JP6622479B2 - Resist composition and method for producing resist pattern - Google Patents

Description

  The present invention relates to a resist composition and a method for producing a resist pattern.

  In a multi-pin thin film mounting of a semiconductor chip, a protruding electrode having a height of about 4 to 150 μm, which is a connection terminal (bump), is disposed on a substrate by a photolithography technique. As a method for forming such connection terminals, Patent Document 1 describes using a resist composition containing a resin containing a structural unit derived from p-hydroxystyrene. Patent Document 2 describes a photoresist composition containing a silane coupling agent having an isocyanate group and / or an amino group for use in improving adhesion in a pattern having a large aspect ratio.

JP 2011-75864 A JP 2010-33027 A

  In the photoresist compositions described in Patent Documents 1 and 2, the resist pattern resolution, scum removal, and adhesion to the substrate may be insufficient.

The present application includes the following inventions.
[1] A resist composition containing a resin (A1) containing a structural unit having an acid labile group, an acid generator (B), a silicon compound (G) having a mercapto group, and a solvent (D).
[2] The resist composition according to [1], wherein the silicon compound (G) having a mercapto group is a polymer comprising a compound represented by the formula (IIA) and / or a unit derived from the compound.
[In the formula (IIA)
R ^j1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms.
R ^j2 to R ^j4, independently of each other, represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group or mercaptoalkyl group having 1 to 5 carbon ^{atoms, R j2} ~ At least one of R ^j4 is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms.
t ⁱ represents an integer of 1 to 10. ]
[3] The resist composition according to [1] or [2], wherein the silicon compound is contained in an amount of 0.001% by mass to 0.45% by mass with respect to the solid content of the resist composition.
[4] A resin having a structural unit containing at least one group selected from the group represented by the formula (1) and the group represented by the formula (2), wherein the resin containing the structural unit having an acid labile group The resist composition according to any one of [1] to [3].
[In Formula (1),
R ^{a1 to} R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 are bonded to each other to form 2 to 2 carbon atoms. 20 represents a divalent hydrocarbon group, and R ^a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * Represents a bond. ]
[In Formula (2),
R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^{a2 ′} and R ^{a3 ′} is bonded to each other to form a divalent heterocyclic ring having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and the methylene group contained in the hydrocarbon group and the divalent heterocyclic group is , Oxygen atom or sulfur atom may be substituted. * Represents a bond. ]
[5] The resist composition according to [4], wherein the structural unit having a group represented by formula (1) is a structural unit represented by formula (a1-1).
[In the formula (a1-1),
R ^a1 , R ^a2 and R ^a3 each have the same meaning as described above.
R ^a4 represents a hydrogen atom or a methyl group. ]
[6] The resist composition according to [4], wherein the structural unit having a group represented by formula (2) is a structural unit represented by formula (a1-2).
[In the formula (a1-2),
R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} each have the same meaning as described above.
R ^a5 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ^a6 may be the same as or different from each other. ]
[7] (1) A step of applying the resist composition according to any one of [1] to [6] to a substrate,
(2) a step of drying the resist composition after coating to form a composition layer;
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern including a step of developing the composition layer after exposure.

  According to the resist composition of the present invention, a resist pattern with high resolution and good adhesion can be produced without generating scum.

In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. Notations such as “(meth) acrylic acid” have the same meaning.
In the groups described in the present specification, any of those capable of taking both a linear structure and a branched structure may be used. When stereoisomers exist, all stereoisomers are included.
Moreover, in this specification, solid content means the sum total of the component remove | excluding the solvent from all the components contained in a resist composition.

<Resist composition>
The resist composition of the present invention comprises:
A resin containing a structural unit having an acid labile group (hereinafter sometimes referred to as resin (A1)),
An acid generator (hereinafter sometimes referred to as an acid generator (B)),
It contains a silicon compound (G) having a mercapto group and a solvent (D).
The resist composition of the present invention may further contain a resin different from the resin (A1) (hereinafter sometimes referred to as resin (A2)), a quencher (C), an adhesion improver (E), and the like. .

<Resin (A1)>
The resin (A1) includes a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”).
The acid labile group means a group that is eliminated by contact with an acid to form a hydrophilic group (for example, a hydroxy group or a carboxy group). In other words, it means that the solubility of the structural unit having an acid labile group in an alkaline aqueous solution is increased by the action of an acid. Therefore, the resin (A1) has increased solubility in an alkaline aqueous solution due to the action of an acid.

“The solubility in an alkaline aqueous solution is increased by the action of an acid” means that the solubility in an alkaline aqueous solution is increased by contact with an acid. It is preferably insoluble or hardly soluble in an aqueous alkali solution before contact with an acid, and soluble in an aqueous alkali solution after contact with an acid.
The resin (A1) is known in the art such as a structural unit having an acid labile group and a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”). A structural unit may be included.

Examples of the acid labile group include a group represented by the formula (1) and a group represented by the formula (2).

[In the formula (1), R ^a1 , R ^a2 and R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R a ^a2 represents a divalent hydrocarbon group having 2 to 20 carbon atoms bonded to each other, and R ^a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * Represents a bond. ]

[In the formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} may be bonded to each other to form a divalent heterocyclic group having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded. The methylene group contained in the hydrocarbon group and the divalent heterocyclic group may be replaced with an oxygen atom or a sulfur atom. * Represents a bond. ]

Examples of the hydrocarbon group for R ^{a1 to} R ^a3 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like, and groups in which these are combined.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond).

Carbon number of the alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably 3 to 16.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, and a 2-alkyladamantan-2-yl group, 1 -(Adamantan-1-yl) alkane-1-yl group etc. are mentioned.
The group in which an alkyl group and an aromatic hydrocarbon group are combined is, for example, an aralkyl group, and specifically includes a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, and the like. Can be mentioned.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent hydrocarbon group include the following groups. The divalent hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the group represented by formula (1) include an alkoxycarbonyl group (preferably a tert-butoxycarbonyl group as a group in which R ^a1 , R ^a2 and R ^a3 are all alkyl groups in formula (1)). 1-alkylcyclopentan-1-yloxycarbonyl group and 1-alkylcyclohexane-1-yloxycarbonyl group (in formula (1), R ^a1 and R ^a2 are combined to form a cyclopentyl group or a cyclohexyl group; R ^a3 is an alkyl group) and 1- (cyclopentan-1-yl) -1-alkylalkoxycarbonyl group and 1- (cyclohexane-1-yl) -1-alkylalkoxycarbonyl group (in the formula (1)) R ^a1 and R ^a2 are alkyl groups, and R ^a3 is a cyclopentyl group or a cyclohexyl group) Is mentioned.

Examples of the hydrocarbon group of R ^{a1 ′ to} R ^{a3 ′} of the group represented by the formula (2) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like, and groups in which these are combined. Can be mentioned.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group and the like.
Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; polycyclic alicyclic carbon groups such as decahydronaphthyl group, adamantyl group, and norbornyl group. A hydrogen group is mentioned.
Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl Groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like. The aromatic hydrocarbon group may further have a substituent, and examples of the substituent include an aryloxy group having 6 to 10 carbon atoms.
Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, an isobornyl group, and a 2-alkyladamantan-2-yl group, 1 -(Adamantan-1-yl) alkane-1-yl group etc. are mentioned.
The group in which an alkyl group and an aromatic hydrocarbon group are combined is, for example, an aralkyl group, and specifically includes a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, a naphthylethyl group, and the like. Can be mentioned.

