# Patent

## Title
Resist composition and method for producing resist pattern

## Abstract

A resist composition contains: a resin having an acid-labile group, an acid generator, a compound having two or more phenolic-hydroxy groups and being other than a resin, and a solvent. The resist composition of the disclosure can provide a resist pattern showing excellent shape and detachability, therefore, the present resist composition can be used for semiconductor microfabrication with resist patterns showing excellent shape.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to Japanese Application No. 2015-73094 filed on Mar. 31, 2015. The entire disclosure of Japanese Application No. 2015-73094 is incorporated hereinto by reference.
BACKGROUND
1. Field of the Invention
The disclosure relates to a resist composition and a method for producing resist pattern.
2. Related Art
In the mounting of the semiconductor chip being thin film and having multi-pin, the protruding electrodes of about 4 to 150 μm height, which is connection terminals (bumps), are formed on a substrate (wafer) by photolithography. As a method for forming such a connection terminal, use of a resist composition containing a resin having a structural unit derived from p-hydroxystyrene has been disclosed in JP2011-75864A1.
SUMMARY
The present application provides the inventions as follow.
[1] A resist composition contains:
a resin having an acid-labile group,
an acid generator,
a compound having two or more phenolic-hydroxy groups and being other than a resin, and
a solvent.
[2] The resist composition according to [1] further contains an alkaline-soluble resin.
[3] The resist composition according to [1] or [2] wherein
the resin having an acid-labile group is a resin having a structural unit represented by formula (a1-2):




wherein Ra5 represents a hydrogen atom or a methyl group,
Ra1′ and Ra2′ each independently represent a hydrogen atom or a C1 to C12 hydrocarbon group, and Ra3′ represents a C1 to C20 hydrocarbon group, or
Ra1′ represents a hydrogen atom or a C1 to C12 hydrocarbon group, and Ra2′ and Ra3′ are bonded together with a carbon atom and an oxygen atom bonded thereto to form a divalent heterocyclic group having 2 to 20 carbon atoms, and a methylene group contained in the hydrocarbon group or the divalent heterocyclic group may be replaced by an oxygen atom or a sulfur atom,
Ra6 in each occurrence independently represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, and
“m” represents an integer of 0 to 4.
[4] The resist composition according to any one of [1] to [3] wherein
the acid generator is a compound having a group represented by formula (B1):




wherein Rb1 represents a C1 to C18 hydrocarbon group in which a hydrogen atom may have a fluorine atom and in which a methylene group may be replaced by an oxygen atom or a carbonyl group.
[5] The resist composition according to any one of [1] to [4] wherein
the compound having two or more phenolic-hydroxy groups is a compound represented by formula (I):




wherein Xi represents a single bond or an oxygen atom,
A represents a C1 to C6 alkanediyl group where a methylene group may be replaced by an oxygen atom, provided that when Xi represents an oxygen atom, a methylene group bonded to Xi is not replaced by an oxygen atom,
“i1” and “i2” each independently represent an integer of 0 to 4, provided that the total number of i1 and i2 is 2 or more,
Ri12 and Ri13 in each occurrence independently represent a halogen atom or a C1 to C12 alkyl group,
“i3” and “i4” each independently represent an integer of 0 to 4,
Ri1 represents a hydrogen atom or an optionally substituted C1 to C6 alkyl group, or Ri1 may be bonded to A together with carbon atoms and Xi to form an optionally substituted 5 to 12-membered saturated ring,
provided that the total number of “i1” and “i3” is 4 or less and the total number of “i1” and “i4” is 5 or less.
[6] A method for producing a resist pattern includes steps (1) to (4);
(1) applying the resist composition according to any one of [1] to [5] onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer; and
(4) developing the exposed composition layer.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1(a) illustrates an excellent cross-sectional view of a photoresist pattern which has substantially rectangle shape at its top and bottom portions, and
FIG. 1(b) illustrates a cross-sectional view of a photoresist pattern which has a round shape at its bottom portion.



DETAILED DESCRIPTION OF DISCLOSURE
In the specification, the term “(meth)acrylic monomer” means a monomer having a structure of “CH2═CH—CO—” or “CH2═C(CH3)—CO—”, as well as “(meth)acrylate” and “(meth)acrylic acid” mean “an acrylate or methacrylate” and “an acrylic acid or methacrylic acid,” respectively. The group described herein, which can take both the linear structure and branch structure, may be either. When stereo isomers exist, it includes all stereoisomers. The indefinite articles “a” and “an” are taken as the same meaning as “one or more”.
The term “solid components” means components other than solvents in a resist composition.
<Resist Composition>
The resist composition according to the disclosure contains
a resin having an acid-labile group (which is sometimes referred to as “resin (A1)”),
an acid generator (which is sometimes referred to as “acid generator (B)”),
a compound having two or more phenolic-hydroxy groups other than a polymer (which is sometimes referred to as “compound (I)”), and
a solvent (which is sometimes referred to as “solvent (D)”).
The resist composition of the disclosure may further contain a resin that is different from the resin (A1) such as alkali-soluble resin (which is sometimes referred to as “resin (A2)”) or such as alkali-insoluble resin (which is sometimes referred to as “resin (A3)”), a quencher (which is sometimes referred to as “quencher (C)”) and an adhesion improver (which is sometimes referred to as “adhesion improver (E)”), or the like.
<Resin (A1)>
The resin (A1) has the structural unit having an acid-labile group (which is sometimes referred to as “structural unit (a1)”).
The “acid-labile group” means a group having a leaving group which is removed therefrom by contacting with an acid resulting in forming a hydrophilic group such as a hydroxy or carboxy group. In other words, the “acid-labile group” means group capable of showing increased solubility group in an alkaline aqueous solution by the action of an acid. Therefore, the resin (A1) shows increased solubility in an alkaline aqueous solution of by the action of an acid.
The “increased solubility in an alkaline aqueous solution by the action of an acid” means to increase the solubility in an alkaline aqueous solution by contact with an acid. The resin is preferably a resin which is insoluble or poorly soluble in an alkali aqueous solution before contact with the acid, and becomes soluble in an alkaline aqueous solution after contact with the acid.
The resin (A1) may further has another type of known structural unit in the art such as a structural unit having no acid-labile group (which is sometimes referred to as “structural unit (a2)”), in addition to the structural unit (a1) having an acid-labile group.
Examples of the acid-labile group include a group represented by the formula (1) and the formula (2).




In the formula (1), Ra1, Ra2 and Ra3 each independently represent a C1 to C8 alkyl group, a C3 to C20 alicyclic hydrocarbon group, or Ra1 and Ra2 may be bonded together with a carbon atom bonded thereto to form a C2 to C20 divalent hydrocarbon group and Ra3 represents a C1 to C8 alkyl group or a C3 to C20 alicyclic hydrocarbon group, and * represents a binding position.




In the formula (2), Ra1′ and Ra2′ each independently represent a hydrogen atom or a C1 to C12 hydrocarbon group, Ra3′ represents a C1 to C20 hydrocarbon group, or Ra1′ represents a hydrogen atom or a C1 to C12 hydrocarbon group, and Ra2′ and Ra3′ are bonded together with a carbon atom and an oxygen atom bonded thereto to form a divalent heterocyclic group having 2 to 20 carbon atoms, and a methylene group contained in the hydrocarbon group or the divalent heterocyclic group may be replaced by an oxygen atom or a sulfur atom, and * represents a binding position.
Examples of the alkyl group for Ra1 to Ra3 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
The alicyclic hydrocarbon group for Ra1 to Ra3 may be a monocyclic or polycyclic group. Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, norbornyl, and the following groups.




In the formula, * represents a binding position.
The alicyclic hydrocarbon group for Ra1 to Ra3 preferably is a C3 to C16 alicyclic hydrocarbon group.
When Ra1 and Ra2 is bonded together to form a divalent hydrocarbon group, examples of the group —C(Ra1)(Ra2)(Ra3) include the following groups. The divalent hydrocarbon group is preferably a C3 to C12 alicyclic hydrocarbon group. In each of the formulae, * represent a binding position to —O—.




Specific examples of the group represented by the formula (1) include
an alkoxycarbonyl group (a group in which Ra1 to Ra3 are alkyl groups, preferably tert-butoxycarbonyl group, in the formula (1)),
1-alkylcyclopentane-1-yloxycarbonyl group and 1-alkylcyclohexane-1-yloxycarbonyl group (a group in which Ra1 and Ra2 form a cyclopentyl or a cyclohexyl group, and Ra3 is an alkyl group, in the formula (1)), and
1-(cyclopentane-1-yl)-1-alkylalkoxycarbonyl group and 1-(cyclohexane-1-yl)-1-alkylalkoxycarbonyl group (a group in which Ra1 and Ra2 are an alkyl group, and Ra3 a cyclopentyl or a cyclohexyl group, in the formula (1)).
The hydrocarbon group for Ra1′ to Ra3′ in formula (2) may be an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a combination thereof.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl and dodecyl groups.
Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups; and a polycyclic alicyclic hydrocarbon group such as decahydronaphthyl, adamantyl, norbornyl, and the following groups.
Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups. The aromatic hydrocarbon group may be substituted with a substituent, and examples of the substituent include a C6 to C10 aryloxy group.
Examples of groups combining the alkyl group and the alicyclic hydrocarbon group include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, isobornyl, 2-alkyladamantane-2-yl and 1-(adamantane-1-yl)alkane-1-yl groups.
Examples of groups combining the aromatic hydrocarbon group and the alkyl group include aralkyl group such as benzyl, phenethyl, phenylpropyl, naphthylmethyl and naphthylethyl groups.
Examples of the divalent heterocyclic group formed by binding with Ra2′ and Ra3′ with a carbon atom and an oxygen atom bonded thereto include the following groups. * represent a binding position.




In each formula, Ra1′ is preferably a hydrogen atom.
Specific examples of the group represented by the formula (2) include the following groups. In each of the formulae, * represent a binding position.




