JP2022042954A - Photosensitive resin composition, resist pattern film manufacturing method, and plated formed product manufacturing method - Google Patents

Abstract

To provide a photosensitive resin composition which improves a T-top shape caused by influence of amine existing in environment where a photosensitive resin composition is used, and can obtain an accurate pattern dimension even when measured from a pattern upper surface, and a pattern formation method.SOLUTION: A photosensitive resin composition contains a polymer (A) having an acid dissociable group (A), a photoacid generator (B) and a surface active agent (C), in which the surface active agent (C) is a fluorine-based or silicon-based surface active agent satisfying the following condition (i) and is contained in an amount of 0.5-6 pts.mass with respect to 100 pts.mass of the polymer (A). Condition (i): Absorbency at an optical length of 10 mm and a wavelength of 300 nm of 0.1 mass% aqueous solution of a surface active agent, which is measured using an ultraviolet visible near-infrared spectrophotometer, of 0.30 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive resin composition, a method for producing a resist pattern film, and a method for producing a plated model.

To improve the performance of mobile devices such as smartphones and tablet terminals, semiconductor chips with different functions are used for FO-WLP (Fan-Out Wafer Level Package), FO-PLP (Fan-Out Panel Level Package), and TSV (Through Silicon). Via), it is done by packaging using high density packaging technology such as silicon interposer.

With such packaging technology, the wiring and bumps used for electrical connections between semiconductor chips are also becoming denser. Therefore, the resist pattern film used for forming wiring and bumps is also required to be fine and dense.

Usually, the wiring and bumps are plated objects, and a photosensitive resin composition is applied onto the metal film of a substrate having a metal film such as a copper film to form a resist coating film, and the resist coating film is coated with the resist coating film. It is manufactured by forming a resist pattern film by exposure and development using a mask, and then plating the substrate using the resist pattern film as a mold (see Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2010-001972 Japanese Unexamined Patent Publication No. 2006-330368

The following characteristics are required for the obtained plated model. The shape of the pattern used as a mold is faithfully transferred, and the mask dimensions are faithful.

Conventionally, a resist for bump processing is a chemically amplified resist composed of a polymer having an acid dissociative functional group that dissociates with an acid to generate an acidic functional group, a component that generates an acid by irradiation with radiation, and other additives. Positive radiation sensitive resin compositions are widely used. The resist composed of these compositions is excellent in sensitivity and resolution.

However, in the above-mentioned chemically amplified positive radiation-sensitive resin composition, when exposed to an amine present in the environment after exposure, the cross-sectional shape of the formed pattern is T as shown in FIG. -It tends to be a top shape. In such a case, since the width and spacing of the pattern are measured from the upper surface of the pattern, the measured width and spacing of the pattern tend to be estimated to be larger than the width and spacing of the actual pattern. This point is also affected more by the reduction of the processing dimensions, so improvement is required.

An object of the present invention is to improve the T-top shape caused by the influence of amines present in the environment in which the photosensitive resin composition is used, and to obtain accurate pattern dimensions even when measured from the upper surface of the pattern. It is to provide a photosensitive resin composition and a pattern forming method. Further, it is an object of the present invention to provide a method for manufacturing a plated model as designed with pattern dimensions using the pattern obtained by the above pattern forming method as a mold.

The present inventors have studied to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by a photosensitive resin composition having the following constitution, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [7].

[1] A polymer (A) having an acid dissociative group, a photoacid generator (B), and a surfactant (C) are contained.
The surfactant (C) is a fluorine-based or silicon-based surfactant that satisfies the following condition (i), and is in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass of the polymer (A). A photosensitive resin composition characterized by being contained in:
Condition (i): The absorbance of a 0.1% by mass aqueous solution of the surfactant measured using an ultraviolet-visible-near-infrared spectrophotometer at an optical path length of 10 mm and a wavelength of 300 nm is 0.30 or less.

[2] The photosensitive resin composition according to Item [1], wherein the surfactant (C) has a weight average molecular weight of 8000 or more.
[3] The photosensitive resin composition according to Item [1] or [2], which further contains a sulfur-containing compound (D) having at least one structure selected from a mercapto group, a sulfide bond and a polysulfide bond.
[4] The photosensitive resin composition according to any one of Items [1] to [3], which further contains a novolak resin (E).

[5] The step (1) of forming the resin film of the photosensitive resin composition according to any one of Items [1] to [4] on the metal film of the substrate having the metal film.
The step (2) of exposing the resin film and
The step (3) of developing the resin film after exposure and
A method for producing a resist pattern film, which comprises.

[6] A method for producing a plated molded product, which comprises a step (5) of performing a plating process using a resist pattern film produced by the production method according to Item [5] as a mold.
[7] The method for producing a plated model according to item [6], which further comprises a step (4) of performing plasma treatment of an oxygen-containing gas before the step (5).

According to the present invention, a photosensitive resin composition in which the T-top shape is improved and accurate pattern dimensions can be obtained even when measured from the upper surface of the pattern, and a resist pattern film using the photosensitive resin composition. It is possible to provide a manufacturing method and a manufacturing method of a plated model using the resist pattern film.

FIG. 1 is a schematic view showing an example of a cross-sectional shape (T-top shape) of a pattern formed by a positive radiation-sensitive resin composition. FIG. 2 is a schematic view showing an example of a cross-sectional shape (T-top shape) of a pattern formed by a positive radiation-sensitive resin composition. FIG. 3 is a schematic view showing an example of a cross-sectional shape (T-top shape) of a pattern formed by a positive radiation-sensitive resin composition. FIG. 4 is a schematic view showing an example of a cross-sectional shape (T-top shape) of a pattern formed by a positive radiation-sensitive resin composition.

Unless otherwise specified, each component exemplified in the present specification, for example, each component in the photosensitive resin composition and each structural unit in the polymer (A) may be contained alone. Two or more kinds may be included.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention (hereinafter, also referred to as “the present composition”) includes a polymer (A) having an acid dissociative group (hereinafter, also referred to as “polymer (A)”) and a photoacid generator (hereinafter, also referred to as “polymer (A)”). B) and a surfactant (C) described later are contained. The present composition further comprises a sulfur-containing compound (D) having at least one structure selected from a mercapto group, a sulfide bond and a polysulfide bond (hereinafter, also simply referred to as "compound (D)"), and a novolak resin (hereinafter, simply referred to as "compound (D)"). It is preferable to contain E).

<Polymer (A)>
The polymer (A) has an acid dissociative group.
The acid dissociative group is a group that can be dissociated by the action of an acid generated from the photoacid generator (B). As a result of the dissociation, acidic functional groups such as a carboxy group and a phenolic hydroxyl group are generated in the polymer (A). As a result, the solubility of the polymer (A) in the alkaline developer changes, and the present composition can form a resist pattern film.

The polymer (A) has an acidic functional group protected by an acid dissociative group. Examples of the acidic functional group include a carboxy group and a phenolic hydroxyl group. Examples of the polymer (A) include a (meth) acrylic resin in which a carboxy group is protected by an acid dissociable group, and a polyhydroxystyrene resin in which a phenolic hydroxyl group is protected by an acid dissociative group.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of the polymer (A) is usually 1,000 to 500,000, preferably 3,000 to 300,000, more preferably 10, It is 000 to 100,000, more preferably 20,000 to 60,000.