^{Examples of the} divalent heterocyclic group formed together with the carbon atom and oxygen atom to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other include the following groups. * Represents a bond.
R ^{a1 ′} is preferably a hydrogen atom.

Specific examples of the group represented by the formula (2) include the following groups.

<Structural unit (a1)>
The monomer that leads to the structural unit (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, and is represented by the group represented by the formula (1) and / or the formula (2). A monomer having a group and an ethylenically unsaturated bond is more preferable.
Resin (A1) may have only 1 type of structural unit (a1), and may have multiple types.

  As the structural unit (a1), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as “structural unit (a1-1)”) and a structural unit represented by the formula (a1-2) (Hereinafter sometimes referred to as “structural unit (a1-2)”) is preferable.

[In Formula (a1-1) and Formula (a1-2),
R ^a1 , R ^a2 , R ^a3 , R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} each have the same meaning as described above.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ^a6 may be the same as or different from each other. ]

In formula (a1-1), R ^a4 is preferably a methyl group.
In the formula (a1-2), R ^{a1 ′} is preferably a hydrogen atom.
R ^{a2 ′} is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^{a3 ′} is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. More preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. When the aromatic hydrocarbon group has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.
R ^a5 is preferably a hydrogen atom.
R ^a6 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.
m is preferably 0 or 1, and more preferably 0.

  Examples of the structural unit (a1-1) include structural units represented by any of the formulas (a1-1-1) to (a1-1-17).

  Examples of the monomer that leads to the structural unit (a1-2) include monomers represented by any one of the formulas (a1-2-1) to (a1-2-13).

In the above monomer, a monomer in which hydrogen atoms corresponding to R ^a4 and R ^a5 are replaced with a methyl group can also be given as a specific example of the monomer.
Among these, from monomers represented by formula (a1-2-2), formula (a1-2-3), (a1-2-4), (a1-2-9), and (a1-2-14) Preferred structural units are derived from monomers represented by the formulas (a1-2-2), (a1-2-3), (a1-2-4), (a1-2-9) A structural unit is more preferable.

The resin (A1) having an acid labile group is preferably a resin having a structural unit (a1-2).
When resin (A1) has a structural unit (a1-1) and / or a structural unit (a1-2), these total content rates are 5-60 with respect to the sum total of all the structural units of resin (A1). It is preferably mol%, more preferably 10 to 55 mol%, still more preferably 15 to 50 mol%, and particularly preferably 20 to 45 mol%.

<Structural unit without acid labile group>
Resin (A1) may have 1 type, or 2 or more types of structural units (a2).

  As the structural unit (a2), for example, a structural unit represented by any of the formulas (a2-1) to (a2-3) (hereinafter, “structural unit (a2-1)” or the like depending on the formula number) In some cases).

[In Formula (a2-1), Formula (a2-2) and Formula (a2-3),
R ^a7 , R ^a8 and R ^a9 each independently represent a hydrogen atom or a methyl group.
R ^a10 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
m ′ represents an integer of 0 to 4. When m ′ is 2 or more, the plurality of R ^a10 may be the same as or different from each other.
R ^a11 represents a hydrogen atom, a primary hydrocarbon group having 1 to 10 carbon atoms, or a secondary hydrocarbon group.
R ^a12 represents a primary or secondary alkyl group having 1 to 6 carbon atoms.
L ^a1 represents an alkanediyl group having 2 to 6 carbon atoms. However, the carbon atom bonded to the oxygen atom is a primary or secondary carbon atom.
n represents an integer of 1 to 30. When n is 2 or more, the plurality of L ^a1 may be the same as or different from each other. ]

^Examples of the alkyl group represented by R ^a10 or R ^a12 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
^Examples of the alkoxy group represented by R ^a10 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the hydrocarbon group represented by R ^a11 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptane group, an octane group, a nonane group, and a decane group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond).
Examples of the group combining the alkyl group and the alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, and a norbornylethyl group. Can be mentioned.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the group in which an alkyl group and an aromatic hydrocarbon group are combined include an aralkyl group such as a benzyl group.

The alkanediyl group of L ^a1, ethylene, propane-1,3-diyl, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane - 1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group and propane-2,2-diyl group; propane-1,2-diyl group, pentane-2,4-diyl Groups, branched alkanediyl groups such as 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; and the like.

R ^a7 is preferably a hydrogen atom.
R ^a8 and R ^a9 are preferably each independently a methyl group.
R ^a10 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
m ′ is preferably 0 or 1, and more preferably 0.
R ^a11 is preferably a primary or secondary alkyl group having 1 to 6 carbon atoms.
L ^a1 is preferably an alkanediyl group having 2 to 4 carbon atoms, such as ethane-1,2-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1, A 4-diyl group is more preferable, and an ethane-1,2-diyl group is more preferable.
n is preferably an integer of 1 to 10.
R ^a12 is preferably a primary or secondary alkyl group having 1 to 3 carbon atoms.

  As the structural unit (a2-1), a structure represented by the formula (a2-1-1), the formula (a2-1-2), the formula (a2-1-3), or the formula (a2-1-4) Units are preferred. Moreover, the monomer which guide | derived a structural unit (a2-1) is described in Unexamined-Japanese-Patent No. 2010-204634, for example.

Examples of the monomer that leads to the structural unit (a2-2) include (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. Acid alkyl esters;
(Meth) acrylic acid cycloalkyl esters such as cyclopentyl (meth) acrylate and cyclohexyl (meth) acrylate;
Polycyclic (meth) acrylic acid esters such as adamantyl (meth) acrylate;
And (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

  Examples of monomers that lead to the structural unit (a2-3) include ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monopropyl ether (meth) acrylate, and ethylene glycol monobutyl ether (meta ) 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, Oct Ethylene glycol monomethyl ether (meth) acrylate of (meth) acrylic acid esters.

  Furthermore, as a monomer for deriving the structural unit (a2), acrylic acid, methacrylic acid, crotonic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, α-methylstyrene, 4-methyl Examples thereof include styrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 4-isopropoxystyrene, and the like.

The structural unit (a2) may be, for example, a structural unit represented by the formula (a2-4).
[In the formula (a2-4),
R ^a13 represents a hydrogen atom or a methyl group.
R ^a14 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
R ^a15 represents a primary hydrocarbon group or a secondary hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. However, the methylene group bonded to the oxygen atom is not substituted with the oxygen atom.
m ″ represents an integer of 0 to 4. When m ″ is 2 or more, a plurality of R ^a14 may be the same as or different from each other.
m ″ ′ represents an integer of 0 to 4. When m ″ ′ is 2 or more, the plurality of R ^a15 may be the same as or different from each other.
However, the sum of m ″ and m ′ ″ is 5 or less.

^Examples of the alkyl group and alkoxy group for R ^a14 include the same groups as R ^a10 .
As the hydrocarbon group for R ^a15, the same groups as those for R ^a11 can be mentioned.

Examples of the hydrocarbon group for R ^a15 include groups in which the bond to the oxygen atom is not a tertiary carbon atom, that is, a group in which one or more atoms other than carbon atoms such as hydrogen atoms are bonded to the bonded carbon. .
R ^a15 is, among these, a linear or branched alkyl group having 1 to 5 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, a phenyl group or a group formed by combining these, or these groups The carbon atom adjacent to the oxygen atom is preferably a group in which a carbonyl group is replaced.

