Manufacturing method for plating objects

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

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a resist pattern film, and a method for producing a plated object. [Background technology]

[0002] The performance of mobile devices such as smartphones and tablet terminals is improved by packaging semiconductor chips with different functions using high-density packaging technologies such as FO-WLP (Fan-Out Wafer Level Package), FO-PLP (Fan-Out Panel Level Package), TSV (Through Silicon Via), and silicon interposers.

[0003] In such packaging technology, the wiring and bumps used for electrical connection between semiconductor chips are becoming denser, and therefore, the resist pattern films used for forming the wiring and bumps are also required to be finer and denser.

[0004] Typically, wiring and bumps are plated objects, and are produced by applying a photosensitive resin composition onto a metal film such as a copper film on a substrate having the metal film to form a resist coating film, exposing and developing the resist coating film using a mask to form a resist pattern film, and then using the resist pattern film as a mold to perform plating on the substrate (see Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-008972 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-330368 Summary of the Invention [Problem to be solved by the invention]

[0006] The resulting plated object must have the following characteristics: The shape of the template pattern must be faithfully transferred, and the dimensions must be faithful to the mask dimensions.

[0007] Conventionally, chemically amplified positive-tone radiation-sensitive resin compositions containing a polymer having an acid-dissociable functional group that dissociates with an acid to generate an acidic functional group, a component that generates an acid upon irradiation with radiation, and other additives have been widely used as resists for bump processing. Resists made from these compositions have excellent sensitivity and resolution.

[0008] However, when the above-described chemically amplified positive-tone radiation-sensitive resin composition is exposed to amines present in the environment after exposure, the cross-sectional shape of the formed pattern tends to become a T-top shape as shown in Figure 1. In such cases, the pattern width and spacing are measured from the top surface of the pattern, and the measured pattern width and spacing tend to be estimated to be larger than the actual pattern width and spacing. This issue has also been affected by the reduction in processing dimensions, and improvements are being sought.

[0009] The present invention aims to provide a photosensitive resin composition and a pattern formation method that can improve the T-top shape caused by the influence of amines present in the environment in which the photosensitive resin composition is used, and can obtain accurate pattern dimensions even when measured from the top surface of the pattern. It is also an object of the present invention to provide a method for producing a plated object with designed pattern dimensions using the pattern obtained by the pattern formation method as a template. [Means for solving the problem]

[0010] The present inventors have conducted research to solve the above problems. As a result, they have found that the above 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].

[0011] [1] A composition comprising a polymer (A) having an acid-dissociable group, a photoacid generator (B), and a surfactant (C), A photosensitive resin composition, characterized in that the surfactant (C) is a fluorine-based or silicon-based surfactant that satisfies the following condition (i), and is contained in an amount of 0.5 to 6 parts by mass per 100 parts by mass of the polymer (A): 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.

[0012] [2] The photosensitive resin composition according to item [1], wherein the surfactant (C) has a weight average molecular weight of 8,000 or more. [3] The photosensitive resin composition according to item [1] or [2], further comprising a sulfur-containing compound (D) having at least one structure selected from the group consisting of a mercapto group, a sulfide bond, and a polysulfide bond. [4] The photosensitive resin composition according to any one of items [1] to [3], further comprising a novolak resin (E).

[0013] [5] A step (1) of forming a resin film of the photosensitive resin composition according to any one of items [1] to [4] on a metal film of a substrate having the metal film; a step (2) of exposing the resin film to light; a step (3) of developing the resin film after exposure; A method for producing a resist pattern film, comprising:

[0014] [6] A method for producing a plated object, comprising the step (5) of performing a plating process using the resist pattern film produced by the method according to item [5] as a mold. [7] The method for producing a plated object according to item [6], further comprising a step (4) of performing a plasma treatment with an oxygen-containing gas before the step (5). [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a photosensitive resin composition that improves the T-top shape and enables accurate pattern dimensions to be obtained even when measured from the top surface of the pattern, a method for producing a resist pattern film using the photosensitive resin composition, and a method for producing a plated object using the resist pattern film. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic diagram showing an example of the cross-sectional shape (T-top shape) of a pattern formed from a positive-tone radiation-sensitive resin composition. [Figure 2] FIG. 2 is a schematic diagram showing an example of the cross-sectional shape (T-top shape) of a pattern formed from a positive-tone radiation-sensitive resin composition. [Figure 3] FIG. 3 is a schematic diagram showing an example of the cross-sectional shape (T-top shape) of a pattern formed from a positive-tone radiation-sensitive resin composition. [Figure 4] FIG. 4 is a schematic diagram showing an example of the cross-sectional shape (T-top shape) of a pattern formed from a positive-tone radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0017] Each of the components exemplified in this specification, for example, each component in the photosensitive resin composition and each structural unit in the polymer (A), may be contained alone or in combination, unless otherwise specified.

[0018] [Photosensitive resin composition] The photosensitive resin composition of the present invention (hereinafter also referred to as "the composition") contains a polymer (A) having an acid-dissociable group (hereinafter also referred to as "polymer (A)"), a photoacid generator (B), and a surfactant (C) described below. The composition preferably further contains a sulfur-containing compound (D) (hereinafter also referred to simply as "compound (D)") having at least one structure selected from a mercapto group, a sulfide bond, and a polysulfide bond, and a novolak resin (E).

[0019] <Polymer (A)> The polymer (A) has an acid-dissociable group. The acid-dissociable 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 carboxyl groups and phenolic hydroxyl groups are generated in the polymer (A). As a result, the solubility of the polymer (A) in an alkaline developer changes, and the composition can form a resist pattern film.

[0020] The polymer (A) has an acidic functional group protected by an acid-dissociable 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 the carboxy group is protected by an acid-dissociable group, and a polyhydroxystyrene resin in which the phenolic hydroxyl group is protected by an acid-dissociable group.

[0021] The weight average molecular weight (Mw) of the polymer (A) in terms of polystyrene measured by gel permeation chromatography is usually 1,000 to 500,000, preferably 3,000 to 300,000, more preferably 10,000 to 100,000, and even more preferably 20,000 to 60,000.

[0022] The ratio (Mw / Mn) of Mw of the polymer (A) to the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is usually 1-5, and preferably 1-3.

[0023] The present composition may contain one or more polymers (A). The content of the polymer (A) in the composition is usually 70 to 99.5 mass%, preferably 80 to 99 mass%, and more preferably 90 to 98 mass%, based on 100 mass% of the solid content of the composition. The solid content refers to all components other than the organic solvent described below.

[0024] <Structural unit (a1)> The polymer (A) usually has a structural unit (a1) having an acid-dissociable group. Examples of the structural unit (a1) include a structural unit represented by formula (a1-10) and a structural unit represented by formula (a1-20), with the structural unit represented by formula (a1-10) being preferred.

[0025] [ka]

[0026] The meanings of the symbols in formulae (a1-10) and (a1-20) are as follows: R 11 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group in which at least one hydrogen atom in the alkyl group has been substituted with another group such as a halogen atom such as a fluorine atom or a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, or an alkoxy group (hereinafter also referred to as a "substituted alkyl group").

[0027] 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-dissociable group.

[0028] m is an integer of 0 to 10, preferably an integer of 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.

[0029] Examples of the divalent organic group having 1 to 10 carbon atoms include alkanediyl groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a decane-1,10-diyl group; and groups in which at least one hydrogen atom in the alkanediyl group has been substituted with another group, such as a halogen atom such as a fluorine atom or a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, or an alkoxy group.

[0030] Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group, a methylphenylene group, and a naphthylene group.

[0031] The acid-dissociable group includes a group that dissociates under the action of an acid and generates an acidic functional group such as a carboxyl group or a phenolic hydroxyl group in the polymer (A) as a result of the dissociation. Specific examples include an acid-dissociable group represented by formula (g1) and a benzyl group, and the acid-dissociable group represented by formula (g1) is preferred.

[0032] [ka]

[0033] In formula (g1), R a1 ~R a3 are each independently an alkyl group, an alicyclic hydrocarbon group, or a group in which at least one hydrogen atom in the alkyl group or the alicyclic hydrocarbon group has been substituted with another group such as a halogen atom such as a fluorine atom or a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, or an alkoxy group; R a1 and R a2 are mutually bonded to form R a1 and R a2 may form an alicyclic structure together with the carbon atom C to which it is bonded.