The ratio (Mw / Mn) of the Mw of the polymer (A) to the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is usually 1 to 5, preferably 1 to 3.

The present composition may contain one or more polymers (A).
The content of the polymer (A) in the present composition is usually 70 to 99.5% by mass, preferably 80 to 99% by mass, and more preferably 90 to 98% of the solid content of the composition. It is mass%. The solid content refers to all components other than the organic solvent described later.

<< Structural unit (a1) >>
The polymer (A) usually has a structural unit (a1) having an acid dissociative group.
Examples of the structural unit (a1) include the structural unit represented by the formula (a1-10) and the structural unit represented by the formula (a1-20), and the structural unit represented by the formula (a1-10) is preferable.

The meanings of the symbols in the formulas (a1-10) and (a1-20) are as follows.
R ¹¹ uses a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or at least one hydrogen atom in the alkyl group as a halogen atom such as a fluorine atom and a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, and an alkoxy. A group substituted with another group such as a group (hereinafter, also referred to as "substituted alkyl group").

R ¹² is a divalent organic group having 1 to 10 carbon atoms.
Ar is an arylene group having 6 to 10 carbon atoms.
R ¹³ is an acid dissociative group.

m is an integer of 0 to 10, preferably 0 to 5, and more preferably an integer of 0 to 3.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a pentyl group and a decyl group.

Examples of the divalent organic group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a decane-1,10-diyl group and the like. Alkanediyl group having 1 to 10 carbon atoms; at least one hydrogen atom in the alkanediyl group is another halogen atom such as a fluorine atom and a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, and an alkoxy group. Examples thereof include a group substituted with a group.

Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group, a methylphenylene group, and a naphthylene group.

Examples of the acid-dissociating group include a group that dissociates due to the action of an acid, and as a result of the dissociation, an acidic functional group such as a carboxy group and a phenolic hydroxyl group is generated in the polymer (A). Specific examples thereof include an acid dissociable group represented by the formula (g1) and a benzyl group, and the acid dissociable group represented by the formula (g1) is preferable.

In the formula (g1), R ^a1 to R ^a3 independently contain an alkyl group, an alicyclic hydrocarbon group, or at least one hydrogen atom in the alkyl group or the alicyclic hydrocarbon group as a fluorine atom and an alicyclic hydrocarbon group. It is a group substituted with a halogen atom such as a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, and another group such as a hydroxyl group, and R ^a1 and R ^a2 are bonded to each other, and R ^a1 and R a ² are bonded to each other. It may form an alicyclic structure together with the carbon atom C.

Examples of the alkyl group of R ^a1 to R ^a3 include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a pentyl group and a decyl group. Be done.

Examples of the alicyclic hydrocarbon group of R ^a1 to R ^a3 include a monocyclic saturated cyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; a cyclobutenyl group and a cyclopentenyl group. Monocyclic unsaturated cyclic hydrocarbon groups such as groups and cyclohexenyl groups; polycyclic saturated cyclic hydrocarbon groups such as norbornyl group, adamantyl group, tricyclodecyl group and tetracyclododecyl group can be mentioned.

The alicyclic structure formed by R ^a1 , Ra ² and carbon atom C includes, for example, monocyclic saturated cyclic hydrocarbon structures such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; cyclobutenyl, cyclopentenyl, cyclo. Monocyclic unsaturated cyclic hydrocarbon structures such as hexenyl; polycyclic saturated cyclic hydrocarbon structures such as norbornyl, adamantyl, tricyclodecyl, tetracyclododecyl and the like.

As the acid dissociative group represented by the formula (g1), the groups represented by the formulas (g11) to (g15) are preferable.

In the formulas (g11) to ( ^g15 ), Ra4 is independently an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and an n-butyl group, and n is 1 to 4 Is an integer of. Each ring structure in the formulas (g11) to (g14) has one or more substituents such as an alkyl group having 1 to 10 carbon atoms, a halogen atom such as a fluorine atom and a bromine atom, a hydroxyl group, and an alkoxy group. You may have. * Indicates a bond.

As the structural unit (a1), in addition to the structural units represented by the formulas (a1-10) and (a1-20), JP-A-2005-208366, JP-A-2000-194127, and US Pat. No. 6,444,394, And the structural unit having an acetal-based acid dissociative group described in US 2006/0210913; the structural unit having a sulton ring described in US 2013/0095425; JP 2000-214587 and US 6,156,481. And the like, the structural unit having a crosslinked acid dissociative group can be mentioned.

The structural units described in the above publication shall be described in the present specification.
The polymer (A) can have one or more structural units (a1).
The content ratio of the structural unit (a1) in the polymer (A) is usually 10 to 50 mol%, preferably 15 to 45 mol%, and more preferably 20 to 40 mol%.

In this specification, the content ratio of each structural unit in the polymer (A) is a value when the total of all the structural units constituting the polymer (A) is 100 mol%. Each of the structural units is usually derived from a monomer during the synthesis of the polymer (A). The content ratio of each structural unit can be measured by ^{1 1} H-NMR.

In one embodiment, the polymer (A) has, as the structural unit (a1), a structural unit represented by the formula (a1-10) in which R ¹¹ is a hydrogen atom, and an alkyl group in which R ¹¹ has 1 to 10 carbon atoms. It is preferable to have a structural unit represented by the formula (a1-10) which is a substituted alkyl group. In such an embodiment, the resolution of the present composition can be further improved, and the swelling resistance and crack resistance of the resist pattern film with respect to the plating solution tend to be further improved.

≪Structural unit (a2) ≫
The polymer (A) can further have a structural unit (a2) having a group that promotes solubility in an alkaline developer (hereinafter, also referred to as “solubility promoting group”). When the polymer (A) has the structural unit (a2), it is possible to adjust the resolution, sensitivity, depth of focus and other lithographic properties of the resin film formed from the present composition.

The structural unit (a2) is, for example, a structural unit having at least one group or structure selected from a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a lactone structure, a cyclic carbonate structure, a sultone structure and a fluoroalcohol structure (however). , Except for those corresponding to the structural unit (a1)). Among these, a structural unit having a phenolic hydroxyl group is preferable because it can form a resist pattern film that is strong against pressing from plating at the time of forming a plated model.

Examples of the structural unit having a carboxy group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 3-. Examples thereof include structural units derived from monomers such as carboxypropyl (meth) acrylate, and structural units described in JP-A-2002-341539.

Examples of the structural unit having a phenolic hydroxyl group include 2-hydroxystyrene, 4-hydroxystyrene, 4-isopropenylphenol, 4-hydroxy-1-vinylnaphthalene, 4-hydroxy-2-vinylnaphthalene, and 4-hydroxyphenyl. Examples thereof include structural units derived from monomers having a hydroxyaryl group such as (meth) acrylate. Examples of the hydroxyaryl group include hydroxyphenyl groups such as hydroxyphenyl group, methylhydroxyphenyl group, dimethylhydroxyphenyl group, dichlorohydroxyphenyl group, trihydroxyphenyl group and tetrahydroxyphenyl group; hydroxynaphthyl group, dihydroxynaphthyl group and the like. Hydroxynaphthyl group of.

Examples of the structural unit having an alcoholic hydroxyl group include a structural unit derived from a monomer such as 2-hydroxyethyl (meth) acrylate and 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran, and JP-A-2009-276607. Examples thereof include the structural units described in the publication.