Examples of the structural unit (a2-4) include structural units represented by formula (a2-4-1) to formula (a2-4-10).

In the structural units represented by formula (a2-4-1) to formula (a2-4-10), the structural unit in which the hydrogen atom corresponding to R ^a13 is replaced with a methyl group is also the structural unit (a2-4). It can mention as a specific example.

  When the resin (A1) has the structural unit (a2-1), the structural unit (a2-2), the structural unit (a2-3), and the structural unit (a2-4), the total content thereof is the resin (A1 1) to 30 mol% is preferable, 1 to 25 mol% is more preferable, 5 to 25 mol% is further preferable, and 5 to 20 mol% is particularly preferable.

  When the resin (A1) has the structural unit (a2), the content ratio of the structural unit (a1) to the structural unit (a2) [structural unit (a1): structural unit (a2)] is preferably 10 on a molar basis. : 90 to 80:20, more preferably 15:85 to 60:40, 15:85 to 45:55, or 20:80 to 60:40.

Examples of the combination of structural units contained in the resin (A1) include those represented by the formulas (A1-1) to (A1-46).

In the structural formula, a monomer in which a hydrogen atom corresponding to R ^a5 or the like is replaced with a methyl group or a methyl group is replaced with a hydrogen atom can also be given as a specific example of the monomer. One resin may contain a monomer having a hydrogen atom and a methyl group.

  The resin (A1) is preferably a resin having the structural unit (a1) and the structural unit (a2), more preferably the structural unit (a1-1) and / or the structural unit (a1-2) and the structural unit. (A2).

Resin (A1) is a resin obtained by reacting a resin containing at least one selected from a carboxyl group and a phenolic hydroxyl group in the side chain with a compound containing at least two or more vinyloxy groups in one molecule. (Hereinafter may be referred to as “resin (A1b)”).
The resin (A1b) is preferably a resin obtained by reacting a resin containing a phenolic hydroxyl group with a compound containing two or more vinyloxy groups in one molecule. Such a resin can be obtained, for example, by reacting a resin containing the structural unit (a2-1) with a compound containing two or more vinyloxy groups in one molecule. Moreover, the resin obtained by making this novolak resin react with the above-mentioned vinyloxy group containing compound using the novolak resin mentioned later as resin containing a phenolic hydroxyl group may be sufficient. Further, it may be a resin obtained by mixing a resin having the structural unit (a2-1) and a novolac resin, and reacting the obtained vinyloxy group-containing compound with the obtained resin mixture. In addition, a resin obtained by reacting a resin containing the structural unit (a2-1) and the above-described vinyloxy group-containing compound, and a resin obtained by reacting a novolac resin and the above-described vinyloxy group-containing compound are used in combination. Also good.

  In the synthesis of the resin (A1b), the usage ratio [carboxyl group and phenolic hydroxyl group: vinyloxy group] of the compound containing at least two vinyloxy groups in one molecule with respect to the carboxyl group and phenolic hydroxyl group is: On a molar basis, it is preferably 60 to 99:40 to 1, more preferably 70 to 95:30 to 5.

Examples of the resin (A1b) include resins described in JP-A-2008-134515 and JP-A-2008-46594.
Examples of the compound containing at least two or more vinyloxy groups in one molecule include 1,4-cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, and the like.

  When resin (A1b) contains novolak resin as a raw material, the content rate is 30-70 mass% with respect to the total amount of resin (A1b).

The resin (A1) can be produced by polymerizing the above-described monomer by a known polymerization method (for example, radical polymerization method).
The weight average molecular weight of the resin (A1) is preferably 5,000 or more, more preferably 10,000 or more, further preferably 15,000 or more, preferably 600,000 or less, more preferably 500,000 or less. is there.
The weight average molecular weight of the resin (A1b) is preferably 5,000 or more, more preferably 10,000 or more, and preferably 300,000 or less, more preferably 200,000 or less.
A weight average molecular weight is calculated | required as a conversion value of a standard polystyrene reference | standard by gel permeation chromatography analysis. Detailed analysis conditions for this analysis are described in the Examples of the present application.

  The content of the resin (A1) is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 30% by mass or more, with respect to the total amount of the resin contained in the resist composition. Is 95 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 70 mass% or less.

<Resin (A2)>
The resist composition of the present invention may further contain a resin (A2) in addition to the resin (A1). The resin (A2) is not particularly limited, but is preferably an alkali-soluble resin. The alkali-soluble resin is a resin that contains an acidic group and is soluble in an alkali developer. Examples of the acidic group include a carboxy group, a sulfo group, and a phenolic hydroxy group.
Examples of the alkali-soluble resin include known alkali-soluble resins in the resist field. A novolak resin, a resin having a structural unit (a2-1) and having no structural unit (a1), for example, polymerization derived from hydroxystyrene Examples thereof include a resin having a unit, a resin having a polymerization unit derived from a (meth) acrylic ester, a polyalkylene glycol, and the like, and preferably a novolak resin. An alkali-soluble resin may be used independently and may be used in combination of 2 or more type.

  A novolak resin is a resin obtained by condensing a phenol compound and an aldehyde in the presence of a catalyst. Examples of the phenol compound include phenol; o-, m- or p-cresol; 2,3-, 2,5-, 3,4- or 3,5-xylenol; 2,3,5-trimethylphenol; 2-, 3- or 4-tert-butylphenol; 2-tert-butyl-4- or 5-methylphenol; 2-, 4- or 5-methylresorcinol; 2-, 3- or 4-methoxyphenol; -, 2,5- or 3,5-dimethoxyphenol; 2-methoxyresorcinol; 4-tert-butylcatechol; 2-, 3- or 4-ethylphenol; 2,5- or 3,5-diethylphenol; , 3,5-triethylphenol; 2-naphthol; 1,3-, 1,5- or 1,7-dihydroxynaphthalene; xylenol and hydroxybenzal Polyhydroxy triphenylmethane compounds obtained by condensation of an hydrate thereof. These phenol compounds can be used alone or in combination of two or more. Among them, as the phenol compound, 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 are preferred.

  As aldehydes, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde; alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural or furylacrolein; Benzaldehyde, o-, m- or p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde or o-, m- or p-hydroxybenzaldehyde And aromatic aldehydes such as phenylacetaldehyde or cinnamic aldehyde. These aldehydes can also be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferable because it is easily available industrially.

  Examples of catalysts used for the condensation of phenolic compounds with aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid or phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid or p-toluenesulfonic acid A divalent metal salt such as zinc acetate, zinc chloride or magnesium acetate. These catalysts can be used alone or in combination of two or more. The amount of the catalyst used is usually 0.01 to 1 mol with respect to 1 mol of aldehyde.

  The condensation reaction of a phenol compound and an aldehyde can be performed according to a known method. The condensation reaction can be performed, for example, by mixing a phenol compound and an aldehyde and reacting at 60 to 120 ° C. for 2 to 30 hours. The condensation reaction may be carried out in the presence of a solvent. Examples of the solvent in the condensation reaction include methyl ethyl ketone, methyl isobutyl ketone, and acetone. After completion of the reaction, a novolac resin can be taken out by adding a solvent insoluble in water to the reaction mixture as necessary, washing the reaction mixture with water, and then concentrating.