<Structural Unit (a1)>

The monomer which derives the structural unit (a1) is preferably a monomer which has an acid-labile group and an ethylene unsaturated bond, and is more preferably a monomer having a group represented by the formula (1) and/or (2) and a ethylene unsaturated bond, provided that the monomers is those other than the monomers which derives the structural unit (a1).
The resin (A1) may have one kind of the structural unit (a1-1) or two or more of them.
Examples of the structural units (a1) preferably include the structural units represented by formula (a1-1) and formula (a1-2), these are sometimes referred to as the “structural unit (a1-1)” and “structural unit (a1-2)”.




In the formulae, Ra1, Ra2, Ra3, Ra1′, Ra2′ and Ra3′ are as defined above,
Ra4 and Ra5 each independently represent a hydrogen atom or a methyl group,
Ra6 in each occurrence independently represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, and
“m” represents an integer of 0 to 4.
In the formula (a1-1), Ra4 is preferably a hydrogen atom.
In the formula (a1-2), Ra1′ is preferably a hydrogen atom.
Ra2′ is preferably a C1 to C12 hydrocarbon group, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of Ra3′ is preferably a C1 to C18 alkyl group, a C3 to C18 alicyclic hydrocarbon group, a C6 to C18 aromatic hydrocarbon group or a combination thereof, and more preferably a C1 to C18 alkyl group, a C3 to C18 alicyclic hydrocarbon group or a C7 to C18 aralkyl group. The alkyl group and the alicyclic group is preferably unsubstituted. When the aromatic hydrocarbon group has been substituted, the substituent is preferably a C6 to C10 aryloxy group.
Ra5 is preferably a hydrogen atom.
Ra6 is preferably a C1 to C4 alkoxy group, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.
“m” is preferably 0 or 1, and more preferably 0.
Examples of the structural unit represented by formula (a1-1) include those represented by formulae (a1-1-1) to (a1-1-17).










Examples of the structural unit represented by formula (a1-2) include those derived from the monomer represented by formulae (a1-2-1) to (a1-2-14).










Examples of the monomers include monomers in which a methyl group corresponding to Ra4 and Ra5 has been replaced by a hydrogen atom.
Among them, the structural units derived from the monomers represented by formulae (a1-2-2), (a1-2-3), (a1-2-4), (a1-2-9) and (a1-2-14) are preferred, and the structural units derived from the monomers represented by formulae (a1-2-2), (a1-2-3), (a1-2-4) and (a1-2-9) are more preferred.
The resin (A1) is preferably a resin having the structural unit (a1-2).
When the resin (A1) has the structural unit(s) represented by formula (a1-1) and/or formula (a1-2), the total content of these is preferably 5 to 60% by mole, more preferably 10 to 55% by mole, still more preferably 15 to 50% by mole, and particularly preferably 20 to 45% by mole with respect to the total structural units (100% by mole) of the resin (A1).
<Structural Unit (a2)>
The resin (A1) may have one kind of the structural unit (a2), or two or more them.
Examples of the structural unit (a2) include structural units represented by formulae (a2-1), (a2-2) and (a2-3), these are sometimes referred to as the “structural unit (a2-1)”, “structural unit (a2-2)” and “structural unit (a2-3)”.




In the formulae, Ra7, Ra8 and Ra9 each independently represent a hydrogen atom or a methyl group,
Ra10 in each occurrence independently represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group,
m′ represents an integer of 0 to 4,
Ra11 represents a hydrogen atom, a C1 to C10 primary or secondary hydrocarbon group,
Ra12 represents a C1 to C6 primary or secondary alkyl group,
La1 represents a C2 to C6 alkanediyl group where the carbon atom bonding to an oxygen atom is a primary or secondary carbon atom, and
n represents an integer of 1 to 30.
Examples of the alkyl group for Ra10 and Ra12 include methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Examples of the alkoxy group for Ra10 include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy groups.
The hydrocarbon group for Ra11 may be an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a combination thereof.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl groups.
The alicyclic hydrocarbon group may include a monocyclic and polycyclic groups.
Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphtyl, adamantyl and norbomyl groups as well as the following groups. In each of the formulae, * represents a binding position.




Examples of groups combining the alkyl group and the alicyclic hydrocarbon group include methylcyclohexyl, dimethylcyclohexyl, methylnorbornyl, cyclohexylmethyl, adamantylmethyl and norbornyletyl groups.
Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups.
Examples of groups combining the alkyl group and the aromatic hydrocarbon group include an aralkyl group such as benzyl group.
Examples of the alkanediyl group for La1 include linear alkanediyl groups such as ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, propane-1,1-diyl and propane-2,2-diyl groups; and branched alkanediyl groups such as propane-1,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl groups.
Ra7 preferably represents a hydrogen atom.
Ra8 and Ra9 are independently preferably a methyl group.
Ra10 is preferably a C1 to C4 alkoxy group, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.
m′ represents preferably 0 or 1, more preferably 0.
Ra11 represents preferably a C1 to C6 primary or secondary alkyl group.
La1 represents preferably a C2 to C4 alkanediyl group such as ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl and butane-1,4-diyl groups, more preferably an ethane-1,2-diyl group.
n represents preferably an integer of 1 to 10.
Ra12 represents preferably a C1 to C3 primary or secondary alkyl group.
Examples of the structural unit represented by formula (a2-1) preferably include those represented by formulae (a2-1-1), (a2-1-2), (a2-1-3) and (a2-1-4). The monomer which derives the structural unit (a1) is preferably monomers described in JP2010-204634A1.




Examples of the monomers which derive the structural units represented by formula (a2-2) include alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate and hexyl(meth)acrylate;
cycloalkyl(meth)acrylates such as cyclopentyl(meth)acrylate and cyclohexyl(meth)acrylate;
polycyclic(meth)acrylates such as adamantyl(meth)acrylate, and
aryl(meth)acrylates such as phenyl(meth)acrylate and benzyl(meth)acrylate.
Examples of the monomers which derive the structural units represented by formula (a2-3) include (meth)acrylates such as ethylene glycol monomethyl ether(meth)acrylate, ethylene glycol monoethyl ether(meth)acrylate, ethylene glycol monopropyl ether(meth)acrylate, ethylene glycol monobuthyl ether(meth)acrylate, diethylene glycol monomethyl ether(meth)acrylate, triethylene glycol monomethyl ether(meth)acrylate, tetraethylene glycol monomethyl ether(meth)acrylate, pentaethylene glycol monomethyl ether(meth)acrylate, hexaethylene glycol monomethyl ether(meth)acrylate, nonaethylene glycol monomethyl ether(meth)acrylate, and octaethylene glycol monomethyl ether(meth)acrylate.
Further, examples of the monomers which derive the structural units represented by formula (a2) include acrylic acid, methacrylic acid, crotonic acid, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene and 4-isopropoxystyrene.
Examples of the structural unit (a2) may include a structural unit represented by formula (a2-4). The structural unit is sometimes referred to as “structural unit (a2-4)”.




(a2-4)
In the formula, Ra13 represents a hydrogen atom or a methyl group,
Ra14 in each occurrence independently represent a C1 to C6 alkyl group or a C1 to C6 alkoxy group,
Ra15 in each occurrence independently represent a primary or a secondary C1 to C12 hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, provided that the methylene group bonding to an oxygen atom may not be replaced by an oxygen,
m′′ represents an integer of 0 to 4, and
m′′′ represents an integer of 0 to 4,
provided that the total number of m′′ and m′′′ is 5 or less.
The hydrocarbon group for Ra15 is a group in which the carbon atom bonding to an oxygen atom is not a tertiary carbon atom, that is, the carbon atom bonding to an oxygen atom has at least one atom other than the carbon atom such as a hydrogen atom.
The structural unit represented by formula (a2-4) does not include the structural unit (I) and the structural unit (a1-2).
Examples of the alkyl group and the alkoxy group for Ra14 are the same examples as the group described in Ra10.
Examples of the hydrocarbon group for Ra15 are the same examples as the group described in Ra11.
Among them, Ra15 is preferably a C1 to C5 liner or branched alkyl group, a C5 to C10 alicyclic hydrocarbon group and phenyl groups as well as a combination thereof, or these groups where a carbon atom bonding to an oxygen atom in these groups may be replaced by a carbonyl group.
Examples of the structural unit (a2-4) include the following ones.







Examples of the structural unit (a2-4) include the structural units represented by the above formulae in which a hydrogen atom corresponding to Ra13 has been replaced by a methyl group.
When the resin (A1) has the structural units (a2-1), (a2-2), (a2-3) and (a2-4), the total content of these is preferably 1 to 30% by mole, more preferably 1 to 25% by mole, still more preferably 5 to 25% by mole, and particularly preferably 5 to 20% by mole with respect to the total structural units (100% by mole) of the resin (A1).
When the resin (A1) has the structural unit (a2), the mole ratio of the structural unit (a1):the structural unit (a2) is preferably 10:90 to 80:20, more preferably 15:85 to 60:40, and still more preferably 15:85 to 45:55.
Examples of combinations of the structural units in the resin (A1) include the following ones.























