Examples of the structural unit having a lactone structure include JP-A-2017-058421, JP-A-2010 / 0316954, JP-A-2010-138330, JP-A-2005 / 0287473, JP-A-2016-098350, and US. The structural units described in 2015/0323865A can be mentioned.

Examples of the structural unit having a cyclic carbonate structure include the structural units described in JP-A-2017-058421, JP-A-2009-223294, and JP-A-2017-044875.

Examples of the structural unit having a sultone structure include the structural units described in JP-A-2017-058421, JP-A-2014-029518, US 2016/0085149, and JP-A-2013-007846. ..

Examples of the structural unit having a fluoroalcohol structure include the structural units described in US 2004/0106755, US 2003/0031952, US 2004/0144752, and JP-A-2005-133066.

The structural units described in the above publication shall be described in the present specification.
The polymer (A) can have one or more structural units (a2).
The content ratio of the structural unit (a2) in the polymer (A) is usually 10 to 80 mol%, preferably 20 to 65 mol%, and more preferably 25 to 60 mol%. When the content ratio of the structural unit (a2) is within the above range, the dissolution rate in an alkaline developer can be increased, and as a result, the resolution of the present composition in a thick film can be improved.

The polymer (A) can have the structural unit (a2) in the same or different polymer as the polymer having the structural unit (a1), but the structural units (a1) to (a1) to (in the same polymer). It is preferable to have a2).

≪Structural unit (a3) ≫
The polymer (A) can further have a structural unit (a3) other than the structural units (a1) and (a2).

As the structural unit (a3), for example,
Structural units derived from vinyl compounds such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-methoxybutyl (meth) acrylate, lauroxytetraethylene glycol (meth) acrylate, lauroxydipropylene glycol (meth) acrylate, lauroxytripropylene glycol (meth) acrylate and other aliphatic (meth) acrylic acids. Structural unit derived from ester compound;
Cyclopentyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, etc. Structural unit derived from alicyclic (meth) acrylic acid ester compound;
Structural units derived from aromatic ring-containing (meth) acrylic acid ester compounds such as phenyl (meth) acrylate and phenethyl (meth) acrylate;
(Meta) Structural units derived from unsaturated nitrile compounds such as acrylonitrile, crotonnitrile, maleinenitrile, and fumaronitrile;
Structural units derived from unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide;
Structural units derived from unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Can be mentioned.

The polymer (A) can have one or more structural units (a3).
The content ratio of the structural unit (a3) in the polymer (A) is usually 40 mol% or less.
The polymer (A) can have the structural unit (a3) in the same or different polymer as the polymer having the structural unit (a1) and / or the structural unit (a2), but in the same polymer. It is preferable to have structural units (a1) to (a3) in.

<< Production method of polymer (A) >>
The polymer (A) can be produced by a known polymerization method such as an ionic polymerization method or a radical polymerization method in a suitable polymerization solvent for the monomer corresponding to each structural unit. Among these, the radical polymerization method is preferable.

Examples of the radical polymerization initiator used in the radical polymerization method include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methyl isobutyrate), and 2,2'-azobis- (2,4). -Azobis compound such as dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauryl peroxide and t-butyl peroxide can be mentioned.

Further, in the polymerization, a molecular weight adjusting agent such as a mercaptan compound or a halogen hydrocarbon can be used, if necessary.

<Photoacid generator (B)>
The photoacid generator (B) is a compound that generates an acid upon exposure. By the action of this acid, the acid dissociative group in the polymer (A) is dissociated to generate an acidic functional group such as a carboxy group and a phenolic hydroxyl group. As a result, the exposed portion of the resin film formed from the present composition becomes easily soluble in the alkaline developer, and a positive resist pattern film can be formed. As described above, this composition functions as a chemically amplified positive photosensitive resin composition.

Examples of the photoacid generator (B) include JP-A-2004-317907, JP-A-2014-157252, US 2003/0008241, JP-A-2017-102260, and JP-A-2016-018575. , And the compounds described in US 2016/0320698. These shall be described herein.

Specifically, as the photoacid generator (B),
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium Hexafluorophosphate, 4-t-butylphenyl / diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl / diphenylsulfonium benzenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7 -Di-n-butoxynaphthyltetrahydrothiophenium bis (trifluoromethanesulfonyl) imide anion, 4,7-di-n-butoxynaphthyltetrahydrothiophenium bis (nonafluorobutylsulfonyl) imide anion, 4,7- Onium salt compounds such as di-n-butoxynaphthyltetrahydrothiophenium tris (nonafluorobutylsulfonyl) methide;
1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloro) Halogen-containing compounds such as methyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine;
Sulfone compounds such as 4-trisphenacyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane;
Sulfonic acid compounds such as benzointosylate, pyrogalloltristrifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl-p-toluenesulfonate;
N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) -4-butyl-naphthylimide , N- (trifluoromethylsulfonyloxy) -4-propylthio-naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) Oxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2] .1.1] Sulfoneimides such as heptane-5,6-oxy-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthylimide, N- (10-campha-sulfonyloxy) naphthylimide, etc. Compound;
Bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl-1,1-dimethylethyl Diazomethane compounds such as sulfonyldiazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane;
Can be mentioned.

Among these, an onium salt compound and / or a sulfoneimide compound is preferable because it can form a resist pattern film having excellent resolution and plating solution resistance.
The present composition can contain one or more photoacid generators (B).

The content of the photoacid generator (B) in the present composition is usually 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the polymer (A). It is preferably 0.5 to 10 parts by mass. When the content of the photoacid generator (B) is within the above range, a resist pattern film having better resolution tends to be obtained.

<Surfactant (C)>
The surfactant (C) is a fluorine-based or silicon-based surfactant that satisfies the following condition (i).

Condition (i): The absorbance of a 0.1% by mass aqueous solution of the surfactant measured using an ultraviolet-visible near-infrared spectrophotometer at an optical path length of 10 mm and a wavelength of 300 nm is 0.30 or less.

The upper limit of the absorbance under the condition (i) is preferably 0.26 or less, more preferably 0.22 or less, still more preferably 0.18 or less, and the lower limit is preferably 0.001 or more, more preferably. Is 0.005 or more, more preferably 0.01 or more.

When a resin film is formed using the present composition containing a hydrophilic surfactant (C) that satisfies the condition (i), the surfactant (C) segregates on the surface of the resin film, whereby the resin film is formed. It is considered that the development solubility of the outermost surface of the above-mentioned surface is improved, and as a result, the above-mentioned T-top shape is improved.

The content of the surfactant (C) in the present composition is 0.5 to 6 parts by mass, preferably 0.8 to 5.5, more preferably 1 with respect to 100 parts by mass of the polymer (A). It is in the range of ~ 5. By containing the surfactant (C) in the above range, it is effective in improving the T-top shape. In the conventional photosensitive resin composition, the surfactant is generally used for the purpose of improving the uniformity (coatability) of the coating film, and the content in that case is 0.1% by mass. The following was common. However, in the present invention, it should be said that the effect of improving the T-top shape has been found in a range greatly deviating from the above range, which is the conventional common general knowledge.