  The mass average molecular weight of the novolak resin is usually 3,000 to 10,000, preferably 6,000 to 9,000, and more preferably 7,000 to 8,000. By setting it within this range, it is possible to effectively prevent thinning and residual residues after development.

  The resin having a polymer unit derived from hydroxystyrene is typically polyvinylphenol, preferably poly-p-vinylphenol. Specifically, resin which consists of a structural unit represented by a formula (a2-1) is mentioned. Such a polyvinylphenol can be obtained by polymerizing the monomer described in JP2010-204634A, for example.

As the resin having a polymerization unit derived from (meth) acrylic acid ester, for example, a resin obtained by polymerizing by a conventional method using the following compounds as monomers and combining one or more of these monomers. Can be mentioned.
Having a carboxyl group, such as (meth) acrylic acid;
Those having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (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, heptaethylene Those having a plurality of ether bonds such as polyethylene glycol monomethyl ether (meth) acrylates such as glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, and nonaethylene glycol monomethyl ether (meth) acrylate.

  (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate and the like (meth) ) Acrylic acid cycloalkyl esters; Polycyclic (meth) acrylic acid esters such as adamantyl (meth) acrylate; ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monopropyl ether (Meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monoalkyl ether (meth) acrylates, and the like may be used in combination.

  The content of the resin (A2) is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 70% by mass or less, more preferably 60% by mass with respect to the total amount of the resin contained in the resist composition. It is below mass%.

<Acid generator (B)>
The resist composition of the present invention contains an acid generator (B). The acid generator generates an acid upon exposure, and the generated acid acts catalytically to desorb a group that is eliminated by the acid of the resin (A1). The acid generator is classified into a nonionic type and an ionic type, and any of the acid generators (B) of the resist composition of the present invention may be used.
Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonate) and sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used.

  As the nonionic acid generator, a compound having a group represented by the formula (B1) is preferable.

[In the formula (B1),
R ^b1 represents a C1-C18 hydrocarbon group which may have a fluorine atom, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. ]

Examples of the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by a combination thereof, a methyl group, an ethyl group, and a propyl group. Alkyl group having 1 to 18 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo C3-C18 alicyclic hydrocarbon group such as octyl group and adamantyl group; phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl Group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl group An aromatic hydrocarbon group having 6 to 18 carbon atoms such as an aryl group-6- ethylphenyl and the like.
The hydrocarbon group is preferably an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably. Is an alkyl group having 1 to 4 carbon atoms. Examples of the group in which the methylene group contained in the hydrocarbon group is substituted with an oxygen atom or a carbonyl group include groups represented by the formula (Y1) to the formula (Y12), preferably the formula (Y7) to the formula ( Group represented by Y9) is mentioned, More preferably, group represented by a formula (Y9) is mentioned.

  Examples of the C1-C18 hydrocarbon group having a fluorine atom include a fluoromethyl group, a fluoroethyl group, a fluoropropyl group, a fluorobutyl group, a fluoropentyl group, a fluorohexyl group, a fluoroheptyl group, a fluorooctyl group, and a fluorononyl group. Group, fluoroalkyl group having 1 to 18 carbon atoms such as fluorodecyl group; cyclofluoropropyl group, cyclofluorobutyl group, cyclofluoropentyl group, cyclofluorohexyl group, cyclofluoroheptyl, cyclofluorooctyl group, fluoroadamantyl group, etc. And an aromatic hydrocarbon group having 6 to 18 carbon atoms such as an aryl group such as a fluorophenyl group, a fluoronaphthyl group, and a fluoroanthryl group.

  As a C1-C18 hydrocarbon group which has a fluorine atom, Preferably the C1-C10 alkyl group which has a fluorine atom, or the aromatic hydrocarbon group which has a fluorine atom is mentioned, More preferably, it is C1. -8 perfluoroalkyl group is mentioned, More preferably, a C1-C4 perfluoroalkyl group is mentioned.

  Examples of the compound having a group represented by the formula (B1) include compounds represented by any of the formulas (b1) to (b3), and preferably represented by the formula (b1) or the formula (b2). More preferred are compounds represented by formula (b1).

[In Formula (b1)-Formula (b3),
R ^b1 represents the same meaning as described above.
R ^{b2 ′} , R ^b3 and R ^b4 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group.
Ring ^Wb1 represents a C6-C14 aromatic hydrocarbon ring or a C6-C14 aromatic heterocyclic ring.
x represents an integer of 0 to 2. When x is 2, a plurality of R ^{b2 ′} may be the same or different. ]

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and a methyl group is preferable.
As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc. are mentioned, Preferably a methoxy group is mentioned.

Examples of the aromatic hydrocarbon ring having 6 to 14 carbon atoms include a benzene ring, a naphthalene ring, and an anthracene ring.
Examples of the aromatic heterocyclic ring include rings having 6 to 14 atoms constituting the ring, preferably the following rings.
^Examples of the substituent that the ring W ^b1 may have include an alkyl group having 1 to 8 carbon atoms, and a naphthalene ring is preferable.

  The compound represented by the formula (b1) is preferably a compound represented by any one of the formulas (b4) to (b7), more preferably a compound represented by the formula (b4). .

[In Formula (b4)-Formula (b7),
R ^b1 represents the same meaning as described above.
R ^b2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^{b5 to} R ^b7 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

  Examples of the compound represented by the formula (b1) include compounds represented by any of the formulas (b1-1) to (b1-11), and preferably the formula (b1-6) or the formula (b1 -7).

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

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

As the ionic acid generator, a compound represented by the formula (b8) or the formula (b9) is preferable.
[In Formula (b8) and Formula (b9),
A ^b1 and A ^b2 each independently represent an oxygen atom or a sulfur atom.
R ^{b8 to} R ^b11 each independently represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
X1 ^- and X2 ^- represents an organic anion. ]

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, and cumenyl group. Groups, mesityl groups, biphenyl groups, phenanthryl groups, 2,6-diethylphenyl groups, aryl groups such as 2-methyl-6-ethylphenyl, and the like.
R ^{b8 to} R ^b11 are independently of each other preferably an aromatic compound having 6 to 12 carbon atoms, and more preferably a phenyl group.

X1 ^- and X2 ^- The sulfonate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion can be mentioned, preferably include sulfonic acid anion, more preferably represented by the formula (b10) Examples include sulfonate anions.
[In the formula (b10),
R ^b12 represents a C 1-18 hydrocarbon group which may have a fluorine atom, and the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. ]
^Examples of R ^b12 include the same groups as R ^b1 in formula (B1).

Examples of the compound represented by the formula (b9) include the following compounds.

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

The acid generator (B) may be synthesized by a known method or may be a commercially available product.
The content of the acid generator (B) is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more with respect to 100 parts by mass of the resin (A). Preferably, it is 30 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

<Silicon compound having a mercapto group>
The silicon compound (G) having a mercapto group may be any compound having a mercapto group and a silicon atom, and includes one or more mercapto groups and one or more siloxane units (—O—Si (R) ₂ —). Or a polymer containing a unit derived from a silicon compound having one or more mercapto groups, or a group derived from a silicon compound having one or more mercapto groups in the side chain. It may be a polymer containing a structural unit or a polymer containing a structural unit derived from a compound having one or more mercapto groups and one or more siloxane units.