Examples of the structural units include structural units in which a hydrogen atom corresponding to Ra5 or the like has been replaced by a methyl group, or a methyl group corresponding to Ra5 or the like has been replaced by a hydrogen atom. The resin may have both structural unit having a hydrogen atom as Ra5 and a structural unit having a methyl group as Ra5.
The resin (A1) is preferably a resin having the structural unit (a1) and the structural unit (a2), more preferably the structural units (a1-1) and/or (a1-2) and the structural unit (a2).
The resin (A1) may be a resin obtained by reacting a resin which has one or both of a carboxy group and a phenolic hydroxyl group at its side chain with a compound which has at least two vinyloxy groups, which is sometimes referred to as “resin (A1 b)”.
The resin (A1 b) is preferably a resin obtained by reacting a resin which has a phenolic hydroxyl group with a compound which has at least two vinyloxy groups. Such resin can be produced by reacting a resin which has the structural unit (a1-2) with the compound which has at least two vinyloxy groups. A novolak resin described below can be used as the resin having a phenolic hydroxyl group, and the resin (A1 b) may be produced by reacting the above described novolak resin with the compound which has at least two vinyloxy groups. The resin (A1b) may be a resin obtained by reacting the compound which has at least two vinyloxy groups with a resin mixture containing a novolak resin and a resin having the structural unit (a1-2). Further, the resin (A1 b) may be a combination of a resin which is obtained by reacting a resin having the structural unit (a1-2) with the above described the compound having at least two vinyloxy groups, with a resin which is obtained by reacting the novolak resin with the above described the compound having at least two vinyloxy groups.
In the synthesis of the resin (A1b), the mole ratio of the resin having a phenolic hydroxyl group and a carboxyl group: the compound having at least two vinyloxy groups may be 60 to 99:40 to 1, and preferably 70 to 95:30 to 5.
Specific examples of the resin (A1b) include the resins described in JP2008-134515A1 and JP 2008-46594A1.
Examples of the compound having at least two vinyloxy groups include 1,4-cyclohexanedimethanoldivinylether and ethyleneglycoldivinylether.
When the resin (A1b) contains the novolak resin as starting materials, the content thereof is 30 to 70% by mass with respect to the total mass of the resin (A1b).
The resin (A1) can be produced by polymerizing the above-mentioned monomers in a known manner such as radical polymerization.
The average weight molecule weight of the resin (A1) is preferably 8,000 or more, more preferably 10,000 or more, and preferably 600,000 or less, more preferably 500,000 or less. In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as the standard product. The detailed condition of this analysis is described in Examples.
The content of the resin (A1) in the resist composition is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 30% by mass or more, and preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 70% by mass or less, with respect to the total amount of the resin in the resist composition.
<Resin (A2)>
The alkaline-soluble resin means a resin which has an acid group and is soluble in an alkaline developer. The acid group includes a carboxy group, a sulfo group or a phenolic-hydroxy group.
The alkaline-soluble resin includes known alkaline-soluble resins in the art such as a novolak resin, a resin having polymerization units derived from a hydroxystylene, a resin having polymerization units derived from a (meth)acrylic acid and a polyalkylene glycol. The resist composition may have the resin (A2) singly or as a combination of two or more of them. Resin (A2) is preferably a novolak resin.
The novolak resin is a resin obtained by condensation of an aromatic hydrocarbon having a phenolic hydroxyl group (which is sometimes referred to as “phenolic compound”) with an aldehyde in the presence of an acidic catalyst.
Examples of the phenolic compound include phenol, o-cresol, m-cresol or p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol, 3,5-dimethoxyphenol, 2-methoxyresorcinol, 4-tert-butylcatechol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2,3,5-triethylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and a polyhydroxy triphenylmethane compound which, can be obtained by condensation of xylenol and hydroxybenzaldehyde. These may be used as a single compound or as a combination of two or more compounds.
Among them, the phenolic compound is preferably o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol.
Examples of the aldehyde include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, acrolein and croton aldehyde; alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde and furylacrolein; aromatic aldehydes such as furfural, benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde and o-, m- or p-hydroxybenzaldehyde; and aromatic aliphatic aldehydes such as phenylacetaldehyde and cinnamaldehyde. As the aldehyde, a single compound or two or more kinds of the compounds may be used.
Among them, formaldehyde is preferred in view of easy industrial availability.
Examples of the catalyst for condensation include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid; organic acid such as formic acid, acetic acid, oxalic acid, trichloroacetic acid and p-toluenesulfonic acid; divalent metal salts such as zinc acetate, zinc chloride and magnesium acetate. These may be used as a single compound or as a combination of two or more compounds.
The amount of the catalyst to be used is usually from 0.01 to 1 mole per 1 mole of aldehyde.
The condensation reaction can be carried out in a known manner. The condensation reaction can be carried out at the temperature in the range of 60 to 120° C. for 2 to 30 hours. The condensation can be carried out in the presence of a solvent such as ethyl cellosolve and methyl ethyl ketone. After condensation reaction, a water-insoluble solvent is added to the reaction mixture, as needed, the reaction mixture is washed with water, and then concentrated, whereby collecting a novolak resin.
The weight average molecular weight of the novolak resin is preferably 3,000 to 10,000, more preferably 6,000 to 9,000 and still more preferably 7,000 to 8,000. When falling within these ranges, it is possible to effectively prevent the obtained film from becoming thinned and generating remaining residues after development.
The resin having polymerization unit derived from a hydroxystylene is typically polyvinylphenol, and preferably poly-p-vinylphenol, such as a resin having the structural unit (a2-1). The polyvinylphenol can be obtained by polymerization of monomers described in JP2010-204634A1.
The resin having polymerization unit derived from a (meth)acrylic acid can be obtained by way of a known polymerization of the following ones as monomers, which may be produced from single monomers or two or more kinds of monomers. Examples of the monomer for the resin include
monomer having a carboxy group such as (meth)acrylic acid;
monomer having a hydroxy group such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth) acrylate;
monomer having multiple ether bonds, polyethylene glycol monomethyl ether (meth)aclylates such as diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, pentaethylene glycol monomethyl ether (meth)acrylates, hexa ethylene glycol monomethyl ether (meth)acrylate, heptaethylene glycol monomethyl ether (meth)acrylate, octaethylene glycol monomethyl ether (meth)acrylate, nonaethylene glycol monomethyl ether (meth acrylate).
The above monomers may be used in combination with any of the followings:
(meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate;
(meth) acrylic acid cycloalkyl esters such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;
polycyclic (meth)acrylic acid esters such as adamantyl (meth)acrylate; and
ethylene glycol monoalkyl ether (meth)acrylates such as ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate.
The content of the resin (A2) in the resist composition is preferably 10% by mass or more, and more preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 50% by mass or less, with respect to the total amount of the resin of the resist composition.
<Resin (A3)>
The resist composition of the present disclosure may further contain the resin (A3), that is an alkaline-insoluble resin, in addition to the resin (A1) and the resin (A2). Examples of the resin (A3) include a resin consisting of the structural unit having no acid-labile group.
Examples of the structural unit having no acid-labile group include the structural unit (a2) described above. Resin (A3) has the structural unit (a2) singly or as a combination of two or more structural units, preferably a combination of the structural unit (a2-1) and the structural unit (a2-4).
Examples of combinations of the structural units in the resin (A3) include the following ones.







The resin (A3) can be produced by polymerizing the above-mentioned monomers which derive the monomer (a2) in a known manner such as radical polymerization.
The weight average molecule weight of the resin (A3) is preferably 8,000 or more, more preferably 10,000 or more, and preferably 600,000 or less, more preferably 500,000 or less.
When the resist composition contains the resin (A3), the content of the resin (A3) in the resist composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less, with respect to the total amount of the resin in the resist composition.
The total content of the resins is preferably 80% by mass to 99% by mass, more preferably 90% by mass to 99% by mass, with respect to the total amount of the solid components in the resist composition.
The proportion of the solid components in the resist composition and that of the resins in the solid components can be measured with a known analytical method such as liquid chromatography and gas chromatography.
<Acid Generator (B)>
The resist composition of the disclosure contains an acid generator (B).
The acid generator is a compound which can be decomposed by light to generate an acid. The acid acts catalytically to the resin (A1) and eliminate a leaving group which is detached by contacting with an acid from the resin (A1). The acid generators may be either ionic or non-ionic one.
Examples of the non-ionic acid generator include organic halide, sulfonate esters (e.g., 2-nitrobenzoate, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyl oxyketone, diazonaphthoquinone 4-sulfonate) and sulfone (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Examples of the ionic acid generator include an onium salt containing an onium cation (e.g., adiazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt). Examples of an anions of the onium salts include a sulfonic acid anion, a sulfonylimide anion and a sulfonylmethide anion.
The acid generator includes compounds which generate an acid upon radiation, which are described in JP63-26653A1, JP 55-164824A1, JP62-69263A1, JP63-146038A1, JP63-163452A1, JP 62-153853A1, JP63-146029A1, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German patent No. 3914407 and European patent No. 126712. The acid generator is available on the market, or it can be prepared by a known method.
The non-ionic acid generator is preferably a compound which has a group represented by formula (B1):




wherein Rb1 represents a C1 to C18 hydrocarbon group in which a hydrogen atom may be replaced by a fluorine atom and in which a methylene group may be replaced by an oxygen atom or a carbonyl group.
The nitrogen atom in formula (B1) may have a double bond, although it is not illustrated therein.
The C1 to C18 hydrocarbon group may be an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a combination thereof.
Examples of the aliphatic hydrocarbon group include an alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl octyl, nonyl and decyl groups.
Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantyl groups.
Examples of the aromatic hydrocarbon group include a C6 to C18 aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl group.
The hydrocarbon group is preferably a C1 to C10 alkyl group or a C6 to C10 aromatic hydrocarbon group, and more preferably a C1 to C8 alkyl group, and still more preferably a C1 to C4 alkyl group.
Examples of the hydrocarbon group in which a methylene group has been replaced by an oxygen atom or a carbonyl group includes those represented by formulae (Y1) to (Y12), preferably those represented by formulae (Y7) to (Y9), more preferably one represented by formula (Y9):







wherein “*” represents a binding position.
Examples of the hydrocarbon group which has a fluorine atom include fluoroalkyl groups such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl and fluorodecyl groups; alicyclic fluorohydrocarbon groups such as cyclofluoropropyl, cyclofluorobutyl, cyclofluoropentyl, cyclofluorohexyl, cyclofluoroheptyl, cycloperfluorooctyl and fluoroadamantyl groups; fluoroaryl groups such as fluorophenyl, fluoronaphthyl and fluoroanthryl groups.
The hydrocarbon group which has a fluorine atom is preferably a C1 to C10 alkyl group which has a fluorine atom and a C6 to C10 aromatic hydrocarbon group which has a fluorine atom, and more preferably a C1 to C8 perfluoroalkyl group, and still more preferably a C1 to C4 perfluoroalkyl group.
Examples of the compound represented by formula (B1) include the compounds represented by formulae (b1), (b2) and (b3), preferably the compounds represented by formulae (b1) and (b2), more preferably the compounds represented by formula (b1).