The surfactant (C) may be any of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, but the fluorine-based surfactant is used. It is preferable because it is easily available. Further, the surfactant (C) may be used alone or in combination of two or more.

Examples of commercially available surfactants (C) are "Megafuck F553", "Megafuck F559", "Megafuck F477", "Megafuck F570", "Megafuck F557", and "Megafuck F556" ( Examples thereof include DIC Corporation, "Futergent 212M", "Futergent 602A" (above, Neos Co., Ltd.), and "Polyflow LE-607" (Kyoeisha Chemical Co., Ltd.).

The weight average molecular weight of the surfactant (C) is preferably 8,000 or more, more preferably 9,000 to 100,000, still more preferably 10,000 to 80,000. When the weight average molecular weight of the surfactant (C) is within the above range, it tends to segregate on the surface of the resin film.

<Compound (D)>
Compound (D) has at least one selected from a mercapto group, a sulfide bond and a polysulfide bond. In one embodiment, when the photoacid generator (B) having these groups or bonds is used, the compound (D) other than the photoacid generator can be selected and used.

The total number of mercapto groups, sulfide bonds and polysulfide bonds in compound (D) is not particularly limited, but is usually 1 to 10, preferably 1 to 6, and more preferably 2 to 4.

Examples of the compound (D) include the compound (D1) represented by the formula (D1), the compound (D2) represented by the formula (D2), the multimer of the compound (D2), and the compound represented by the formula (D3), which will be described below. (D3) can be mentioned. The compound (D1) and the compound (D2) are preferable, and the compound (D2) is more preferable, because peeling of the resist pattern film from the substrate during the plating treatment can be suppressed.

Compound (D) tends to be highly hydrophobic in one embodiment. The partition coefficient is an index for the hydrophobicity of compound (D). The partition coefficient of compound (D) is preferably 2 to 10, more preferably 3 to 7. The partition coefficient is the value of the octanol / water partition coefficient (logP) calculated by the ClogP method, and the larger the value, the higher the hydrophobicity (fat solubility).

The present composition may contain one or more compounds (D).
The content of the compound (D) in the present composition is usually 0.01 part by mass, preferably 0, as the lower limit of the content with respect to 100 parts by mass of the polymer component containing the polymer (A). It is 0.05 parts by mass, more preferably 0.1 parts by mass, particularly preferably 0.2 parts by mass, and the upper limit of the content is usually 10 parts by mass, preferably 3.0 parts by mass, more preferably 3.0 parts by mass. It is 2.0 parts by mass, particularly preferably 1.0 part by mass. In such an embodiment, the positive composition can more exert the above-mentioned effects. For example, when the content of the compound (D) is 0.2 parts by mass or more, a resist pattern film having a higher rectangularity tends to be formed. Further, for example, when the content of the compound (D) is 2.0 parts by mass or less, the adhesion of the plated model to the substrate having the metal film tends to be higher.

≪Compound (D1) ≫
The compound (D1) is a compound represented by the formula (D1).

In the formula (D1), R ³¹ is an independently monovalent hydrocarbon group or a group in which at least one hydrogen atom in the monovalent hydrocarbon group is substituted with a mercapto group (hereinafter, also referred to as “mercapto substituent”). ). p is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 2 to 3. For example, when p is 3, compound (D1) has a trisulfide bond. When p is 1, it is preferable that at least one R ³¹ is a group in which at least one hydrogen atom in the monovalent hydrocarbon group is substituted with a mercapto group.

The monovalent hydrocarbon group of R ³¹ is usually a monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group and an arylalkyl group.

Examples of the alkyl group of R ³¹ include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a pentyl group and a decyl group.
Examples of the aryl group of R ³¹ include an aryl group having 6 to 10 carbon atoms such as a phenyl group, a methylphenyl group and a naphthyl group.

Examples of the arylalkyl group of R ³¹ include an arylalkyl group having 7 to 12 carbon atoms such as a benzyl group and a phenethyl group.
Examples of the mercapto substituent include a 4-mercaptophenyl group.

In compound (D1), a sulfide bond (when p = 1), a polysulfide bond (when p = an integer of 2 or more) or a mercapto group (when R ³¹ is a mercapto substituent) is bound to a hydrocarbon structure. There is. Therefore, it is presumed that compound (D1) has high hydrophobicity.

Examples of the compound (D1) include compounds represented by the following formulas (D1-1) to (D1-3).

<< Compound (D2) and its multimer >>
The compound (D2) is a compound represented by the formula (D2).

The meaning of each symbol in the formula (D2) is as follows.
R ³² is a divalent hydrocarbon group, preferably an alkanediyl group, an arylene group or an arylene alkanediyl group, among which an alkanediyl group can be satisfactorily produced. Is more preferable.

R ³³ is a divalent hydrocarbon group or a group in which at least one -CH _2- group (excluding both ends) in the divalent hydrocarbon group is replaced with -S- or -O-. Preferred is an alkanediyl group, a group in which at least one -CH ₂ -group (excluding both ends) in the alkanediyl group is substituted with -S- or -O- (hereinafter, also referred to as "substituted alkanediyl group"). It is an arylene group or an arylene alkanediyl group, and among these, an alkanediyl group is more preferable because a plated model can be satisfactorily produced.

The number of carbon atoms of the alkanediyl group is usually 1 to 12, preferably 2 to 12. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. , Octane-1,8-diyl group, decane-1,10-diyl group, dodecane-1,12-diyl group and other linear alkanediyl groups; 1-methylpropane-1,3-diyl group, 2- Examples thereof include branched alkanediyl groups such as methylpropane-1,3-diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group. Among these, a linear alkanediyl group is preferable.

Examples of the substituted alkanediyl group include a group represented by -CH ₂ -CH ₂ -S-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH _2- . Examples are groups represented by CH _2- .

Examples of the arylene group include an arylene group having 6 to 10 carbon atoms such as a phenylene group, a methylphenylene group and a naphthylene group.

The arylene alkanediyl group is a divalent group in which one or more arylene groups and one or more alkanediyl groups are bonded in any order. Examples of the respective arylene group and alkanediyl group include the above-mentioned specific examples.

R ³⁴ shows a glycoluril ring structure or an isocyanul ring structure. Although the glycoluril ring structure and the isocyanul ring structure have a bond that can reduce the hydrophobicity, it is presumed that the hydrophobicity of the compound (D2) is not deteriorated because of its high structural symmetry. To.

m is 1 or 0.
q is an integer of 1 to 4. When R ³⁴ has a glycoluril ring structure, q is an integer of 1 to 4. When R ³⁴ has an isocianul ring structure, q is an integer of 1 to 3. When q is an integer of 2 or more, the groups represented by-(R ³² -S) _m -R ³³ -SH in the formula (D2) may be the same or different.

In compound (D2), the mercapto group or sulfide bond (when m is 1) is bonded to a hydrocarbon structure or a structure having a part of —S— or —O— in the hydrocarbon structure. Therefore, it is presumed that the compound (D2) has high hydrophobicity.

As the compound (D2), the compound (D2-1) represented by the formula (D2-1) and the compound (D2-2) represented by the formula (D2-2) are preferable, and the compound (D2-1) is more preferable. ..

