0.01/0.02)
W-3


Comparative


Example


 7
none
(—)
z38
(0.4)
R-2
PEA
(0.02)
W-1


 8
none
(—)
z38
(0.5)
R-2
PEA
(0.02)
W-4


 9
none
(—)
z58
(0.4)
R-1
DIA
(0.02)
W-4



















Line Edge Roughness




Solvent
(ratio by mass)
Defocus Latitude Depended on Line Pitch (nm)
(nm)
Pattern Profile





Example


24
A1/B1
(60/40)
27.4
4.4
slightly tapered


25
A1/B1
(60/40)
28.0
4.5
rectangular


26
A1/A4
(80/20)
28.5
4.6
slightly tapered


27
A1/B1
(60/40)
23.3
3.7
rectangular


28
A1/B1
(60/40)
28.9
4.6
slightly tapered


29
A1/B1
(60/40)
26.0
4.2
slightly tapered


Comparative


Example


 7
A1/B1
(60/40)
39.9
7.7
tapered


 8
A1/B1
(80/20)
36.2
9.6
tapered


 9
A1/A3
(60/40)
40.5
8.6
tapered









The weight average molecular weight and dispersity of each of Resins (R-1) to (R-5) used in Table 3 are shown in Table 4 below.











TABLE 4








Weight Average
Dispersity



Resin
Molecular Weight
(Mw/Mn)









R-1
13000
1.2



R-2
11000
1.7



R-3
13000
1.2



R-4
10000
1.8



R-5
11000
1.8










As apparent from the results in Table 3, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile also as a positive resist composition for exposure with a KrF excimer laser.
Examples 30 to 35 and Comparative Examples 10 to 12
Preparation of Resist
The components shown in Table 5 below were dissolved in a solvent, and the resulting solution was filtered through a 0.1-μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid content concentration of 14 mass %.
The prepared negative resist solutions were evaluated in the same manner as in Example 24. The results obtained are shown in Table 5.







TABLE 5





KrF, Negative
























Compound






Surfactant



(A)
(g)
Acid Generator
(g)
Resin (10 g)
Basic Compound
(g)
(0.03 g)





Example


30
A-1
(0.1)
z38
(0.4)
P-1
PEA
(0.02)
W-4


31
A-33
(0.1)
z14
(0.5)
P-3
PEA/DIA
(0.01/0.02)
W-4


32
A-6
(0.1)
z38
(0.4)
P-3
DIA
(0.02)
W-1


33
A-8
(0.3)
z38
(0.3)
P-2
PIA
(0.01/0.02)
W-4


34
A-11
(0.1)
z59
(0.3)
P-2
PEA/DIA
(0.03/0.01)
W-4


35
A-3
(0.1)
z61
(0.5)
P-1
PEA
(0.02)
W-3


Comparative


Example


10
none
(—)
z38
(0.4)
P-1
HAP
(0.02)
W-1


11
none
(—)
z38
(0.5)
P-3
DIA
(0.02)
W-4


12
none
(—)
z58
 (0.45)
P-2
PEA
(0.02)
W-4




















Defocus Latitude







Crosslinking Agent
Depended on Line Pitch
Line Edge Roughness



Solvent
(ratio by mass)
(g)
(nm)
(nm)
Pattern Profile





Example


30
A1/B1
(60/40)
CL-1 (3)
24.1
3.8
slightly tapered


31
A1/B1
(80/20)
CL-2 (2)
25.0
4.0
rectangular


32
A1/B1
(60/40)
CL-3 (2)
29.1
3.8
slightly tapered


33
A1/B1
(60/40)
CL-4 (3)
25.3
4.0
rectangular


34
A1/A4
(80/20)
CL-5 (2)
29.3
3.6
slightly tapered


35
A1/B1
(60/40)
CL-6 (2)
24.8
4.0
slightly tapered


Comparative


Example


10
A1/B1
(60/40)
CL-1 (3)
40.1
8.8
tapered


11
A1/B1
(70/30)
CL-2 (2)
35.6
7.6
tapered


12
A1/A3
(90/10)
CL-3 (2)
29.8
9.0
tapered









The structure, molecular weight and molecular weight distribution of each alkali-soluble resin and the crosslinking agents in Table 5 are shown below.