In the formulae, Rb1 is as the defined above,
Rb2′, Rb3 and Rb4 in each occurrence independently represent a hydrogen atom, a C1 to C8 alkyl group or a C1 to C8 alkoxy group, and
ring Wb1 represents a C6 to C14 aromatic hydrocarbon ring or a C6 to C14 aromatic heterocyclic group; and
“x” represents an integer of 0 to 2.
Examples of the alkyl group include methyl, ethyl, propyl, butyl and pentyl groups, preferably a methyl group.
Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy groups, preferably a methoxy group.
Examples of the aromatic hydrocarbon ring include benzene, naphthalene and anthracene rings.
Examples of the aromatic heterocyclic group include a six-membered to fourteen-membered ring, which preferably includes the following ones:




Examples of the substituent which may bind to the ring Wb1 include a C1 to C5 alkyl group.
The ring Wb1 is preferably a naphthalene ring.
The compound represented by formula (b1) is preferably a compound represented by any one of formulae (b4) to (b7), more preferably a compound represented by formula (b4).




In the formulae,
Rb1 is as defined above,
Rb2, Rb5, Rb6 and Rb7 each independently represent a hydrogen atom, or a C1 to C8 alkyl group.
Examples of the compound represented by formula (b1) include preferably those represented by formulae (b1-1) to (b1-14), more preferably those represented by formulae (b1-6) and (b1-7).







Examples of the compound represented by formula (b2) include the following ones.




Examples of the compound represented by formula (b3) include the following ones.




The ionic acid generator is preferably a compound represented by formula (b8) or (b9):




wherein Ab1 and Ab2 each independently represent an oxygen atom or a sulfur atom,
Rb8, Rb9, Rb10 and Rb11 each independently represent a C1 to C10 alkyl group or a C6 to C12 aromatic hydrocarbon group, and
X1− and X2− each independently represent an organic anion.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl group and octyl groups.
Examples of the aromatic hydrocarbon groups include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-buthylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
Rb8, Rb9, Rb10 and Rb11 are each independently preferably a C6 to C12 aromatic hydrocarbon group, more preferably a phenyl group.
Examples of the organic anion for X1− and X2− include a sulfonic acid anion, a bis(alkylsulfonyl)amide anion and a tris(alkylsulfonyl)methide anion. The sulfonic acid anion is preferred, and the sulfonic acid anion represented by formula (b10) is more preferred.




In the formula,
Rb12 represents a C1 to C18 hydrocarbon group that may have a fluorine atom, and a methylene group contained in the hydrocarbon group may be replaced by an oxygen atom or a carbonyl group.
Examples of Rb12 include the same ones as the group of Rb1.
Examples of the compound represented by formula (b9) include the following ones.




Examples of the compound represented by formula (b10) include the following ones.




As the acid generator (B), a single salt or a mixture of two or more of the salts can be used.
The content of the acid generator (B) is preferably 0.3 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 parts by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less, with respect to 100 parts by mass of the whole resins.
<Compound (I)>
The compound (I) is a compound which has two or more phenolic-hydroxy groups. The compound (I) is neither resins nor polymer. In the specification, a compound having at least several hundred atoms and/or a compound having repeating units of at least tens is called a resin or a polymer, thus such compound is different from the compound (I). The compound may be a compound represented by the following:




wherein Xi represents a single bond or an oxygen atom,
A represents a C1 to C6 alkanediyl group where a methylene group may be replaced by an oxygen atom, provided that when Xi represents an oxygen atom, a methylene group bonded to Xi is not replaced by an oxygen atom,
“i1” and “i2” each independently represent an integer of 0 to 4, provided that the total number of “i1” and “i2” is 2 or more,
Ri12 and Ri13 in each occurrence independently represent a halogen atom or a C1 to C12 alkyl group,
“i3” and “i4” each independently represent an integer of 0 to 4, and
Ri1 represents a hydrogen atom or an optionally substituted C1 to C6 alkyl group, or Ri1 may be bonded to A together with a carbon atom and Xi to form an optionally substituted 5 to 12-membered saturated ring,
provided that the total number of “i1” and “i3” is 4 or less and the total number of “i1” and “i4” is 5 or less.
The compound (I) is preferably a compound represented by formula (Ia) or formula (Ib).




In the formulae, A, Ri12, Ri13 and “i1” to “i4” are as defined above,
Ri6 represents a hydrogen atom or an optionally substituted C1 to C12 alkyl group,
Ri8, Ri9, Ri10 and Ri11 each independently represent a hydrogen atom or a C1 to C9 alkyl group, or Ri8 and Ri9 may be bonded to each other to form an optionally substituted C3 to C12 saturated ring and/or Ri10 and Ri11 may be bonded to each other to form an optionally substituted C3 to C12 saturated ring.
Here, examples of the substituent for the saturated ring include a C1 to C12 alkyl group, a C1 to C12 alkenyl group, a C3 to C12 cycloalkyl group and a C5 to C18 aryl group.
The compound represented by formula (Ib) is preferably a compound represented by formula (Ib-1).




In the formulae, Ri12, Ri13 and “i1” to “i4” are as defined above,
Ri14 and Ri15 in each occurrence independently represent a C1 to C12 alkyl group, a C1 to C12 alkenyl group, a C3 to C12 cycloalkyl group or a C5 to C18 aryl group,
“i5” represents an integer of 0 to 4, and
“i6” represents an integer of 0 to 5.
Examples of each group in formulae (I), (Ia), (Ib) and (Ib-1) are described as follow.
The alkanediyl group may be any of a chain alkanediyl group and a branched alkanediyl group. Examples of the alkanediyl group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methyl-propane-1,3-diyl, 2-methyl-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl groups.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
Examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl and hexenyl groups.
The cycloalkyl group may be any of monocyclic or polycyclic group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl and cyclododecyl groups.
Examples of the aryl group include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
In the formulae, A represents preferably a methylene group, Ri1 represents preferably a hydrogen atom or a methyl group, more preferably a methyl group, Ri12 and Ri13 each independently represent preferably a methyl or ethyl group, more preferably a methyl group, the total number of “i1” and “i2” is preferably 3 or 4, more preferably 4. Ri8 and Ri9 each independently represent preferably a C1 to C4 alkyl group, and also preferably represent together an optionally substituted C5 to C6 saturated hydrocarbon ring. Ri10, Ri11 and Ri14 each independently represent a hydrogen atom or a methyl group. In the formula (Ia), “i3” to “i5” is each independently preferably 0 to 2.
In formula (Ib-1), “i3” to “i5” is independently preferably 0 or 1, more preferably 0, and “i6” is preferably 0.
Examples of the compound (I) include the following ones.













As the compound (I), the compound described in JPH03-191351A1 and JPH08-99922A1 can be used. Further, the compound (I) can be synthesized by way of a known method. As the compound (I), available products on the market and compound synthesized by way of a known method can be used. The resist composition may contain a single compound or a combination of two or more compounds as the compound (I).
The average molecular weight of the compound (I) is generally 200 to 800.
The content of the compound (I) is preferably 1 parts by mass or more, and more preferably 3 parts by mass or more, preferably 10 parts by mass or less, and more preferably 8 parts by mass or less with respect to 100 parts by mass of the whole resins.
<Solvent (D)>
There is no particular limitation on the solvent (D) as along as it dissolves the components contained in the resist composition of the disclosure, examples of the solvent includes a glycol ether ester such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; a glycol ether such as propylene glycol monomethyl ether; an ester such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; a ketone such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; a lactone such as γ-butyrolactone; and a combination thereof.
The content of the solvent is usually 40 to 75% by mass, preferably 45 to 70% by mass, and more preferably 50 to 68% by mass with respect to total amount of the resist composition of the disclosure. With this range, the resist composition layer having a thickness of about 3 to 150 μm can easily be formed when producing a resist pattern.
<Quencher (C)>
The resist composition of the disclosure preferably further contains a quencher.
The quencher is a compound having a property trapping an acid generated from the acid generator by exposure of light. Examples of the quencher include a basic nitrogen-containing organic compound.
Examples of the basic nitrogen-containing organic compound include an amine compound such as an aliphatic amine and an aromatic amine, and an ammonium salt. Examples of the aliphatic amine include a primary amine, a secondary amine and a tertiary amine.
Examples of amine compounds include those represented by the formulae (C1) and (C2).




In the formula, Rc1, Rc2 and Rc3 each independently represent a hydrogen atom, a C1 to C6 alkyl group, a C5 to C10 alicyclic hydrocarbon group or a C6 to C10 aromatic hydrocarbon group, and a hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by a hydroxy group, an amino group or a C1 to C6 alkoxy group, and a hydrogen atom contained in the aromatic hydrocarbon group may be replaced by a C1 to C6 alkyl group, a C1 to C6 alkoxy group or a C5 to C10 alicyclic hydrocarbon group.
Examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, an alkoxy group and an alkanediyl group include the same examples as the group described above.
Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, methyldipentylamine, dihexylmethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, tris[2-(2-methoxyethoxyl)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino-3,3′-diethyldiphenylmethane. Among them, preferred is diisopropylaniline, and more preferred is 2,6-diisopropylaniline.




In the formula, the ring W1 represents a nitrogen-containing heterocyclic ring, or a benzene ring having a substituted or unsubstituted amino group, and a hydrogen atom contained in the heterocyclic ring and benzene ring may be replaced by a hydroxy group or a C1 to C4 alkyl group;
A1 represents a phenyl group or a naphthyl group, and
“nc” represents an integer of 2 or 3.
The substituted or unsubstituted amino group is represented by —N(Rc4)(Rc5), where Rc4 and Rc5 each independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C10 alicyclic hydrocarbon group or a C6 to C14 aromatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, butyl, pentyl, hexyl, heptyl and octyl groups.
Examples of the alicyclic hydrocarbon group include the same examples as the group described for Ra1, Ra2 and Ra3 in the formula (1), and examples of the aromatic hydrocarbon group include the same examples as the group described for Ra1′, Ra2′ and Ra3′ in the formula (2), described above.
The nitrogen-containing heterocyclic ring is any of an aromatic or non-aromatic ring, or a ring having a hetero atom other than a nitrogen atom such as an oxygen atom and a sulfur atom. The hetero ring may have 1 to 3 nitrogen atom(s). Examples of the hetero ring include a ring represented by any one of formulae (Y13) to (Y28). In each ring of the formulae, he position where one hydrogen atom has been removed therefrom is a binding position to A1.