In the formulas (D2-1) and (D2-2), X is independently a hydrogen atom or a monovalent group represented by the formula (g2). However, in the formula (D2-1), at least one X is a monovalent group represented by the formula (g2), and preferably all Xs are monovalent groups represented by the formula (g2). Further, in the formula (D2-2), at least one X is a monovalent group represented by the formula (g2), and preferably all Xs are monovalent groups represented by the formula (g2).

In formula (g2), R ³² , R ³³ and m are synonymous with R ³² , R ³³ and m in formula (D2), respectively, and * is in formula (D2-1) or (D2-2). It is a bond with the nitrogen atom of.

Examples of the compound (D2-1) include 1,3,4,6-tetrakis [2-mercaptoethyl] glycoluril and 1,3,4,6-tetrakis [3- (2-mercaptoethylsulfanyl) propyl]. Glycoluryl, 1,3,4,6-tetrakis [3- (3-mercaptopropylsulfanyl) propyl] glycoluril, 1,3,4,6-tetrakis [3- (4-mercaptobutylsulfanyl) propyl] glycoluril , 1,3,4,6-tetrakis [3- (5-mercaptopentylsulfanyl) propyl] glycoluril, 1,3,4,6-tetrakis [3- (6-mercaptohexylsulfanyl) propyl] glycoluril, 1 , 3,4,6-Tetrakiss [3- (8-mercaptooctylsulfanyl) propyl] glycoluril, 1,3,4,6-tetrakis [3- (10-mercaptodecylsulfanyl) propyl] glycoluril, 1,3 , 4,6-Tetrakiss [3- (12-mercaptododecylsulfanyl) propyl] glycoluryl, 1,3,4,6-tetrakis {3- [2- (2-mercaptoethylsulfanyl) ethylsulfanyl] propyl} glycoluryl , 1,3,4,6-tetrakis (3- {2- [2- (2-mercaptoethoxy) ethoxy] ethylsulfanyl} propyl) glycoluril.

Examples of the compound (D2-2) include 1,3,5-tris [2-mercaptoethyl] isocyanurate, 1,3,5-tris [3- (2-mercaptoethylsulfanyl) propyl] isocyanurate, 1 , 3,5-Tris [3- (3-mercaptopropylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (4-mercaptobutylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (5-Mercaptopentylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (6-mercaptohexylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (8-) Mercaptooctylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (10-mercaptodecylsulfanyl) propyl] isocyanurate, 1,3,5-tris [3- (12-mercaptododecylsulfanyl) propyl] Isocyanurate, 1,3,5-tris {3- [2- (2-mercaptoethylsulfanyl) ethylsulfanyl] propyl} isocyanurate, 1,3,5-tris (3- {2- [2- (2- (2- (2- (2- (2- (2- (2-) Mercaptoethoxy) ethoxy] ethylsulfanyl} propyl) isocyanurate.

The compound (D2) can be synthesized, for example, by the methods described in JP-A-2016-169174, JP-A-2016-164135, and JP-A-2016-164134.

Compound (D2) may form a multimer. The multimer is a multimer obtained by forming a disulfide bond by coupling a plurality of compounds (D2) with a mercapto group. The multimer is, for example, a dimer to pentamer of compound (D2).

≪Compound (D3) ≫
The compound (D3) is a compound represented by the formula (D3).

In formula (D3), R ³⁵ and R ³⁶ are independently hydrogen atoms or alkyl groups, respectively. R ³⁷ is a single bond or an alkanediyl group. R ³⁸ is an r-valent aliphatic group that may contain an atom other than a carbon atom. r is an integer of 2 to 10.

Examples of the alkyl group of R ³⁵ and R ³⁶ include an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a pentyl group and a decyl group. Be done. As R ³⁵ and R ³⁶ , a combination in which one is a hydrogen atom and the other is an alkyl group is preferable.

The carbon number of the arcandyl group of R ³⁷ is usually 1 to 10, preferably 1 to 5. Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a decane-1,10-diyl group. Linear alkanediyl groups such as 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1, Examples thereof include a branched alkanediyl group such as a 4-diyl group. Among these, a linear alkanediyl group is preferable.

R ³⁸ is an r-valent (2 to 10-valent) aliphatic group that may contain an atom other than a carbon atom. Examples of the atom other than the carbon atom include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The structure of the aliphatic group may be linear, branched or cyclic, or may be a combination of these structures.

Examples of the aliphatic group include an r-valent hydrocarbon group having 2 to 10 carbon atoms, an oxygen-containing aliphatic group having an r-valent carbon number of 2 to 10 carbon atoms, and a trivalent group having an isocyanul ring structure and 6 to 10 carbon atoms. The basis of is mentioned.

Examples of the compound (D3) include compounds represented by the following formulas (D3-1) to (D3-4).

<Novolak resin (E)>
The novolak resin (E) may be any as long as it has alkali solubility, and may be obtained by a usual method. The polymer (A) of the present composition has hydrophobicity, while the surfactant (C) has hydrophilicity. By using the novolak resin (E) in this composition, although the reason is not clear, the composition is obtained when a hydrophilic component and a hydrophobic component are mixed like the polymer (A) and the surfactant (C). The compatibility of things is improved. Further, since the alkali solubility can be appropriately controlled, a rectangular pattern shape can be obtained by adjusting the mixing ratio with the polymer (A) and the composition of the novolak resin (E) described later.

The novolak resin (E) is subjected to, for example, condensation polymerization of the phenol compound with aldehydes such as formaldehyde, acetaldehyde or substituted or unsubstituted benzaldehydes, or substitution or substitution with the phenol compound by using an acid catalyst. It can be produced by condensation polymerization with a methylol compound which has not been used.

Suitable novolak resins (E) include phenolic compounds such as phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol and the like, and aldehyde compounds such as formaldehyde, acid or polyvalent. Examples thereof include those obtained by a condensation reaction in the presence of a metal ion catalyst.

The weight average molecular weight of the novolak resin (E) is usually 1,000 to 30,000, preferably 1,000 to 15,000, and more preferably 1,000 to 10,000.
The novolak resin (E) can also be a blend of two or more kinds.

As the novolak resin (E) used in the present invention, a cresol-based novolak resin is preferable. Cresol novolak resins using m-cresol and p-cresol as phenol compounds and formaldehyde as aldehydes are particularly preferable in terms of abundant types, easy availability, and adjustment of alkali solubility.

<Quencher>
The composition can further contain a quencher.
The citric acid is, for example, a component used to control the diffusion of the acid generated by exposure from the photoacid generator (B) in the resin film, and as a result, the resolution of the present composition is improved. Can be made to.

Examples of the quencher include a basic compound and a compound that generates a base. For example, JP-A-2011-029636, JP-A-2014-0133881, JP-A-2015-526752, JP-A-2016- Examples thereof include the compounds described in Japanese Patent Application Laid-Open No. 099483 and JP-A-2017-03732. These shall be described herein.

Examples of the quencher include alkylamines such as n-hexylamine, n-heptylamine, di-n-butylamine and triethylamine; aromatic amines such as aniline and 1-naphthylamine; alkanolamines such as triethanolamine; ethylenediamine, 1,3-Bis [1- (4-aminophenyl) -1-methylethyl] Polyamino compounds such as benzene and polyethyleneimine; Amido compounds such as formamide; Urea compounds such as urea and methylurea; Nitrogen heterocyclic compounds; N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) -4-hydroxypiperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, Examples thereof include nitrogen-containing compounds having an acid dissociative group such as N- (t-butoxycarbonyl) -2-phenylbenzimidazole.