Mw
Mw/Mn







 










P-1




16000
2.30


 


P-2




12000
1.2


 


P-3




 6000
1.2
















As apparent from the results in Table 5, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile also as a negative resist composition for exposure with a KrF excimer laser.
Examples 36 to 41 and Comparative Examples 13 to 15
Preparation of Resist
The components shown in Table 3 were dissolved in a solvent, and the resulting solution was filtered through a 0.1-μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 12 mass %.
<Evaluation of Resist>
The prepared positive resist solution was uniformly coated by a spin coater on a silicon substrate treated with hexamethyldisilazane, and dried under heating on a hot plate at 120° C. for 60 seconds to form a resist film having a thickness of 0.3 μm.
This resist film was irradiated by an electron beam projection lithography apparatus manufactured by Nikon Corp. (accelerating voltage: 100 KeV) and immediately after the irradiation, heated on a hot plate at 110° C. for 90 seconds. Furthermore, the resist film was developed with an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38 mass % at 23° C. for 60 seconds, rinsed with pure water for 30 seconds and then dried to form a line-and-space pattern. The defocus latitude depended on line pitch, the line edge roughness and the pattern profile were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 6.







TABLE 6







EB, positive











Defocus Latitude





Depended on
Line Edge



Line Pitch (nm)
Roughness (nm)
Pattern Profile














Example





36
23.9
3.8
slightly tapered


37
24.8
3.0
rectangular


38
28.9
3.7
slightly tapered


39
29.1
3.3
rectangular


40
24.8
3.9
slightly tapered


41
26.7
3.3
slightly tapered


Comparative


Example


13
40.8
10.1
tapered


14
40.1
10.0
tapered


15
38.2
9.1
tapered









As apparent from the results in Table 6, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile also as a positive resist composition for electron beam irradiation.
Examples 42 to 47 and Comparative Examples 16 to 18
Preparation of Resist
The components shown in Table 5 were dissolved in a solvent, and the resulting solution was filtered through a 0.1-μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid content concentration of 12 mass %.
<Evaluation of Resist>
The prepared negative resist solution was uniformly coated by a spin coater on a silicon substrate treated with hexamethyldisilazane, and dried under heating on a hot plate at 120° C. for 60 seconds to form a resist film having a thickness of 0.3 nm.
This resist film was irradiated by an electron beam projection lithography apparatus manufactured by Nikon Corp. (accelerating voltage: 100 KeV) and immediately after the irradiation, heated on a hot plate at 110° C. for 90 seconds. Furthermore, the resist film was developed with an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38 mass % at 23° C. for 60 seconds, rinsed with pure water for 30 seconds and then dried to form a line-and-space pattern. The defocus latitude depended on line pitch, the line edge roughness and the pattern profile were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 7.







TABLE 7







EB, negative











Defocus Latitude





Depended on
Line Edge



Line Pitch (nm)
Roughness (nm)
Pattern Profile














42
22.8
3.6
slightly tapered


43
27.4
3.4
rectangular


44
25.6
4.5
slightly tapered


45
24.1
3.8
rectangular


46
23.9
4.2
slightly tapered


47
25.5
3.9
slightly tapered


Comparative


Example


16
36.3
10.9
tapered


17
33.3
10.3
tapered


18
36.7
10.6
tapered









As apparent from the results in Table 7, the photosensitive composition of the present invention is excellent in the defocus latitude depended on line pitch, the line edge roughness and the pattern profile also as a negative resist composition for electron beam irradiation.
Examples 48 to 53 and Comparative Examples 19 to 21
Preparation of Resist
The components shown in Table 3 were dissolved in a solvent, and the resulting solution was filtered through a 0.1-μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 8 mass %.
<Evaluation of Resist>
The prepared positive resist solution was uniformly coated by a spin coater on a silicon substrate treated with hexamethyldisilazane, and dried under heating on a hot plate at 120° C. for 60 seconds to form a resist film having a thickness of 0.15 μm. The obtained resist film was subjected to surface exposure with EUV light (wavelength: 13 nm) while changing the exposure amount in 0.5-mJ steps in the range from 0 to 10.0 mJ and baked at 110° C. for 90 seconds. Thereafter, the dissolution rate at each exposure amount was measured by using an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution, and a sensitivity curve was obtained from the measured values. The sensitivity was defined as the exposure amount when the dissolution rate of resist was saturated on this sensitivity curve. Also, the dissolution contrast (γ value) was calculated from the gradient in the straight line part of the sensitivity curve. As the γ value is larger, the dissolution contrast is better.
The evaluation results are shown in Table 8 below.







TABLE 8







EUV










Sensitivity (mJ/cm2)
γ Value













Example




48
2.2
15.9


49
2.6
16.1


50
2.1
14.9


51
1.8
15.2


52
2
16.9


53
2.3
15.5


Comparative


Example


19
4.5
6.9


20
5.0
7.3


21
5.6
6.8









As apparent from the results in Table 8, the resist composition of the present invention is excellent in terms of high sensitivity and high contract in the characteristic evaluation by the irradiation of EUV light as compared with the compositions of Comparative Examples.
According to the present invention, a photosensitive composition assured of small line edge roughness, good pattern profile and low defocus latitude depended on line pitch and improved in the sensitivity and dissolution contrast at the exposure with EUV light, a compound for use in the photosensitive composition, and a pattern forming method using the photosensitive composition can be provided.
The entire disclosure of each and every foreign patent application from which the benefit of foreign priority has been claimed in the present application is incorporated herein by reference, as if fully set forth.