The silicon compound (G) having a mercapto group is preferably a compound having one or more mercapto groups and one or more siloxane units. Specifically, a compound represented by the formula (IIA) can be given.
[In the formula (IIA)
R ^j1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms.
R ^j2 to R ^j4, independently of each other, represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group or mercaptoalkyl group having 1 to 5 carbon ^{atoms, R j2} ~ At least one of R ^j4 is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms.
t ⁱ represents an integer of 1 to 10. ]

Examples of the aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the mercaptoalkyl group include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group.

R ^j1 is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or a mercaptopropyl group.
R ^{j2 to} R ^j4 are each independently preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or an alkoxy group having 1 or 2 carbon atoms, and more preferably a methyl group or a methoxy group. However, at least one of these is preferably a mercapto group or a mercaptoalkyl group having 1 to 3 carbon atoms, and more preferably a mercapto group or a mercaptopropyl group.
R ^j2 and R ^j3 may be the same or different from each other, but are preferably the same from the viewpoint of productivity.

Examples of the compound of the formula (IIA) include compounds represented by the following formulas (II-1) to (II-7).
Of these, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like are preferable.

A polymer containing a unit derived from a silicon compound having one or more mercapto groups may be used, a polymer containing a structural unit having a group derived from a silicon compound having one or more mercapto groups in the side chain, or 1 The polymer containing a structural unit derived from a compound having the above mercapto group and one or more siloxane units is, for example, a structural unit containing a unit derived from a compound represented by the formula (IIA) and a polymerizable group And those obtained by polymerizing two or more of the above. The polymerizable group may include a linking group including an amide bond, an ether bond, a thioether bond, an ester bond, and the like, for example, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, or a methacryloyloxy group. Can be mentioned.
In the polymer, the above-described structural units may be used alone or in combination of two or more.

  The silicon compound (G) having a mercapto group may be synthesized by a known method or a commercially available product.

  The silicon compound (G) having a mercapto group may be used alone or in combination of two or more. When two or more kinds are used in combination, each compound may be blended as it is, each may be blended as a polymer, or a polymer of two or more compounds (partially hydrolyzed copolymer). (Condensate). Moreover, the mixture of these compounds, a polymer (partial hydrolysis condensate), and a polymer (partial hydrolysis cocondensate) may be sufficient.

  The content of the silicon compound (G) having a mercapto group is preferably 0.001 to 0.9 mass%, more preferably 0.002 to 0.3 mass% in the solid content of the resist composition. Yes, and particularly preferably 0.003% to 0.02% by mass.

<Solvent (D)>
The solvent (D) is not particularly limited as long as it dissolves the components contained in the resist composition of the present invention. For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate Glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; lactones such as γ-butyrolactone; And mixed solvents thereof.
The content of the solvent (D) is generally 40% by mass to 75% by mass, preferably 45% by mass to 70% by mass, and more preferably 50% by mass with respect to the total amount of the resist composition of the present invention. It is 68 mass% or less.
When the content of the solvent (D) is within the above range, a composition layer having a thickness of about 3 to 150 μm is easily formed when a resist pattern is produced.

<Quencher (C)>
The resist composition of the present invention may contain a quencher (C).
The quencher (C) is a compound having an action of capturing an acid generated from the acid generator upon exposure. Examples of the quencher (C) include basic nitrogen-containing organic compounds.
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Amines include aliphatic and aromatic amines; primary amines, secondary amines and tertiary amines.

Examples of the amine include compounds represented by the formula (C1) or the formula (C2).
[In the formula (C1),
R ^{c1 to} R ^c3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group The atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon having 5 to 10 carbon atoms. ]

  Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, and alkanediyl group in the formula (C1) are the same as those described above.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 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, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dibutylmethylamine, methyldipentylamine, dihexyl Dimethylamine, dicyclohexylmethylamine, diheptylmethylamine, methyldioctylamine, methyldinonylamine, didecylmethylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine Ethyldidecylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4, 4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and the like, preferably diisopropylaniline, and more Mashiku can be mentioned 2,6-diisopropylaniline.

[In the formula (C2),
Ring W ¹ represents a heterocyclic ring containing a nitrogen atom in the atoms constituting the ring, or a benzene ring having a substituted or unsubstituted amino group, and the heterocyclic ring and the benzene ring are a hydroxy group, a carbon number of 1 to You may have at least 1 type chosen from the group which consists of 4 alkyl groups.
A ¹ represents a phenyl group or a naphthyl group.
nc represents 2 or 3. ]

The substituted or unsubstituted amino group is represented by —NR ⁴ R ⁵ , and R ⁴ and R ⁵ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 alicyclic hydrocarbon groups or C6-C14 aromatic hydrocarbon groups are represented.
Examples of the aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
Examples of the alicyclic hydrocarbon group include the same groups as those in R ^{a1 to} R ^a3 in the formula (1). Examples of the aromatic hydrocarbon group include the same groups as those in R ^{a1 ′ to} R ^{a3 ′} in formula (2).

The heterocyclic ring containing a nitrogen atom in the atoms constituting the ring may be an aromatic ring or a non-aromatic ring, and may have another hetero atom (for example, an oxygen atom or a sulfur atom) together with the nitrogen atom. The number of nitrogen atoms that the heterocyclic ring has is, for example, 1 to 3. Examples of the heterocyclic ring include a ring represented by any of formulas (Y13) to (Y28). 0.00 one hydrogen atom contained in the ring, the bond to A ^1.

Ring W ¹ is preferably a heterocyclic ring containing a nitrogen atom as an atom constituting the ring, more preferably a 5-membered or 6-membered aromatic heterocyclic ring containing a nitrogen atom as an atom constituting the ring, More preferably, it is a ring represented by any one of formulas (Y20) to (Y25).

  Examples of the compound represented by the formula (C2) include compounds represented by any one of the formula (C2-1) to the formula (C2-11), preferably the formula (C2-2) to the formula (C2-8). ).

  The content of the quencher (C) is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 4% by mass, and further preferably 0.001 to 3% by mass in the solid content of the resist composition. %, Particularly preferably 0.01 to 1.0% by mass, and particularly preferably 0.1 to 0.7% by mass.

<Adhesion improver (E)>
The adhesion improver (E) is not particularly limited as long as it can prevent corrosion and / or improve adhesion to a metal or the like used for a substrate or wiring. By preventing the corrosion of the metal, the effect of rust prevention is exhibited. In addition to these effects, the adhesion between the resist composition and the substrate or metal can be improved.
Examples of the adhesion improver (E) include a ring-containing sulfur-containing compound, an aromatic hydroxy compound, a benzotriazole-based compound, and a triazine-based compound. These can be used alone or in combination of two or more.

The compound having a cyclic structure having a ring is more preferably a heterocyclic compound having at least one sulfide bond and a mercapto group. The heterocyclic ring may be either a monocyclic ring or a polycyclic ring, may be a saturated or unsaturated ring, and preferably contains a hetero atom other than a sulfur atom. Examples of the hetero atom include an oxygen atom and a nitrogen atom. As a hetero atom, a nitrogen atom is preferable.
As the heterocyclic ring, a heterocyclic ring having 2 to 12 carbon atoms is preferable, and a heterocyclic ring having 2 to 6 carbon atoms is more preferable. The heterocycle is preferably a monocycle. The heterocycle is preferably unsaturated. The heterocycle is preferably unsaturated and monocyclic.

Examples of the heterocyclic ring include the following heterocyclic rings.