The ring W1 is preferably a nitrogen-containing heterocyclic ring, more preferably a 5- or 6-membered aromatic heterocyclic ring having a nitrogen atom in its ring, and still more preferably a ring represented by any one of formulae (Y20) to (Y25).
The compound represented by formula (C2) includes those represented by formulae (C2-1) to (C2-11), preferably those represented by formulae (C2-2) to (C2-8).







The content of the quencher is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, still more preferably 0.001 to 3% by mass, further still preferably 0.01 to 1.0% by mass, and particularly preferably 0.1 to 0.70% by mass with respect to the total amount of solid components of the resist composition.
<Adhesion Improver (E)>
There is no particular limitation on the adhesion improver (E) as along as corrosion of a metal such as aluminum and copper used in a substrate, wiring, or the like can be prevented. An effect of preventing rusting is exhibited by prevention of corrosion of the metal. Furthermore, in addition to those effects, it is possible to enhance the adhesive characteristics between the resist composition and the substrate or the metal.
The adhesion improver (E) may include a sulfur-containing compound, an aromatic hydroxyl compound, a benzotriazol compound, a triazine compound and a silicon-containing compound. These may be used as a single compound or as a combination of two or more compounds.
The sulfur-containing compound may include a compound that has a sulfide bond and/or a mercapto group. The sulfur-containing compound may be a chain compound or a compound having a ring structure.
Examples of the chain compound include dithiodiglycolic glycerol [S(CH2CH(OH)CH2(OH))2], bis (2,3-dihydroxypropylthio)ethylene [CH2CH2 (SCH2CH(OH)CH2(OH))2], 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonic acid sodium salt [CH2(OH)CH(OH)CH2SCH2CH(CH3)CH2SO3Na], 1-thioglycerol [HSCH2CH(OH)CH2(OH)], 3-mercapto-1-propanesulfonic acid sodium salt [HSCH2CH2CH2SO3Na], 2-mercaptoethanol [HSCH2CH2(OH)], thioglycolic acid [HSCH2CO2H], 3-mercapto-1-propanol [HSCH2CH2CH2].
The sulfur-containing compound is preferably a compound that has a sulfide bond and a mercapto group, more preferably a heterocyclic compound that has a sulfide bond and a mercapto group. There is no particular limitation on how many sulfide bonds and mercapto groups are presented in the sulfur-containing compound, as long as both of these groups are presented respectively therein.
The heterocyclic ring may be a monocyclic or a polycyclic ring, and the ring may be a saturated or an unsaturated ring. The heterocyclic ring preferably has a hetero atom other than a sulfur atom. Examples of the hetero atom include an oxygen atom and a nitrogen atom, and preferably a nitrogen atom.
The heterocyclic ring has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms.
The heterocyclic ring is preferably a monocyclic ring or an unsaturated ring, and more preferably a monocyclic unsaturated ring.
Examples of the heterocyclic ring include the following ones.




The sulfur-containing compound may be a polymer. The polymer preferably has a structural unit which has a sulfide bond and a mercapto group in its side chain. A structure having a sulfide bond and a mercapto group (which is sometimes referred to as “unit (1)”) and a main chain are preferably bonded together with a linking group such as an amido bond, an ether bond, a thioether bond and ester bond.
The polymer may be a homopolymer or a copolymer.
When the polymer is a copolymer, the copolymer may have the structural unit (a1) and/or the structural unit (a2) described above.
The weight average molecular weight of the polymer is usually 3,000 or more, preferably 5,000 or more, while it is usually 100,000 or less, and preferably 50,000 or less.
When the sulfur-containing compound is a polymer, the content of the structural unit which has a sulfide bond and a mercapto group is usually 0.1 to 50% by mole, preferably 0.5 to 30% by mole, and more preferably 1 to 20% by mole with respect to the total structural units of the polymer.
The sulfur-containing compound is preferably a compound represented by formula (IA) or a polymer having a structural unit represented by formula (IB):




wherein Ri1 represents a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group, a C6 to C14 aromatic hydrocarbon group, —SR11 or —N(R12)(R13);
R11, R12 and R13 each independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C10 alicyclic hydrocarbon group, a C6 to C14 aromatic hydrocarbon group or a C1 to C12 acyl group and a hydrogen atom contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group or the acyl group may be replaced by a hydroxy group;
Ri2 and Ri3 in each occurrence independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C14 aromatic hydrocarbon group;
A and B each independently represent a nitrogen atom or a carbon atom; and
“n1” and “m1” each independently represent 0 or 1,
provided that n is 0 when A is a nitrogen atom, n is 1 when A is a carbon atom, m is 0 when B is a nitrogen atom, and m is 1 when B is a carbon atom.
Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
Examples of the aromatic hydrocarbon group include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
The alicyclic hydrocarbon group may be any one of a monocyclic or polycyclic group, examples of the alicyclic hydrocarbon group include a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl group, and the polycyclic alicyclic hydrocarbon group such as decahydronaphthyl, adamantyl and norbornyl groups.
R11 is preferably an aliphatic hydrocarbon group or an acyl group, R12 and R13 are each independently preferably a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an acyl group.
Examples of the acyl group include acetyl, propionyl, butyryl, valeryl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, decylcarbonyl, dodecylcarbonyl and benzoyl groups.
Ri1 is more preferably a hydrogen atom or a mercapto group.
Ri2 and Ri3 is each independently preferably a hydrogen atom or a C1 to C4 alkyl group, and more preferably a hydrogen atom.
At least one of A and B is preferably a nitro atom, and both of them are more preferably nitrogen atoms.




In the formula, Ri21 and Ri31 in each occurrence independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C14 aromatic hydrocarbon group,
A1 and B1 each independently represent a nitrogen atom or a carbon atom,
Ri4 represents a hydrogen atom or a methyl group,
Xi1 represents a sulfur atom or a NH group,
Li1 represents a C1 to C20 divalent hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and
“n2” and “m2” each independently represent 0 or 1,
provided that “n2” is 0 when A1 is a nitrogen atom, “n2” is 1 when A1 is a carbon atom, “m2” is 0 when B1 is a nitrogen atom and/or “m2” is 1 when B1 is a carbon atom.
Examples of aliphatic hydrocarbon group for Ri21 and Ri31 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, preferably a C1 to C4 alkyl group.
Examples of the aromatic hydrocarbon group for R′21 and Ri31 include an aryl group such as phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl and 2-methyl-6-ethylphenyl groups, and preferably a C6 to C10 aryl group.
The alicyclic hydrocarbon group for Ri21 and Ri31 may be any one of a monocyclic or polycyclic group, examples of the alicyclic hydrocarbon group include a cycloalkyl group such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl group, and the polycyclic alicyclic hydrocarbon group such as decahydronaphthyl, adamantyl and norbornyl groups, and preferably a C5 to C10 alicyclic hydrocarbon group.
Ri21 and Ri31 are each independently preferably a hydrogen atom or a C1 to C4 alkyl group.
Examples of the divalent hydrocarbon group for Li1 include an alkanediyl group such methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-iyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl;
a divalent monocyclic saturated alicyclic hydrocarbon group, i.e., a cycloalkanediyl group such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cycloalkanediyl such as cyclooctane-1,5-diyl groups;
a divalent polycyclic saturated alicyclic hydrocarbon group such as a norbomane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups;
an arylene group such as phenylene, tolylene and naphthylene groups.
Li1 is preferably a C2 to C14 alkanediyl group having an ester bond or a combination of a C6 to C10 arylene group with a C1 to C11 alkanediyl group.
The structural unit represented by formula (IB) is preferably one represented by formula (IB-1) or formula (IB-2).




In the formulae, Ri22 and Ri32 each independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C14 aromatic hydrocarbon group;
A2 and B2 each independently represent a nitrogen atom or a carbon atom;
Ri5 represents a hydrogen atom or a methyl group;
Xi11 represents a sulfur atom or an NH group;
Li2 represents a C1 to C18 divalent hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group, and
“n3” and “m3” each independently represent 0 or 1,
provided that “n1” is 0 when A2 is a nitrogen atom, “n1” is 1 when A2 is a carbon atom, “m1” is 0 when B2 is a nitrogen atom and“m1” is 1 when B2 is a carbon atom;
Ri23 and Ri33 each independently represent a hydrogen atom, a C1 to C10 aliphatic hydrocarbon group, a C3 to C18 alicyclic hydrocarbon group or a C6 to C14 aromatic hydrocarbon group;
A3 and B3 each independently represent a nitrogen atom or a carbon atom;
Ri7 represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group;
Xi12 represents a sulfur atom and an NH group;
Li3 represents a C1 to C14 divalent hydrocarbon group where a methylene group may be replaced by an oxygen atom or a carbonyl group; and
“n4” and “m4” each independently represent 0 or 1,
provided that “n4” is 0 when A3 is a nitrogen atom, “n4” is 1 when A3 is a carbon atom, “m4” is 0 when B3 is a nitrogen atom, and/or “m4” is 1 when B3 is a carbon atom.
Examples of the C1 to C10 aliphatic hydrocarbon group for Ri22, Ri32, Ri23 and Ri33 each independently include the same ones as the group of Ri21 and Ri31.
Examples of the C6 to C14 aromatic hydrocarbon group for Ri22, Ri32, Ri23 and Ri33 each independently include the same ones as the group of Ri21 and Ri31.
Examples of the C3 to C18 alicyclic hydrocarbon group for Ri22, Ri32, Ri23 and Ri33 each independently include the same ones as the group of Ri21 and Ri31.
Examples of the C1 to C18 divalent hydrocarbon group for Li2 include an alkanediyl group such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diy, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl;
a divalent monocyclic saturated alicyclic hydrocarbon group, i.e., cycloalkanediyl group such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cycloalkanediyl such as cyclooctane-1,5-diyl groups;
a divalent polycyclic saturated alicyclic hydrocarbon group such as a norbornane-1,4-diyl, norbomane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups.
Li2 is preferably a C1 to C14 alkanediyl group, and more preferably a C1 to C11 alkanediyl group.
Examples of the C1 to C14 divalent hydrocarbon group for Li3 include an alkanediyl group such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diy, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methyl propane-1,2-diyl, pentane-1,4-diyl and 2-methyl butane-1,4-diyl;
a divalent monocyclic saturated alicyclic hydrocarbon group, i.e., cycloalkanediyl group such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cycloalkanediyl such as cyclooctane-1,5-diyl groups;
a divalent polycyclic saturated alicyclic hydrocarbon group such as a norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2,6-diyl groups.
Li3 is preferably a C1 to C14 alkanediyl group, and more preferably a C1 to C11 alkanediyl group.
Li3 is preferably bonded to a phenylene group so as to form a para-position with respect to a main chain.
Examples of the sulfur-containing compound include compounds represented by formulae (I-1) to (I-26), among them, those represented by formulae (I-1) to (I-13) are preferred, and those represented by formulae (I-1), (I-4) and (I-11) are more preferred.