The composition may contain one or more quenchers.
The content of the quencher in the present composition is usually 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymer (A).

<Other ingredients>
The present composition may further contain other components.
Examples of the other components include a surfactant other than the surfactant (C), which has an effect of improving the coatability, defoaming property, etc. of the photosensitive resin composition, and a photoacid by absorbing exposure light. A sensitizer that improves the acid generation efficiency of the generator, an alkali-soluble resin or low-molecular-weight phenol compound that controls the dissolution rate of the resin film formed from the photosensitive resin composition in an alkaline developer, and scattered light during exposure. Examples thereof include an ultraviolet absorber that blocks a light reaction due to wraparound to an unexposed portion, a thermal polymerization inhibitor that enhances the storage stability of the photosensitive resin composition, an antioxidant, an adhesion aid, and an inorganic filler.

<Organic solvent>
The composition may further contain an organic solvent. The organic solvent is, for example, a component used for uniformly mixing each component contained in the present composition.

Examples of the organic solvent include alcohol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monoethyl ether, ethyl lactate, and propylene glycol monomethyether; ethyl acetate, ethyl 2-hydroxypropionate, 2-. Ester solvents such as ethyl hydroxy-2-methylpropionate, methyl acetoacetate, ethyl ethoxyacetate, γ-butyrolactone; ketone solvents such as methylamylketone and cyclohexanone; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, Alkylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether; alkylene glycols such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol mono-n-propyl ether acetate. Examples include monoalkyl ether acetate.

The present composition may contain one or more organic solvents.
The content ratio of the organic solvent in the present composition is usually 40 to 90% by mass.

<Manufacturing of photosensitive resin composition>
The present composition can be produced by uniformly mixing each of the above-mentioned components. Further, in order to remove foreign substances, the above-mentioned components can be uniformly mixed, and then the obtained mixture can be filtered with a filter.

[Photosensitive resin composition kit]
As one embodiment of the present invention, a first agent containing a compound (D) and an organic solvent, a polymer (A) having an acid dissociating group, a photoacid generator (B), and a surfactant (C) Examples thereof include a photosensitive resin composition kit having a second agent containing and. The details of each component are as described above.

The content ratio of the compound (D) in the first agent is usually 0.0001 to 10% by mass, preferably 0.001 to 1% by mass. The second agent may also contain the above-mentioned quencher, other components, an organic solvent and the like. The content (content ratio) of each component in the second agent is the same as the content (content ratio) of each component in the above-mentioned photosensitive resin composition or its solid content.

In the photosensitive resin composition kit, for example, the first agent is applied onto the metal film of a substrate having a metal film, and then the second agent is applied onto the metal film surface-treated by the first agent. It can be used by forming a resin film. Subsequent steps are the same as the steps (2) and (3) described below. It is considered that the effect of the present invention is also exhibited by this method due to the above-mentioned presumed reason that a film containing the compound (D) is formed on the metal film.

[Manufacturing method of resist pattern film]
The method for producing a resist pattern film of the present invention is a step of forming a resin film of the photosensitive resin composition of the present invention on the metal film of a substrate having a metal film, and a step of exposing the resin film (1). 2) and the step (3) of developing the resin film after exposure are included.

<Process (1)>
Examples of the substrate include a semiconductor substrate and a glass substrate. The shape of the substrate is not particularly limited, and the surface shape may be flat plate or uneven, and the shape of the substrate may be circular or square. Moreover, there is no limit to the size of the substrate.

Examples of the metal film include metals such as aluminum, copper, silver, gold and palladium, and a film containing two or more alloys containing the metal, including a copper film, that is, a copper and / or copper alloy. A membrane is preferred. The thickness of the metal film is usually 100 to 10,000 Å, preferably 500 to 2,000 Å. The metal film is usually provided on the surface of the substrate. The metal film can be formed by a method such as a sputtering method.

The resin film is usually formed by applying the present composition onto the metal film of a substrate having a metal film. Examples of the coating method of the present composition include a spin coating method, a roll coating method, a screen printing method, and an applicator method, and among these, the spin coating method and the screen printing method are preferable.

After the present composition is applied, the applied present composition can be heat-treated for the purpose of volatilizing the organic solvent or the like. The conditions for the heat treatment are usually 50 to 200 ° C. for 0.5 to 20 minutes.
The thickness of the resin film is usually 1 to 100 μm, preferably 5 to 80 μm.

<Process (2)>
In the step (2), the resin film formed in the step (1) is exposed.

The exposure is usually carried out selectively on the resin film by 1x projection exposure or reduced projection exposure via a photomask having a predetermined mask pattern. Examples of the exposure light include ultraviolet rays or visible light having a wavelength of 150 to 600 nm, preferably 200 to 500 nm. Examples of the light source of the exposure light include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, and a laser. The exposure amount can be appropriately selected depending on the type of exposure light, the type of the photosensitive resin composition, and the thickness of the resin film, and is usually 100 to 20,000 mJ / cm ² .

After exposure to the resin film and before development, the resin film can be heat-treated. The conditions for the heat treatment are usually 70 to 180 ° C. for 0.5 to 10 minutes. By the heat treatment, the dissociation reaction of the acid dissociable group by the acid in the polymer (A) can be promoted.

<Process (3)>
In the step (3), the resin film exposed in the step (2) is developed to form a resist pattern film. Development is usually carried out using an alkaline developer. Examples of the developing method include a shower method, a spray method, a dipping method, a liquid filling method, and a paddle method. The developing conditions are usually 10 to 30 ° C. for 1 to 30 minutes.

Examples of the alkaline developer include an aqueous solution containing one or more alkaline substances. Examples of alkaline substances include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, and tetramethylammonium hydro. Examples thereof include oxide, tetraethylammonium hydroxide, choline, pyrrole, and piperidine. The concentration of the alkaline substance in the alkaline developer is usually 0.1 to 10% by mass. The alkaline developer can further contain, for example, an organic solvent such as methanol, ethanol and / or a surfactant.

The resist pattern film formed by development can be washed with water or the like. After that, the resist pattern film can be dried using an air gun or a hot plate.

As described above, it is possible to form a resist pattern film as a mold for forming a plated model while suppressing the formation of a T-top shape on the metal film of the substrate. Therefore, the resist pattern film ( A plating substrate having a mold) on a metal film can be obtained. The thickness of the resist pattern film is usually 1 to 100 μm, preferably 5 to 80 μm. As the shape of the opening of the resist pattern film, a shape suitable for the type of the plated model can be selected. When the plated model is wiring, the pattern shape is, for example, a line and space pattern, and when the plated model is a bump, the shape of the opening is, for example, a cube-shaped hole pattern.

By using a plating substrate having a mold in which the formation of the T-top shape is suppressed, it is possible to manufacture a plated model as designed with the pattern dimensions.

[Manufacturing method of plated objects]
In the method for producing a plated molded product of the present invention, a plating substrate having a resist pattern film produced by the method for producing a resist pattern film of the present invention on a metal film is plated using the resist pattern film as a mold. The step (5) to be performed is included. Further, the method for producing a plated molded product of the present invention may further include a step (4) of performing plasma treatment of an oxygen-containing gas after the step (3) and before the step (5). ..