  The sulfur-containing compound may be a polymer. The polymer preferably includes a structural unit having a sulfide bond and a mercapto group in the side chain. The structure having a sulfide bond and a mercapto group (hereinafter sometimes referred to as unit (1)) and the main chain may be bonded by a linking group such as an amide bond, an ether bond, a thioether bond, or an ester bond. preferable. The polymer may be a homopolymer or a copolymer.

When the polymer is a copolymer, it may contain the structural unit (a1) having an acid labile group, the structural unit (a2) having no acid labile group, and the like.
The weight average molecular weight of the polymer is usually 3000 or more, preferably 5000 or more, and usually 100,000 or less, preferably 50,000 or less.
When the sulfur-containing compound is a polymer, the content of the structural unit having a sulfide bond and a mercapto group is usually 0.1 to 50 mol% with respect to all the structural units of the polymer of the sulfur-containing compound, preferably It is 0.5-30 mol%, More preferably, it is 1-20 mol%.

The sulfur-containing compound having a ring is, for example, a compound represented by the formula (IA) or a structural unit represented by the formula (IB), preferably a structural unit represented by the formula (IB-1) or the formula (IB- A polymer having a structural unit represented by 2) is preferred.

[In the formula (IB-1),
R ⁱ²² and R ⁱ³² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Represents.
A ² and B ³ each independently represent a nitrogen atom or a carbon atom.
n3 and m3 each independently represents 0 or 1. However, when ^{A 2} is a nitrogen atom, n3 represents 0, when ^{A 2} is a carbon atom, n3 represents 1, when ^{B 2} is a nitrogen atom, m3 is 0, ^{B 2} is When it is a carbon atom, m3 represents 1.
X ⁱ¹¹ represents a sulfur atom and an NH group.
L ⁱ² represents a divalent hydrocarbon group having 1 to 18 carbon atoms. The methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.
R ⁱ⁵ represents a hydrogen atom or a methyl group.
In formula (IB-2),
R ⁱ²³ and R ⁱ³³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Represents.
A ³ and B ³ each independently represent a nitrogen atom or a carbon atom.
n4 and m4 each independently represents 0 or 1. However, when ^{A 3} is a nitrogen atom, n4 is 0, when ^{A 3} is a carbon atom, n4 represents 1, if ^{B 3} is a nitrogen atom, m4 is 0, the ^{B 3} When it is a carbon atom, m4 represents 1.
X ⁱ¹² represents a sulfur atom and an NH group.
^Li3 represents a C1-C14 bivalent hydrocarbon group. The methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.
R ⁱ⁷ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
R ⁱ⁶ represents a hydrogen atom or a methyl group.
mx represents an integer of 0 to 4. ]
R ⁱ⁶ , R ⁱ⁷ and R ⁱ⁸ each independently represent a hydrogen atom or a methyl group.
X ⁱ¹ , X ⁱ¹¹ and X ⁱ¹² each independently represent a sulfur atom and an NH group.
L ⁱ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
L ⁱ² represents a divalent hydrocarbon group having 1 to 18 carbon atoms.
^Li3 represents a C1-C14 bivalent hydrocarbon group. The methylene group contained in these hydrocarbon groups may be substituted with an oxygen atom or a carbonyl group. ]

^Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ⁱ²² , R ⁱ³² , R ⁱ²³ and R ^{i33 include} an aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ⁱ²¹ and R ⁱ³¹ , and The same can be mentioned.
The aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁱ²² , R ⁱ³² , R ⁱ²³ and R ^{i33 includes} an aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁱ²¹ and R ⁱ³¹ , and The same can be mentioned.
The alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by R ⁱ²² , R ⁱ³² , R ⁱ²³ and R ⁱ³³ is an alicyclic hydrocarbon having 3 to 18 carbon atoms represented by R ⁱ²¹ and R ^i31. The same thing as a group is mentioned.

Examples of the divalent hydrocarbon group having 1 to 18 carbon atoms represented by L ^i2, methylene group, ethylene group, propane-1,3-diyl, butane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane -1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16- Diyl group and heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane- 2,4-jii Group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.
^Li2 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms.

Examples of the divalent hydrocarbon group having 1 to 14 carbon atoms represented by L ^i3, methylene group, ethylene group, propane-1,3-diyl, butane-1,4-diyl group, pentane-1,5 -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane -1,11-diyl group, dodecane-1,12-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2- Diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1 Alkanediyl groups such as, 4-diyl groups;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.
^Li3 is preferably an alkanediyl group having 1 to 14 carbon atoms, and more preferably an alkanediyl group having 1 to 11 carbon atoms.
L ⁱ³ is preferably bonded to the p-position with reference to the position bonded to the main chain in the phenyl group.

Examples of the sulfur-containing compound include a compound represented by any one of a compound represented by formula (I-1) to a compound represented by formula (I-26). Especially, it is preferably a compound represented by formula (I-1) to a compound represented by formula (I-13), more preferably a compound represented by formula (I-1), formula (I- 4) and a compound represented by (I-11).

Examples of the sulfur-containing compound include a homopolymer composed of any one of the structural units represented by the formulas (I-27) to (I-38) or a copolymer containing one or more of these structural units. Can be mentioned.
Preferably, it is a copolymer containing one or more structural units represented by formula (I-27) to formula (I-36), more preferably a copolymer containing a structural unit represented by formula (I-33). is there.

  Examples of such copolymers include copolymers composed of structural units represented by formula (I-39) to formula (I-48). Among these, a polymer having a structural unit represented by formula (I-39) to formula (I-44) is preferable.

  The sulfur-containing compound may be synthesized by a known method (for example, JP 2010-79081 A) or may be a commercially available product (for example, Bismuthiol (manufactured by Tokyo Chemical Industry Co., Ltd.)). The polymer containing a sulfur compound may be a commercially available product or may be synthesized by a known method (for example, JP-A-2001-75277).

Examples of the aromatic hydroxy compound include phenol and cresol.
Examples of the benzotriazole compounds include compounds represented by the formula (I).
[In the formula (I),
R ¹ and R ² are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, an amino group, a hydroxyl group, a cyano group, a formyl group, or a sulfonylalkyl group. Or represents a sulfo group.
Q represents a hydrogen atom, a hydroxyl group, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, an aryl group, or ** — R ³ —N (R ⁴ ) —R ⁵ , wherein the hydrocarbon The group may have an amide bond or an ester bond in the structure.
R ³ represents an alkanediyl group having 1 to 6 carbon atoms. ** represents a bond with a nitrogen atom contained in the ring.
R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 1 to 6 carbon atoms. ]

The hydrocarbon group for R ¹ , R ² and Q may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may have a saturated and / or unsaturated bond. These examples are as described above. Examples of the alkanediyl group of R ³ are also as described above.
Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a dihydroxyethyl group, and the like.
Examples of the alkoxyalkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, and an ethoxypropyl group.

  Examples of the benzotriazole compounds include benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole, 1-hydroxymethylbenzotriazole, 1 -Methyl benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 1-methoxy-benzotriazole, 1- (2,2-dihydroxyethyl) -benzotriazole, 1- (2,3-dihydroxypropyl) benzotriazole, or " 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, commercially available from Ciba Specialty Chemicals as the “Irgamet” series, , 2 '-{[(5-Methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, 2,2'-{[(4-Methyl-1H-benzotriazol-1-yl) methyl] Imino} bisethane or 2,2 ′-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bispropane.