Example for the sulfur-containing compound include a homopolymer and a copolymer which has at least one of the structural unit represented by any one of formulae (I-27) to (I-38), a copolymer which has at least one of the structural unit represented by any one of formulae (I-27) to (I-36) are preferred, a copolymer which has the structural unit represented by formula (I-33) is more preferred.













Example of such copolymer include a copolymer represented by formulae (I-39) to (I-48), and a copolymer represented by formulae (I-39) to (I-44) are preferred.













The sulfur-containing compound may be synthesized by a known method (for example, these disclosed in JP2010-79081A1), or may be available product on the market. The polymer that is a sulfur-containing compound may be available product on the market (for example, bismuthiol, manufactured by Tokyo Chemical Industry Co., Ltd.), or may be synthesized by a known method (for example, that disclosed in JP2001-75277A1).
Examples of the aromatic hydroxy compound include phenol, cresol, xylenol, pyrocatechol (=1,2-dihydroxybenzene), tert-butyl catechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzene triol, salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxy benzyl alcohol, p-hydroxy phenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol, amino resorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic benzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and gallic acid.
Examples of the benzotriazole compound include a compound represented by formula (IX):




wherein R1 and R2 each independently represent a hydrogen atom, an optionally substituted C1 to C10 hydrocarbon group, a carboxyl group, an amino group, a hydroxyl group, a cyano group, a formyl group, a sulfonyl alkyl group or a sulfone group.
Q represents a hydrogen atom, a hydroxyl group, an optionally substituted C1 to C10 hydrocarbon group, an aryl group or **—R3—N(R4)—R5, the hydrocarbon group may has an amide bond or an ester bond,
R3 represents an alkanediyl group,
** represents a binding position with a nitrogen atom included the ring, and
R4 and R5 each independently represent a hydrogen atom, a hydroxyl group, a C1 to C6 alkyl group, a C1 to C6 hydroxyalkyl group or a C1 to C6 alkoxyalkyl group.
The hydrocarbon group for R1, R2 and Q may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may have a saturated and/or unsaturated bond.
The aliphatic hydrocarbon group is preferably an alkyl group. Examples of the alkyl group include methyl, ethyl, n propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, methylpentyl, n-hexyl and n-heptyl groups.
The aromatic hydrocarbon group is preferably an aryl group. Examples of the aryl group include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantyl-phenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl, phenanthryl, 2, 6-diethylphenyl and 2-methyl-6-ethylphenyl groups.
Examples of the alkanediyl group for R3 include the same ones as the group described above.
Examples of the substituent for the hydrocarbon group include a hydroxyl alkyl and an alkoxyalkyl groups.
Examples of the hydroxylalkyl group include hydroxymethyl and hydroxyethyl groups.
Examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl and dimethoxyethyl groups.
When the resist composition of the disclosure is applied to a substrate that includes copper layer, it is preferred to use a compound in which Q in formula (IX) is **—R3—N(R4)(R5). Among them, although the benzotriazole compound in which Q is **—R3—N(R4)(R5) and at least one of R4 and R5 is a C1 to C6 alkyl group exhibits reduced solubility in water when at least one of R4 and R5 is a C1 to C6 alkyl group, the compound is preferably used provided that another component capable of dissolving the compound is present therein.
When the resist composition of the disclosure is applied to a substrate that has an inorganic material layer (for example, polysilicon film and amorphous silicon film), Q in formula (IX) is preferably a water soluble group, and more specifically a hydrogen atom, a C1 to C3 alkyl group, a C1 to C3 hydroxyalkyl group or a hydroxyl group. In this manner, the anticorrosive properties of the substrate are effectively exerted.
Examples of the benzotriazole compounds include benzotriazole, 5,6-dimethyl benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethyl benzotriazole, 1-benzotriazole carboxylic acid methyl ester, 5-benzotriazole carboxylic acid, 1-methoxy-benzotriazole, 1-(2,2-dihydroxy-ethyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, or 2,2′-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2′-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2′-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethane and 2,2′-{[(4-methyl-1H-benzotriazole-1-yl) methyl]imino}bispropane which are available on the market from Ciba Specialty Chemicals as “Irgamet” series.
Examples of the triazine compound include a compound represented by formula (II):




wherein R6, R7 and R8 each independently represent a halogen atom, a hydrogen atom, a hydroxy group, an amino group, a mercapto group, an optionally substituted C1 to C10 hydrocarbon group, an optionally substituted C1 to C10 alkoxy group or an amino group substituted with a C1 to C10 hydrocarbon group.
Examples of the halogen atom include a fluorine, chlorine, bromine and iodine atoms.
Examples of the hydrocarbon group and an alkyl group include the same ones as the group described above.
Examples of triazine compounds include 1,3,5-triazine-2,4,6-trithiol.
Examples of the silicon-containing compound include a compound represented by formula (IIA):




wherein Rj1 represents a C1 to C5 aliphatic hydrocarbon group or a C1 to C5 mercaptoalkyl group,
Rj2 to Rj4 each independently represent a C1 to C5 aliphatic hydrocarbon group, a C1 to C5 alkoxy group, a mercapto group or a C1 to C5 mercaptoalkyl group, at least one of Rj2 to Rj4 is a mercaptoalkyl group or a C1 to C5 mercapto group, and
ti represents an integer of 1 to 10.
Examples of the aliphatic hydrocarbon group include an alkyl group such as methyl, ethyl, propyl butyl and pentyl groups
Examples of the alkoxy group include methoxy and ethoxy groups.
Examples of the mercapto alkyl group include methylmercapto, entylmercapto and puropylmercapto groups.
Rj1 is preferably a C1 or C2 aliphatic hydrocarbon group and a C1 to C3 mercaptoalkyl group, and more preferably a methyl group or a mercaptopropyl group.
Rj2 to Rj4 are each independently preferably a C1 or C2 aliphatic hydrocarbon group, a C1 or C2 alkoxy group, and more preferably a methyl group and a methoxy group. At least one of these is preferably a mercapto group or a C1 to C3 mercaptoalkyl group, and more preferably a mercapto group or a mercaptopropyl group.
Rj2 and Rj3 may be the same or different from each other, and are preferably the same in view of productivity,
Examples of the compound represented by formula (IIA) include the compounds represented by formula (II-1) to formula (II-7).