<Process (4)>
By performing plasma treatment of the oxygen-containing gas (surface treatment of the plating substrate) in the step (4), the affinity between the metal film surface and the plating solution can be enhanced.

In the step (4), for example, a plating substrate having a resist pattern film on a metal film is placed in a vacuumed apparatus, oxygen plasma is emitted, and the surface of the plating substrate is treated. The plasma processing conditions are that the power output is usually 50 to 300 W, the flow rate of the oxygen-containing gas is usually 20 to 150 mL, the pressure inside the device is usually 10 to 30 Pa, and the processing time is usually 0.5. ~ 30 minutes. The oxygen-containing gas may contain one or more selected from, for example, hydrogen, argon and methane tetrafluoride, in addition to oxygen. The plating substrate surface-treated by the plasma treatment can be washed with water or the like.

<Process (5)>
In the step (5), the resist pattern film is used as a mold, and a plated model is formed by a plating process in the opening (the portion removed by development) defined by the resist pattern film.

Examples of the plated model include bumps and wiring. The plated model is made of, for example, a conductor such as copper, gold, or nickel. The thickness of the plated object varies depending on its use, but for example, in the case of a bump, it is usually 5 to 100 μm, preferably 10 to 80 μm, more preferably 20 to 60 μm, and in the case of wiring, it is usually 1 to 30 μm. It is preferably 3 to 20 μm, more preferably 5 to 15 μm.

Examples of the plating treatment include a plating liquid treatment using a plating liquid. Examples of the plating solution include a copper plating solution, a gold plating solution, a nickel plating solution, and a solder plating solution. Specific examples thereof include a copper plating solution containing copper sulfate or copper pyrophosphate, and gold plating containing gold potassium cyanide. Examples include a liquid, a nickel plating liquid containing nickel sulfate or nickel carbonate. Among these, a copper plating solution is preferable. The plating solution usually contains a hydrophilic solvent such as water and alcohol.

Specific examples of the plating treatment include wet plating treatments such as electrolytic plating treatment, electroless plating treatment, and hot-dip plating treatment. When forming bumps and wiring in processing at the wafer level, it is usually performed by electroplating.

In the case of the electrolytic plating treatment, the plating film formed on the inner wall of the resist pattern film by the sputtering method or the electroless plating treatment can be used as the seed layer, and the metal film on the substrate can also be used as the seed layer. Further, the barrier layer may be formed before the seed layer is formed, and the seed layer may be used as the barrier layer.

The conditions for the electrolytic plating treatment can be appropriately selected depending on the type of plating solution and the like. In the case of the copper plating solution, the temperature is usually 10 to 90 ° C., preferably 20 to 70 ° C., and the current density is usually 0.3 to 30 A / dm ² , preferably 0.5 to 20 A / dm ² . Is. In the case of the nickel plating solution, the temperature is usually 20 to 90 ° C., preferably 40 to 70 ° C., and the current density is usually 0.3 to 30 A / dm ² , preferably 0.5 to 20 A / dm ² . Is.

As the plating process, different plating processes can be sequentially performed. For example, a solder copper pillar bump can be formed by first performing a copper plating treatment, then performing a nickel plating treatment, and then performing a melt solder plating treatment.

<Other processes>
The method for producing a plated model of the present invention can further include a step of removing the resist pattern film after the step (5). Specifically, this step is a step of peeling off and removing the remaining resist pattern film, and examples thereof include a method of immersing a substrate having a resist pattern film and a plated model in a peeling liquid. The temperature and immersion time of the stripping solution are usually 20 to 80 ° C. for 1 to 10 minutes.

Examples of the stripping solution include a stripping solution containing at least one selected from tetramethylammonium hydroxide, dimethyl sulfoxide and N, N-dimethylformamide.

The method for producing a plated model of the present invention can further include a step of removing the metal film other than the region where the plated model is formed by a method such as a wet etching method.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

<Weight average molecular weight (Mw) of polymer>
The weight average molecular weight (Mw) of the polymer and the surfactant was measured by the gel permeation chromatography method under the following conditions.
-GPC device: Tosoh Corporation, device name "HLC-8220-GPC"
-Column: TSK-M and TSK2500 of columns manufactured by Tosoh Corporation are connected in series.-Solvent: Tetrahydrofuran-Temperature: 40 ° C.
・ Detection method: Refractive index method ・ Standard material: Polystyrene

<Asorbance>
Prepare a 0.1% by mass aqueous solution of the surfactant and put it in a quartz cell with an optical path length of 10 mm. ]) Was used to measure the absorbance at an optical path length of 10 mm and a wavelength of 300 nm.

[Synthesis Examples 1 and 2]
Polymers (A-1) to (A-3) having the structural units shown in Table 1 and their content ratios are produced by radical polymerization using 2,2'-azobis (methyl isobutyrate) as a radical polymerization initiator. did. Details of the structural units shown in Table 1 are shown in the following formulas (a1-1), (a1-4), (a2-1) to (a2-4), (a3-1), (a4-1). The unit of the numerical values in columns a1-1 to a4-1 in Table 1 is mol%. The content ratio of each structural unit was measured by ¹ H-NMR.

<Manufacturing of photosensitive resin composition>
[Examples 1A to 11A, Comparative Examples 1A to 3A] Production of Photosensitive Resin Composition Examples 1A to 11A and Comparative Examples 1A to 3A by uniformly mixing the components of the types and amounts shown in Table 3 below. The photosensitive resin composition of the above was produced. The details of each component other than the polymer component are as follows. The unit of the numerical values in Table 3 is the mass part.
B1: Compound represented by the following formula (B1) B2: Compound represented by the following formula (B2) B3: Compound represented by the following formula (B3)

C1: Fluorosurfactant "Megafuck F553" (manufactured by DIC Corporation)
C2: Fluorosurfactant "Futergent 602A" (manufactured by Neos Co., Ltd.)
C3: Fluorosurfactant "Megafuck F559" (manufactured by DIC Corporation)
C4: Fluorosurfactant "Megafuck F477" (manufactured by DIC Corporation)
C5: Fluorosurfactant "Futergent 212M" (manufactured by Neos Co., Ltd.)
C6: Fluorine-based surfactant "Megafuck F-570" (manufactured by DIC Corporation)
C7: Fluorine-based surfactant "Megafuck F-563" (manufactured by DIC Corporation)
The absorbance and weight average molecular weight of the surfactants (C1) to (C7) under the above condition (i) are shown in Table 2 below.

D1: "Karensu MT (registered trademark) PE1" manufactured by Showa Denko KK
D2: "Karensu MT (registered trademark) NR1" manufactured by Showa Denko KK

E1: Cresol novolak resin (m-cresol: p-cresol = 6: 4 (molar ratio), polystyrene-equivalent weight average molecular weight = 12,000)
E2: Cresol novolak resin (m-cresol: p-cresol = 4: 6 (molar ratio), polystyrene-equivalent weight average molecular weight = 5,000)

S1: Propylene glycol monomethyl ether acetate S2: 3-Methoxybutyl acetate S3: γ-Butyrolactone

<Manufacturing of resist pattern film>
[Examples 1B to 11B, Comparative Examples 1B to 3B]
Using the photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A, two patterning substrates were prepared by the methods described in the following conditions 1 and 2, and resists were prepared according to the evaluation methods and criteria described later. The T-top shape of the pattern film was evaluated.