## Claims

1. A photosensitive composition comprising: (A) a compound capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation:




wherein R1 and R2 each independently represents a monovalent organic group, provided that at least either one of R1 and R2 has a proton acceptor functional group, R1 and R2 may combine to form a ring and the ring formed may have a proton acceptor functional group; and
X1 and X2 each independently represents —CO— or —SO2—, said compound (A) being a sulfonium salt compound of the compound represented by formula (I) or an iodonium salt compound of the compound represented by formula (I);
(B) a compound capable of generating an acid upon irradiation with actinic rays or radiation; and
(C) a resin capable of decomposing under an action of an acid to increase the solubility of the resin (C) in an alkali developer,
wherein:
the proton acceptor functional group has a partial structure selected from the group consisting of a crown ether structure, an aza-crown ether structure, a tertiary amine structure, a secondary amine structure, a primary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and an aniline structure;
when the proton acceptor functional group contains a tertiary amine, a secondary amine, or a primary amine, as a partial structure, a carbon atom connected to a nitrogen atom in the tertiary amine, the secondary amine, or the primary amine connects only to one or more hydrogen, carbon, and/or oxygen atoms;
the resin (C) has no aromatic group; and
the compound (A) capable of generating a compound represented by formula (I) upon irradiation with actinic rays or radiation is a compound represented by the following formula (A1) or (A2):




wherein R201, R202 and R203 each independently represents an organic group, provided that when two members out of R201 to R203 are both an alkylene group, the two alkylene groups may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group;
X represents an anion of the compound represented by formula (I); and
R204 and R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

2. The photosensitive composition according to claim 1,
wherein the compound represented by formula (I) is represented by formula (II):




wherein R1 and R3 each independently represents a monovalent organic group, provided that at least either one of R1 and R3 has a proton acceptor functional group, R1 and R3 may combine to form a ring and the ring formed may have a proton acceptor functional group;
X1, X2 and X3 each independently represents —CO— or —SO2—;
A represents a divalent linking group;
B represents a single bond, an oxygen atom or —N(Rx)-;
Rx represents a hydrogen atom or a monovalent organic group;
when B is —N(Rx)-, R3 and Rx may combine to form a ring; and
n represents 0 or 1.

3. A pattern forming method comprising:
forming a photosensitive film from a photosensitive composition according to claim 1; and
exposing and developing the photosensitive film.

4. The photosensitive composition according to claim 1,
wherein the compound as the component (B) is a sulfonium salt of fluoro-substituted alkanesulfonic acid, fluorine-substituted benzenesulfonic acid or fluorine-substituted imide acid.

5. The photosensitive composition according to claim 1,
wherein the resin as the component (C) has a repeating unit having a lactone group.

6. The photosensitive composition according to claim 1,
wherein R1 and R2 combine to form a ring and the ring formed has a proton acceptor functional group, and the ring formed includes a structure where the organic groups of R1 and R2 are further bonded through an alkylene group, an oxy group or an imino group.

7. The photosensitive composition according to claim 1,
wherein at least either one of X1 and X2 is —SO2—.

8. The photosensitive composition according to claim 2,
wherein the divalent linking group as A is a divalent linking group having a carbon number of 1 to 8 and containing a fluorine atom.

9. The photosensitive composition according to claim 2,
wherein X1, X2 and X3 each is —SO2—.

10. The photosensitive composition according to claim 1,
wherein the resin (C) contains a repeating unit having an alicyclic hydrocarbon-containing partial structure represented by formulae (pI):




wherein in formulae (pI), R11 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group; and
Z represents an atomic group necessary for forming a monocyclic cycloalkyl group together with the carbon atom.

11. The photosensitive composition according to claim 1, which further comprises:
a solvent having at least one ketone structure.

12. The photosensitive composition according to claim 1, wherein the proton acceptor functional group contains a non-cyclic tertiary amine as a partial structure.

13. The photosensitive composition according to claim 1, wherein the proton acceptor functional group contains at least one selected from the group consisting of a pyrrolidine structure, a piperidine structure, a piperazine structure, a pyridine structure, an imidazole structure, a pyrazine structure, and an aniline structure.

14. The photosensitive composition according to claim 1, wherein the proton acceptor functional group contains a primary amine as a partial structure.

15. The photosensitive composition according to claim 1, wherein the proton acceptor functional group contains a secondary amine as a partial structure.