Among them, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane are preferred.
The content of the adhesion improver (E) is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more, especially preferably 0.008% by mass or more, and preferably 20 by mass % or less, more preferably 10% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, especially preferably 1% by mass or less, more preferably especially 0.1% by mass or less, with respect to the total amount of the solid content of the resist composition. The resist composition within this range can form a resist pattern with high accuracy, ensuring the adhesion between the resist pattern and the substrate.
<Other Component (which is Sometimes Referred to as “Other Component (F)”)>
The resist composition of the disclosure may contain other components, as needed. Examples of the other component (F) include various additives known in the art such as surfactants, sensitizers, dissolution inhibitors, stabilizers and dyes.
When the other component (F) is used, the content may be adjusted depending upon the kinds thereof.
<Preparing the Resist Composition>
The resist composition can usually be prepared by mixing the resin (A1), the acid generator (B), the compound (I) and the solvent (D) as well as the resin (A2), the resin (A3), the quencher (C), the adhesion improver (E) and/or other component (F), as needed.
There is no particular limitation on the order of mixing. The temperature of mixing may be adjusted within the range of 10 to 40° C. depending on the kinds of the resin and solubility to the solvent. The time of mixing may be adjusted within the range of 0.5 to 24 hours depending on temperature during mixing. There is no particular limitation to the tool for mixing. An agitation mixing may be used.
After mixing the above components, the mixture is preferably filtrated through a filter having about 0.11 to 50 μm pore diameter.
<Method for Producing Resist Pattern>
The method for producing a resist pattern of the disclosure includes the steps of:
(1) applying the resist composition of the disclosure onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer; and
(4) developing the exposed composition layer.
In the step (1), the applying of the composition on a substrate is usually conducted using a conventional apparatus such as spin coater. Examples of the substrate include silicon wafers. A substrate on which semiconductor elements (e.g., a transistor, a diode) has been formed in advance can be used for the process. When the resist composition is to be used for bump formation, a substrate on which a conductive material has been laminated is preferred. Examples of the conductive material include a metal such gold (Au), copper (Cu), nickel (Ni), tin (Sn), palladium (Pd), and silver (Ag), and an alloy which contains one or more of these metals. Copper and an alloy containing copper are preferred.
The substrate may be washed or coated with an anti-reflecting layer. For forming the anti-reflecting layer, a composition for an organic anti-reflecting layer as available on the market can be used.
In the step (2), the composition layer is usually formed on the substrate by drying the applied composition to remove the solvent therefrom. The drying is carried out with a heating apparatus such as hot plate (i.e., prebake) for a heat drying, a decompressor for a decompression drying, or a combination thereof.
The temperature is preferably 50 to 200° C., and the operation pressure is preferably 1 to 1.0×105 Pa.
The thickness of the film obtained by step (2) is in the range of preferably 3 to 150 μm, more preferably 4 to 100 μm.
In the step (3), the film is preferably exposed to light using an exposure system. The exposure is usually carried out through a mask having a pattern corresponding to a desired resist pattern. The exposure source can be selected depending on resolution of the intended resist pattern, examples of the exposure source preferably include known one such as a light source emitting a light of 345 to 436 nm of wavelength or a light source emitting a light of 345 to 400 nm of wavelength, more preferably g ray (wavelength: 436 nm), h ray (wavelength: 405 nm) and i ray (wavelength: 365 nm).
The process may further has baking the exposed film, so called post-exposure bake, after the step (3), preferably heating with a heating apparatus. The baking the exposed film can be carried out with heating means such as hot plates. The temperature of baking the exposed film is preferably 50 to 200° C., and more preferably 60 to 120° C. The time of baking is usually 40 to 400 seconds, preferably 50 to 350 seconds.
In the step (4), the development of the exposed resist composition layer is usually carried out. When heating has been carried out, the development of the baked resist composition layer is usually carried out. An alkaline developer is usually used for the development.
Examples of the alkaline developer include an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as “choline”).
After development, the formed resist pattern is preferably washed with ultrapure water, and the remained water on the resist pattern and the substrate is preferably removed.
<Application>
The resist composition of the disclosure contains the resin (A1), the resin (A2), the acid generator (B) and the solvent (D) is useful for forming a thick film, in particular, for forming a resist film having 3 to 150 μm-thick
Further, the resist composition is useful for producing bumps. When the bump is formed using the resist composition, bumps can be produced by the process including the following steps;
laminating a conductive material (seed metal) on a wafer which has semiconductor elements thereon to form a conductive film,
producing a resist pattern on the conductive film from the composition of the disclosure,
plating an electrode material such as Cu, Ni or solder, using the resist pattern as its mold, and
removing the resist film and the conductive film under the resist film by etching or the like, whereby forming the bumps. The electrode material which has been melted by heating after removing the conductive film may be used as a bump, as needed.
EXAMPLE
The disclosure will be described more specifically by way of examples, which are not construed to limit the scope of the disclosure.
All percentages and parts expressing the content or amounts used in the Examples and Comparative Examples are based on mass, unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography.
Apparatus: HLC-8120GPC type (Tosoh Co. Ltd.)
Column: TSK gel Multipore HXL-M×3+guardcolumn (Tosoh Co. Ltd.)
Eluant: tetrahydrofuran
Flow rate: 1.0 mL/min
Detecting device: RI detector
Column temperature: 40° C.
Injection amount: 100 μL
Standard material for calculating molecular weight: standard polystyrene (Tosoh Co. ltd.)
Synthesis Example 1: Synthesis of Resin A1-1
Forty five parts of polyvinylphenol (Trade name VP-8000, Product of Nippon Soda Co., Ltd.) were dissolved in 540 parts of methylisobutylketone, followed by concentrating it with an evaporator. To a four-necked flask with a stirring device, a reflux condenser and a thermometer, the concentrated resin solution and 0.005 parts of p-toluenesulfonic acid monohydrate were poured and then 10.96 parts of cyclohexylvinylether was dropped thereinto at a temperature of 20 to 25° C. over 15 minutes. The obtained mixture was stirred at the above-mentioned temperature for 3 hours and then diluted with 21 parts of methylisobutylketone, followed by washing it with 425 parts of ion-exchanged water four times to obtain an organic layer. The washed organic layer was concentrated until its amount became 110 parts using an evaporator, and 300 parts of propyleneglycolmonomethylether acetate were added thereto, followed by concentrating it again to obtain 125 parts of propyleneglycolmonomethylether acetate solution (39% of solid content) of resin A1-1. The weight average molecular weight of the resin was 1.57×104. In the resin the introduction rate of cyclohexyloxy ethoxy group was 21.0%. Resin A1-1 had the following structural units.




Synthesis Example 2: Synthesis of Resin A1-2
Forty five parts of polyvinylphenol (Trade name VP-8000, Product of Nippon Soda Co., Ltd.) were dissolved in 540 parts of methylisobutylketone, followed by concentrating it with an evaporator. To a four-necked flask with a stirring device, a reflux condenser and a thermometer, the concentrated resin solution and 0.005 parts of p-toluenesulfonic acid monohydrate were poured and then 15.69 parts of cyclohexylvinylether was dropped thereinto at a temperature of 20 to 25° C. over 15 minutes. The obtained mixture was stirred at the above-mentioned temperature for 3 hours and then diluted with 21 parts of methylisobutylketone, followed by washing it with 430 parts of ion-exchanged water four times to obtain an organic layer. The washed organic layer was concentrated until its amount became 120 parts using an evaporator, and 340 parts of propyleneglycolmonomethylether acetate were added thereto, followed by concentrating it again to obtain 136 parts of propyleneglycolmonomethylether acetate solution (40% of solid content) of resin A1-2. The weight average molecular weight of the resin was 1.83×104. In the resin, the introduction rate of cyclohexyloxy ethoxy group was 30.0%. Resin A1-2 had the following structural units.




Synthesis Example 3: Synthesis of Resin A1-3
20 parts of polyvinylphenol [VP-15000; manufactured by Nippon Soda] was dissolved in 240 parts of methylisobutylketone and the obtained solution was concentrated using an evaporator. The concentrated resin solution and 0.003 parts of p-toluenesulfonic acid dihydrate were charged into a four-necked flask provided with a reflux condenser tube, a stirrer and a thermometer. The temperature was maintained at 20 to 25° C. and 5.05 parts of ethyl vinyl ether was dropped over 10 minutes into the resulting mixture. The mixture was continuously stirred for two hours while maintaining the same temperature. The resulting reaction mixture was diluted with 200 parts of methylisobutylketone and separation-washed five times in ion-exchanged water. The resulting organic layer was concentrated to 45 parts using an evaporator, 150 parts of propylene glycol monomethyl ether acetate were added and re-concentration was carried out to obtain 78 parts of a propylene glycol monomethyl ether acetate solution of resin A1-3 (solid component 29%). The weight average molecular weight of the resin A1-3 was 2.21×104. In the resin, the introduction rate of ethoxyethyl groups was 38.5%. The resin A1-3 had the structural units as shown below.




Synthesis Example 4: Synthesis of Resin A1-4
120 g of phenol novolak resin (PSM-4326 manufactured by Gun Ei Chemical Industry) was charged into a flask and dissolved in 960 g of methylisobutylketone. The obtained phenol novolak resin solution was washed 5 times with ion-exchanged water. The resulting resin solution was concentrated to 327.3 g. The resin concentration of the resin solution was 35.2%.
A portion, 56.8 g of the resulting resin solution obtained above (unit molecular weight: 189 mmol), 76.52 g of methyl isobutyl ketone and 3.6 mg of p-toluensulfonic acid hydrate (0.0189 mmol) were charged into a flask. 6.54 g of ethyl vinyl ether (0.0907 mmol) was dropped into the resin solution, and then react was conducted for three hours at room temperature. Then ion-exchanged water was added to the reaction solution and stirred, and allowed to stand, followed by separating an organic layer therefrom. Washing by use of the ion-exchanged water was conducted four times, for the total of five times. Thereafter, the organic layer was removed and concentrated. Then, propylene glycol monomethyl ether acetate was added thereto for azeotropic removal of the aqueous fraction and methyl isobutyl ketone, and the obtained organic layer was concentrated again to obtain 59.77 g of resin solution. The resulting liquid was a solution of a resin in which the hydroxyl groups of the phenyl novolak resin had been partially 1-ethoxyethylated. When the resin was analyzed using 1H-NMR, 36.3% of hydroxyl groups were found to be 1-ethoxyethylated. The concentration of the resin solution was measured using a dry mass reduction method and found to be 38.8%. The resin was referred to as be resin A1-4. The weight average molecular weight of the novolak resin A1-4 was 5.1×103.




Synthesis Example 5: Synthesis of Resin A1-5
80 g of phenol novolak resin (PSM-4326 manufactured by Gun Ei Chemical Industry) was charged into a flask and dissolved in 640 g of methylisobutylketone. The obtained phenol novolak resin solution was washed 5 times with ion-exchanged water. The resulting resin solution was concentrated to 218 g. The resin concentration of the resin solution was 35.2%.
56.8 g of the resin solution obtained above (unit molecular weight: 189 mmol), 76.52 g of methyl isobutyl ketone and 3.6 mg of p-toluensulfonic acid hydrate (0.0189 mmol) were charged into a flask. 9.14 g of cyclohexyl vinyl ether (72.5 mmol) was dropped into the resin solution, and then the reaction was conducted for three hours at room temperature. After that, ion-exchanged water was added to the reaction solution and stirred, allowed to stand, followed by separating an organic layer therefrom. Washing by use of the ion-exchanged water was conducted four times, for the total of five times. Thereafter, the organic layer was removed and concentrated. Then, propylene glycol monomethyl ether acetate was added thereto for azeotropic removal of the aqueous fraction and methyl isobutyl ketone, and the obtained organic layer was concentrated again to obtain 54.6 g of resin solution. The resulting liquid was a solution of a resin in which the hydroxyl groups of the phenyl novolak resin had been partially 1-cyclohexyloxyethylated. When the resin was analyzed using 1H-NMR, 29.0% of hydroxyl groups were found to be 1-(cyclohexyloxy)ethylated. The concentration of the resin solution was measured using a dry mass reduction method and found to be 45.8%. The resin was referred to as resin A1-5.