Examples of the triazine compound include 1,3,5-triazine-2,4,6-trithiol.
In addition, you may utilize the well-known compound as described in Unexamined-Japanese-Patent No. 2004-347951, 2004-361872 etc., for these adhesive improvement agents, for example.

  The content of the adhesion improver (E) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.05% by mass with respect to the total solid content of the resist composition. % Or more, particularly preferably 0.08 mass% or more. Moreover, it is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 4% by mass or less, and particularly preferably 3% by mass or less.

<Other components (hereinafter sometimes referred to as “other components (F)”)>
The resist composition of this invention may contain the other component (F) as needed. The other component (F) is not particularly limited, and examples thereof include additives, quenchers, sensitizers, dissolution inhibitors, surfactants, stabilizers and dyes known in the resist field.
When using other component (F), the content is suitably selected according to the kind of other component (F).

<Method for producing resist composition>
The resist composition of the present invention comprises a resin (A1) containing a structural unit having an acid labile group, an acid generator (B), a silicon compound (G) having a mercapto group, a solvent (D), and as necessary. It can be prepared by mixing the resin (A2), quencher (C), and other components (F) used. The mixing order is not particularly limited. The temperature at the time of mixing is 10-40 degreeC normally. The mixing time is usually 0.5 to 24 hours. The mixing means is not limited, and stirring and mixing can be used. After mixing each component, it is preferable to filter using a filter having a pore size of about 0.11 to 50 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention to a board | substrate,
(2) a step of drying the resist composition after coating to form a composition layer;
(3) a step of exposing the composition layer; and (4) a step of developing the composition layer after exposure.

Application of the resist composition of the present invention on the substrate in the step (1) can be performed by a coating apparatus such as a spin coater, which is usually used in the field. Examples of the substrate include a silicon wafer, and a semiconductor element (for example, a transistor, a diode, or the like) may be formed on the substrate in advance. When the resist composition of the present invention is used for forming a bump, it is preferable that the substrate is further laminated with a conductive material. Examples of the conductive material include at least one metal selected from the group consisting of gold, copper, nickel, tin, palladium, molybdenum, tungsten, and silver, or an alloy containing at least one metal selected from the group. Examples thereof include copper or an alloy containing copper.
These substrates may be cleaned in advance, or an antireflection film may be formed on the substrate. For the formation of this antireflection film, a commercially available composition for organic antireflection film can be used.

In the step (2), the composition after application is dried to remove the solvent and form a composition layer on the substrate. Drying is performed by, for example, heat drying (so-called pre-baking) using a heating device such as a hot plate, vacuum drying using a decompression device, or a combination of these means. The temperature in this case is preferably about 50 to 200 ° C. The pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.
The film thickness of the composition layer obtained in the step (2) is preferably 3 to 150 μm, and more preferably 4 to 100 μm.

  In the step (3), the composition layer is preferably exposed using an exposure machine. At this time, exposure is usually performed through a mask corresponding to a required pattern. The exposure light source of the exposure machine may be selected according to the resolution of the resist pattern to be manufactured, but a light source that emits light with a wavelength of 345 to 436 nm is preferable, and g-line (wavelength: 436 nm), h-line (wavelength) : 405 nm) or i-line (wavelength: 365 nm) is more preferable.

  After the step (3), a step of heating the composition layer after exposure (so-called post-exposure baking) may be added. Preferably, it is a process of developing with a heating device. An example of the heating device is a hot plate. The heating temperature is usually 50 to 200 ° C, preferably 60 to 120 ° C. The heating time is usually 40 to 400 seconds, preferably 50 to 350 seconds.

In step (4), the composition layer after exposure is preferably developed with a developing device. When performing the said heating process, the composition layer after a heating is developed. For the development, an alkali developer is usually used. Examples of the alkaline developer include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline).
After the development, it is preferable to perform a rinsing process with ultrapure water or the like and further remove moisture remaining on the substrate and the resist pattern.

<Application>
The resist composition of the present invention is useful for producing a thick resist film.
The resist composition for producing a resist film having a thickness of 3 to 150 μm is one of the present inventions.
Furthermore, the resist composition of the present invention is useful for the production of bumps.
When manufacturing a bump using a resist composition, it can usually form with the following procedures.
First, a conductive material (seed metal) is laminated on a wafer on which a semiconductor element or the like is formed to form a conductive layer, and then a resist pattern is formed on the conductive layer with the resist composition of the present invention. Next, by depositing an electrode material (for example, copper, nickel, solder, etc.) by plating using the resist pattern as a mold, the resist pattern and the conductive layer remaining under the resist pattern are removed by etching or the like. , Bumps can be formed. After removing the conductive layer, a bump obtained by melting the electrode material by heat treatment may be used as necessary.

  Since the resist composition of the present invention can produce a resist pattern having high resolution and good adhesion without generating scum, it is useful for producing bumps.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight of the resin is a value determined by gel permeation chromatography under the following analysis conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μL
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

Synthesis Example 1 [Synthesis of Resin A1-1]
20 parts of polyvinylphenol (VP-15000; manufactured by Nippon Soda Co., Ltd.) was dissolved in 240 parts of methyl isobutyl ketone and concentrated with an evaporator. A four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer was charged with the resin solution after concentration and 0.003 part of p-toluenesulfonic acid dihydrate. While maintaining the temperature at 20 to 25 ° C., 5.05 parts of ethyl vinyl ether was added dropwise to the obtained mixture over 10 minutes. The mixture was stirred for 2 hours while maintaining the same temperature. The obtained reaction mixture was diluted with 200 parts of methyl isobutyl ketone and subjected to liquid separation washing with ion-exchanged water 5 times. The obtained organic layer was concentrated to 45 parts using an evaporator, 150 parts of propylene glycol monomethyl ether acetate was added and concentrated again, and 78 parts of a propylene glycol monomethyl ether acetate solution of resin A1-1 ( 29% solids) was obtained. The weight average molecular weight of the resin A1-1 was 2.21 × 10 ⁴ , and the introduction rate of ethoxyethyl groups was 38.5%. Resin A1-1 has the following structural units.

Synthesis Example 2 [Synthesis of Novolak Resin A2-1]
In a four-necked flask equipped with a stirrer, 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, 826.9 parts of methanol Was heated to a reflux state and kept for 4 hours. After cooling, 1320 parts of methyl isobutyl ketone was charged into the resulting mixture, and 1075 parts were distilled off at normal pressure. To the obtained mixture, 762.7 parts of m-cresol and 29.0 parts of 2-tert-butyl-5-methylphenol were added, the temperature was raised to 65 ° C., and 678 parts of 37% formalin was brought to 87 ° C. at the end of dropping. It was added dropwise over 1.5 hours while controlling the temperature. The obtained mixture was kept at 87 ° C. for 10 hours, 1115 parts of methyl isobutyl ketone was added, and the mixture was washed three times with ion-exchanged water. To the obtained resin liquid, 500 parts of methyl isobutyl ketone was added and concentrated under reduced pressure until the total amount reached 3435 parts. Methyl isobutyl ketone (3796 parts) and n-heptane (4990 parts) were added to the resulting resin-containing solution, the temperature was raised to 60 ° C., and the mixture was stirred for 1 hour, followed by liquid separation to obtain a resin liquid. The solution containing the obtained resin was diluted with 3500 parts of propylene glycol monomethyl ether acetate and concentrated to obtain 1690 parts of propylene glycol monomethyl ether acetate solution of novolak resin A2-1 (solid content: 43%). The weight average molecular weight of the novolak resin A2-1 was 7 × 10 ³ .