<< Condition 1 >> (Substrate preparation without leaving time)
The photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A were applied onto the copper sputtered film of the silicon wafer substrate provided with the copper sputtered film using a spin coater, and at 120 ° C. on a hot plate. It was heated for 60 seconds to form a coating film having a film thickness of 6 μm. The coating film was exposed using a stepper (manufactured by Nikon Corporation, model "NSR-i10D") via a pattern mask. The exposed coating film was heated at 90 ° C. for 60 seconds in an environment where the atmospheric amine concentration was controlled to 5 ppb, and then immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 180 seconds for development. .. Then, it was washed with running water and blown with nitrogen to spread the resist pattern films of Examples 1B to 11B and Comparative Examples 1B to 3B (line width: 2 μm, line width / space width = 1/1) on the copper sputter film of the substrate. Formed. The substrate on which the resist pattern film thus obtained is formed is referred to as "patterning substrate-1". The time required from exposure to heating after exposure under this condition is within 30 minutes.

<< Condition 2 >> (Substrate preparation in 24 hours after exposure)
The photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A were applied onto the copper sputtered film of the silicon wafer substrate provided with the copper sputtered film using a spin coater, and at 120 ° C. on a hot plate. It was heated for 60 seconds to form a coating film having a film thickness of 6 μm. The coating film was exposed using a stepper (manufactured by Nikon Corporation, model "NSR-i10D") via a pattern mask. The exposed coating is exposed for 24 hours in an environment contaminated with 5 ppb atmospheric amines, then heated at 90 ° C. for 60 seconds and then immersed in 2.38 mass% tetramethylammonium hydroxide aqueous solution for 180 seconds. And developed. Then, it was washed with running water and blown with nitrogen to spread the resist pattern films of Examples 1B to 11B and Comparative Examples 1B to 3B (line width: 2 μm, line width / space width = 1/1) on the copper sputter film of the substrate. Formed. The substrate on which the resist pattern film thus obtained is formed is referred to as "patterning substrate-2".

≪Evaluation method and criteria≫
With respect to the patterning substrate-1 and the patterning substrate-2 prepared using each photosensitive resin composition, the T-top shape of the obtained resist pattern film was observed with an electron microscope. Then, as shown in FIG. 1 and the like, the pattern width when the resist pattern is observed from directly above with an electron microscope is set to W1, and the T-top shape end portion (overhanging portion) when the cross section of the resist pattern is observed with an electron microscope. ) And the width of the pattern connecting the points 3a and 3b intersecting the pattern side wall extending in the direction perpendicular to the substrate is W2, and the total T-top width (W1-W2) is obtained, and the ratio to the pattern width W2 ( (W1-W2) / W2 × 100 = Wt (%)) was calculated. Let Wt of the patterning substrate-1 be Wt1 and Wt of the patterning substrate-2 be Wt2. The form of the pattern side wall is not limited to the form extending straight in the vertical direction from the patterning substrate as shown in FIG. 1, for example, bulging from the patterning substrate as shown in FIG. 2 like a barrel shape. A form extending vertically in a state, a form extending vertically from a patterning substrate as shown in FIG. 3, a form extending vertically from a patterning substrate as shown in FIG. 4, and a form extending vertically from a patterning substrate as shown in FIG. And so on. For each photosensitive resin composition, Wt2-Wt1 was calculated and evaluated according to the following criteria. The evaluation results are shown in Table 4.

⊚: (Wt2-Wt1) is 0% or more and less than 10%.
〇: (Wt2-Wt1) is 10% or more and less than 20%.
Δ: (Wt2-Wt1) is 20% or more and less than 30%.
X: (Wt2-Wt1) is 30% or more.

In each photosensitive resin composition, Wt1 hardly generated the T-top shape due to the influence of the environmental amine, but the larger (Wt2-Wt1), the more the T-top shape was derived from the influence of the environmental amine. It is probable that it occurred.

Further, with respect to the obtained patterning substrate-1, the state of the interface between the resist pattern film and the copper sputter film was observed with an electron microscope, and the adhesion of the resist pattern film was evaluated according to the following criteria. The evaluation results are shown in Table 4.

⊚: No pattern peeling including isolated wiring part in 2 μmLS pattern.
〇: No pattern peeling except for the isolated wiring part in the 2 μmLS pattern.
X: Pattern peeling was occasionally observed in the 2 μmLS pattern.

<Manufacturing of plated objects>
[Examples 1C to 11C, Comparative Examples 1C to 3C]
Using the resist pattern film-1 as a mold, electrolytic plating was performed to produce a plated model. Except for Example 11C, as a pretreatment for the electrolytic plating treatment, treatment with oxygen plasma (output 100 W, oxygen flow rate 100 ml, treatment time 60 seconds) was performed, and then washing with water was performed.

The pretreated patterning substrate-1 (the untreated patterning substrate in Example 11C) was immersed in 1 L of a copper plating solution (product name "MICROFAB SC-40", manufactured by MacDermid Performance Solutions Japan Co., Ltd.). The plating bath temperature was set to 25 ° C. and the current density was 8.5 A / dm ² , and the electric field plating treatment was performed for 2 minutes and 10 seconds to manufacture a plated model.

The state of the manufactured plated model was observed with an electron microscope and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 4 below.

〇: A rectangular shape was obtained without peeling of the plating.
X: A rectangular shape could not be obtained due to peeling of the plating or peeling of the pattern.

1 ... Substrate 2 ... Pattern 3a, 3b ... The point where the T-top shape and the side wall of the pattern extending in the direction perpendicular to the substrate intersect when the cross section of the resist pattern is observed with an electron microscope W1 ... Pattern width when the resist pattern is observed from directly above with an electron microscope W2 ... Width of the pattern connecting the above 3a and 3b when the cross section of the resist pattern is observed with an electron microscope.

Claims (7)

It contains a polymer (A) having an acid dissociative group, a photoacid generator (B), and a surfactant (C).
The surfactant (C) is a fluorine-based or silicon-based surfactant that satisfies the following condition (i), and is in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass of the polymer (A). A photosensitive resin composition characterized by being contained in:
Condition (i): The absorbance of a 0.1% by mass aqueous solution of the surfactant measured using an ultraviolet-visible-near-infrared spectrophotometer at an optical path length of 10 mm and a wavelength of 300 nm is 0.30 or less. The photosensitive resin composition according to claim 1, wherein the surfactant (C) has a weight average molecular weight of 8000 or more. The photosensitive resin composition according to claim 1 or 2, further comprising a sulfur-containing compound (D) having at least one structure selected from a mercapto group, a sulfide bond and a polysulfide bond. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a novolak resin (E). The step (1) of forming the resin film of the photosensitive resin composition according to any one of claims 1 to 4 on the metal film of the substrate having the metal film.
The step (2) of exposing the resin film and
The step (3) of developing the resin film after exposure and
A method for producing a resist pattern film, which comprises. A method for producing a plated molded product, which comprises a step (5) of performing a plating process using a resist pattern film produced by the production method according to claim 5 as a mold. The method for producing a plated model according to claim 6, further comprising a step (4) of performing plasma treatment of an oxygen-containing gas before the step (5).

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