Synthesis Example 6: Synthesis of Novolak Resin A2-1
To a four-necked flask with a stirring device, a reflux condenser and a thermometer, 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid and 826.9 parts of methanol were poured, the temperature is increased to a reflux state, and the temperature maintained for 4 hours. After cooling, 1320 parts of methylisobutylketone were charged, and 1075 parts were distilled away at ordinary pressure. Then 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methyphenol were added thereto and the temperature was increased to 65° C. 678 parts of 37% formalin was dropped thereinto over 1.5 hours while the temperature was adjusted to 87° C. at the time of completion of it. Then the temperature maintained at 87° C. for 10 hours, and 1115 parts of methylisobutylketone were added thereto, and then separation-washing was carried out three times using ion-exchanged water. 500 parts of methylisobutylketone was added to the resulting resin solution, and vacuum concentration was carried out until the total amount reached 3435 parts. 3796 parts of methylisobutylketone and 4990 parts of n-heptane were added to the resulting resin solution, the temperature was increased to 60° C. After one hour stirring, separation was carried out, the lower layer, that was the resin solution, was diluted using 3500 parts of propylene glycol monomethyl ether acetate, and concentrated to obtain 1690 parts of a propylene glycol monomethyl ether acetate solution of novolak resin A2-1 (solid component 43%). The weight average molecular weight of the resin A2-1 was 7×103.
Examples 1 to 18 and Comparative Example 1
<Preparing Resist Compositions>
Resist compositions were prepared by mixing and dissolving each of the components (parts) shown in Table 1, and then filtrating through a fluororesin filter having 5.0 μm pore diameter.














TABLE 1











Adhesion




Resin
Acid Generator
Quencher
Compound (I)
Improver
PB/PEB






















Ex. 1
A1-1 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 2
A1-1 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./90° C.



A2-1 = 5.400


Ex. 3
A1-1 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 4
A1-1 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./90° C.



A2-1 = 5.400


Ex. 5
A1-2 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 6
A1-2 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./90° C.



A2-1 = 5.400


Ex. 7
A1-2 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 8
A1-2 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./90° C.



A2-1 = 5.400


Ex. 9
A1-3 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 10
A1-3 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 11
A1-3 = 7.425,
B1 = 0.24
C1 = 0.051
I-3: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 12
A1-3 = 7.425,
B2 = 0.29
C1 = 0.060
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 13
A1-3 = 7.425,
B3 = 0.30
C1 = 0.060
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 14
A1-4 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 15
A1-4 = 7.425,
B1 = 0.24
C1 = 0.051
I-2: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 16
A1-4 = 7.425,
B2 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 17
A1-5 = 7.425,
B1 = 0.24
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Ex. 18
A1-3 = 7.425,
B4 = 0.28
C1 = 0.051
I-1: 0.675
E1 = 0.01
110° C./—



A2-1 = 5.400


Comp.
A1-3 = 7.425,
B1 = 0.24
C1 = 0.051

E1 = 0.01
110° C./—


Ex. 1
A2-1 = 5.400









The above resist compositions of Examples and Comparative Examples further contain 0.002 parts of polyether modified silicone oil (Toray silicone SH8400; Product of Toray Dow Corning, Co., Ltd.) as a surfactant
<Resin>
A1-1: Resin A1-1
A1-2: Resin A1-2
A1-3: Resin A1-3
A1-4: Resin A1-4
A1-5: Resin A1-5
A2-1: Novolak Resin A2-1
<Acid Generator>
B1: N-hydroxynaphthalimide triflate, trade name “NAI-105”, product by Midori Kagaku, Co., Ltd.




B2: The following compound, PAI-101 product by Midori Kagaku, Co., Ltd.




B3: The following compound, PAG-103 product by BASF




B4: Trade name (SP-606) product by ADEKA Corporation
B5: The following compound, PAG-121 product by BASF




<Quencher>

C1: 2,4,5-triphenylimidazole (Product of Tokyo Chemical Industry, Co., Ltd.)
<Adhesion Improver (E)>
E1: Bismuthiol (Product of Tokyo Chemical Industry, Co., Ltd.)
<Compound (I)>
I-1: synthesized according to the description of JPH03-185447A1




I-2: synthesized according to the description of JPH08-99922A1




I-3: synthesized according to the description of JPH09-31044A1




<Solvent>

Propyleneglycolmonomethylether acetate 25 parts
<Preparation of Resist Pattern>
On a 4-inches substrate where copper had been vapor-deposited on a silicon wafer, each of the resist compositions prepared as the above was spin-coated so that the thickness of the resulting film became 5 μm after pre-baking.
Then the substrate was subjected to pre-baking on direct hotplate at the temperature as shown in the column “PB” of Table 1 for 180 seconds.
Using an i-ray stepper (“NSR 1755i7A” manufactured by Nikon, NA=0.5) and a mask for foil ing a line and space pattern with line width and pitch=1:1, each wafer thus formed with the respective film was subjected to exposure with the exposure quantity being varied stepwise.
After exposure, each wafer was subjected to post-exposure baking on a hotplate at the temperature as shown in the columns “PEB” of Table 1 for 60 seconds.
After that, each wafer was subjected to paddle development for 180 seconds with an aqueous solution of 2.38% by mass tetramethylammonium hydroxide to obtain resist patterns.
The Effective Sensitivity (ES) means the exposure quantity in the production which made the line and space patterns having 2 μm in the line width (line width: pitch=1:1). The obtained patterns were observed using a scanning microscope observation.
Shape:
The resist patterns having the line width 2 μm were obtained by way of the process where the exposure was carried out at the exposure quantity of ES, and then each pattern was observed using a scanning electron microscope at 4000-fold magnification. When the profile of pattern was rectangle at both top and bottom sites as shown in FIG. 1(a), it was marked by “circle” (good). When the profile of pattern was a round shape at its top site as shown in FIG. 1(b), it was marked by “X” (bad).
Detachability:
The obtained resist pattern was subjected to plasma treatment, and then the substrate with the resist patterns was subjected to an electrolytic plating using a copper plating solution for 3 minutes at 25° C. The resulting substrate was immersed for 10 minutes in N-methylpyrrolidone at 25° C., and then it was washed with 2-propanol. The obtained each pattern was observed with a scanning electron microscope. When the residues of the resist pattern were not observed, it was marked by “circle” (good). When the residues of the resist pattern were observed, it was marked by “X” (bad).
The results of the evaluation are listed in Table 2.










TABLE 2







Shape
Detachability




















Ex. 1
∘(a)
∘



Ex. 2
∘(a)
∘



Ex. 3
∘(a)
∘



Ex. 4
∘(a)
∘



Ex. 5
∘(a)
∘



Ex. 6
∘(a)
∘



Ex. 7
∘(a)
∘



Ex. 8
∘(a)
∘



Ex. 9
∘(a)
∘



Ex. 10
∘(a)
∘



Ex. 11
∘(a)
∘



Ex. 12
∘(a)
∘



Ex. 13
∘(a)
∘



Ex. 14
∘(a)
∘



Ex. 15
∘(a)
∘



Ex. 16
∘(a)
∘



Ex. 17
∘(a)
∘



Ex. 18
∘(a)
∘



Comp.
∘(a)
x



Ex. 1










The resist composition of the disclosure can provide a resist pattern showing excellent shape and detachability.
The present resist composition can be used for semiconductor microfabrication with resist patterns showing excellent shape.

## Claims

1. A resist composition comprising:
a resin having an acid-labile group,
a novolak resin of which the weight average molecular weight is 3,000 to 10,000,
an acid generator,
a compound having two or more phenolic-hydroxy groups and being other than a resin, and
a solvent.

2. The resist composition according to claim 1 wherein
the resin having an acid-labile group is a resin having a structural unit represented by formula (a1-2):




wherein Ra5 represents a hydrogen atom or a methyl group,
Ra1′ and Ra2′ each independently represent a hydrogen atom or a C1 to C12 hydrocarbon group, and Ra3′ represents a C1 to C20 hydrocarbon group, or
Ra1′ represents a hydrogen atom or a C1 to C12 hydrocarbon group, and Ra2′ and Ra3′ are bonded together with a carbon atom and an oxygen atom bonded thereto to form a divalent heterocyclic group having 2 to 20 carbon atoms, and a methylene group contained in the hydrocarbon group or the divalent heterocyclic group may be replaced by an oxygen atom or a sulfur atom,
Ra6 in each occurrence independently represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, and
“m” represents an integer of 0 to 4.

3. The resist composition according to claim 1 wherein
the acid generator is a compound having a group represented by formula (B1):




wherein Rb1 represents a C1 to C18 hydrocarbon group in which a hydrogen atom may have a fluorine atom and in which a methylene group may be replaced by an oxygen atom or a carbonyl group.

4. The resist composition according to claim 1 wherein
the compound having two or more phenolic-hydroxy groups is a compound represented by formula (I):




wherein Xi represents a single bond or an oxygen atom,
A represents a C1 to C6 alkanediyl group where a methylene group may be replaced by an oxygen atom, provided that when Xi represents an oxygen atom, a methylene group bonded to Xi is not replaced by an oxygen atom,
“i1” and “i2” each independently represent an integer of 0 to 4, provided that the total number of i1 and i2 is 2 or more,
Ri12 and Ri13 in each occurrence independently represent a halogen atom or a C1 to C12 alkyl group,
“i3” and “i4” each independently represent an integer of 0 to 4,
Ri1 represents a hydrogen atom or an optionally substituted C1 to C6 alkyl group, or Ri1 may be bonded to A together with carbon atoms and Xi to form an optionally substituted 5 to 12-membered saturated ring,
provided that the total number of “i1” and “i3” is 4 or less and the total number of “i1” and “i4” is 5 or less.

5. A method for producing a resist pattern comprising steps (1) to (4);
(1) applying the resist composition according to claim 1 onto a substrate;
(2) drying the applied composition to form a composition layer;
(3) exposing the composition layer; and
(4) developing the exposed composition layer.