Examples 1-7 and Comparative Examples 1-3
(Preparation of resist composition)
Each of the components shown in Table 1 or Table 2 is mixed in the parts by mass shown in Table 1 or Table 2 and dissolved in a solvent, and then filtered through a fluororesin filter having a pore size of 0.5 μm to obtain a resist composition. Was prepared.

In this specification, each code | symbol shown in a table | surface represents the following materials.
<Resin>
A1-1: Resin A1-1
A2-1: Novolac resin A2-1
<Acid generator>
B1: N-hydroxynaphthalimide triflate; (NAI-105; manufactured by Midori Chemical Co., Ltd.)
<Quencher>
C1: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Silicon compound (G)>
I1: 3-mercaptopropyltrimethoxysilane (Z-6062: manufactured by Toray Dow Corning Co., Ltd.)
I2: Shin-Etsu Silicone X-41-1818 (manufactured by Shin-Etsu Chemical Co., Ltd.)
I3: Shin-Etsu Silicone X-41-1810 (manufactured by Shin-Etsu Chemical Co., Ltd.)
I4: Shin-Etsu Silicone X-41-1805 (manufactured by Shin-Etsu Chemical Co., Ltd.)
S1: 3-phenylaminopropyltrimethoxysilane (Z-6883: manufactured by Toray Dow Corning Co., Ltd.)
<Solvent>
Propylene glycol monomethyl ether acetate <Surfactant>
Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

(Production of resist pattern): Examples 1 to 4, 6, 7 and Comparative Examples 1 to 3
The above resist composition was spin-coated on a substrate having copper deposited on a 4-inch silicon wafer so that the film thickness after pre-baking was 8 μm.
Then, the composition layer was formed by pre-baking for 180 seconds with the temperature shown in the "PB" column of Table 1 or Table 2 with a direct hot plate.
Next, an i-line stepper [NSR-2005i9C; manufactured by Nikon Corporation, NA = 0.5] was used for the composition layer, and the exposure amount was changed stepwise to form a contact hole pattern (hole diameter: 20 μm, The film was exposed through a mask for forming a pitch (20 μm).
After exposure, post-exposure baking is performed for 180 seconds at the temperature shown in the “PEB” column of Table 1 on a hot plate, and further paddle development is performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained.
The obtained resist pattern was observed with a scanning electron microscope, and the exposure amount at which the hole diameter of the contact hole pattern was 20 μm was defined as effective sensitivity.

(Manufacture of resist pattern): Example 5
The above resist composition was spin-coated on a substrate having copper deposited on a 4-inch silicon wafer so that the film thickness after pre-baking was 25 μm.
Thereafter, the composition layer was formed by pre-baking with a direct hot plate for 180 seconds at the temperature shown in the “PB” column of Table 1.
Next, an i-line stepper [NSR-2005i9C; manufactured by Nikon Corporation, NA = 0.5] was used for the composition layer, and the exposure amount was changed stepwise to form a contact hole pattern (hole diameter: 20 μm, The film was exposed through a mask for forming a pitch (20 μm).
After exposure, a resist pattern was obtained by performing paddle development for 60 seconds with an aqueous 2.38 mass% tetramethylammonium hydroxide solution.
The obtained resist pattern was observed with a scanning electron microscope, and the exposure amount at which the hole diameter of the contact hole pattern was 20 μm was defined as effective sensitivity.

(Bump formation)
The substrate after producing the pattern was subjected to electrolytic plating with “Microfab Au660 (manufactured by Nippon Electroplating Engineers Co., Ltd.)”.

  Resolution evaluation: A contact hole pattern having a hole diameter of 20 μm obtained in effective sensitivity was observed with a scanning electron microscope. Those in which a 20 μm contact hole pattern was resolved were marked with ◯, and those that were not resolved were marked with ×. The results are shown in Table 3.

  Adhesion evaluation: The substrate after plating was observed with an optical microscope. The plating solution eroded the resist bottom and the substrate was discolored. The case where the contact hole pattern of 20 μm was not resolved or the case where scum was generated at the bottom of the contact hole pattern of 20 μm and the plating evaluation was not performed was −. The results are shown in Table 3.

  Scum evaluation: A contact hole pattern having a hole diameter of 20 μm obtained in effective sensitivity was observed with a scanning electron microscope. The bottom part of the 20 μm contact hole pattern was observed, and “X” indicates that scum is generated, and “◯” indicates that the scum is not generated. The results are shown in Table 3.

  From the above results, it can be seen that according to the resist composition of the present invention, a resist pattern having high resolution and good adhesion to a copper substrate can be obtained without generating scum.

  The resist composition of the present invention can produce a resist pattern with high resolution and good adhesion without generating scum.

Claims (7)

A resist composition comprising a resin (A1) containing a structural unit having an acid labile group, a novolac resin, an acid generator (B), a silicon compound (G) having a mercapto group, and a solvent (D). The resist composition according to claim 1, wherein the silicon compound (G) having a mercapto group is a polymer containing a compound represented by the formula (IIA) and / or a unit derived from the compound.
[In the formula (IIA)
R ^j1 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a mercaptoalkyl group having 1 to 5 carbon atoms.
R ^j2 to R ^j4, independently of each other, represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a mercapto group or mercaptoalkyl group having 1 to 5 carbon ^{atoms, R j2} ~ At least one of R ^j4 is a mercapto group or a mercaptoalkyl group having 1 to 5 carbon atoms.
t ⁱ represents an integer of 1 to 10. ]   The resist composition according to claim 1 or 2, wherein the silicon compound is contained in an amount of 0.001% by mass to 0.45% by mass with respect to the solid content of the resist composition. The resin containing a structural unit having an acid labile group is a resin having a structural unit containing at least one group selected from the group represented by formula (1) and the group represented by formula (2). Item 4. The resist composition according to any one of Items 1 to 3.
[In Formula (1),
R ^{a1 to} R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 are bonded to each other to form 2 to 2 carbon atoms. 20 represents a divalent hydrocarbon group, and R ^a3 represents an alkyl group having 1 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. * Represents a bond. ]
[In Formula (2),
R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^{a2 ′} and R ^{a3 ′} is bonded to each other to form a divalent heterocyclic ring having 2 to 20 carbon atoms together with the carbon atom and oxygen atom to which they are bonded, and the methylene group contained in the hydrocarbon group and the divalent heterocyclic group is , Oxygen atom or sulfur atom may be substituted. * Represents a bond. ] The resist composition according to claim 4, wherein the structural unit having a group represented by the formula (1) is a structural unit represented by the formula (a1-1).
[In the formula (a1-1),
R ^a1 , R ^a2 and R ^a3 each have the same meaning as described above.
R ^a4 represents a hydrogen atom or a methyl group. ] The resist composition according to claim 4, wherein the structural unit having a group represented by the formula (2) is a structural unit represented by the formula (a1-2).
[In the formula (a1-2),
R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} each have the same meaning as described above.
R ^a5 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ^a6 may be the same as or different from each other. ] (1) The process of apply | coating the resist composition in any one of Claims 1-6 to a board | substrate,
(2) a step of drying the resist composition after coating to form a composition layer;
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern including a step of developing the composition layer after exposure.