[0034] R a1 ~R a3 Examples of the alkyl group include alkyl groups 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.

[0035] R a1 ~R a3Examples of the alicyclic hydrocarbon group include monocyclic saturated cyclic hydrocarbon groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; monocyclic unsaturated cyclic hydrocarbon groups such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic saturated cyclic hydrocarbon groups such as a norbornyl group, an adamantyl group, a tricyclodecyl group, and a tetracyclododecyl group.

[0036] R a1 , R a2 and carbon atom C, examples of the alicyclic structure include monocyclic saturated cyclic hydrocarbon structures such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; monocyclic unsaturated cyclic hydrocarbon structures such as cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic saturated cyclic hydrocarbon structures such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl.

[0037] As the acid-dissociable group represented by formula (g1), groups represented by formulae (g11) to (g15) are preferred.

[0038] [ka]

[0039] In formulas (g11) to (g15), R a4 are each independently an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, or an n-butyl group, and n is an integer of 1 to 4. Each ring structure in formulas (g11) to (g14) may have one or more substituents, such as an alkyl group having 1 to 10 carbon atoms, a halogen atom such as a fluorine atom or a bromine atom, a hydroxyl group, or an alkoxy group. * indicates a bond.

[0040] Examples of the structural unit (a1), in addition to the structural units represented by formulae (a1-10) and (a1-20), include structural units having an acetal-based acid-dissociable group described in JP 2005-208366 A, JP 2000-194127 A, U.S. Pat. No. 6,444,394 A, and U.S. Pat. No. 2006 / 0210913 A; structural units having a sultone ring described in U.S. Pat. No. 2013 / 0095425 A; and structural units having a crosslinked acid-dissociable group described in JP 2000-214587 A and U.S. Pat. No. 6,156,481 A, etc.

[0041] The structural units described in the above publications are intended to be as described in this specification. The polymer (A) can have one or more types of structural units (a1). The content 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 %.

[0042] In this specification, the content of each structural unit in polymer (A) is a value when the total of all structural units constituting polymer (A) is 100 mol %. Each of the structural units is usually derived from a monomer used in synthesizing polymer (A). The content of each structural unit is expressed as follows: 1 It can be measured by H-NMR.

[0043] In one embodiment, the polymer (A) contains, as the structural unit (a1), R 11 is a hydrogen atom, and R 11 and a structural unit represented by formula (a1-10), wherein R is an alkyl group or a substituted alkyl group having 1 to 10 carbon atoms. In such an embodiment, the resolution of the composition can be further improved, and the swelling resistance and cracking resistance of the resist pattern film to a plating solution tend to be further improved.

[0044] <Structural unit (a2)> The polymer (A) may further include a structural unit (a2) having a group that promotes solubility in an alkaline developer (hereinafter also referred to as a "solubility-promoting group"). The polymer (A) may include the structural unit (a2), which allows adjustment of the lithographic properties, such as the resolution, sensitivity, and depth of focus, of a resin film formed from the composition.

[0045] Examples of the structural unit (a2) include structural units 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 (excluding those corresponding to the structural unit (a1)). Among these, a structural unit having a phenolic hydroxyl group is preferred because it can form a resist pattern film that is resistant to indentation from plating during the formation of a plated object.

[0046] Examples of structural units having a carboxy group include structural units derived from monomers such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and 3-carboxypropyl (meth)acrylate, as well as structural units described in JP-A-2002-341539.

[0047] Examples of structural units having a phenolic hydroxyl group include structural units derived from monomers having a hydroxyaryl group, such as 2-hydroxystyrene, 4-hydroxystyrene, 4-isopropenylphenol, 4-hydroxy-1-vinylnaphthalene, 4-hydroxy-2-vinylnaphthalene, and 4-hydroxyphenyl(meth)acrylate. Examples of hydroxyaryl groups include hydroxyphenyl groups such as hydroxyphenyl, methylhydroxyphenyl, dimethylhydroxyphenyl, dichlorohydroxyphenyl, trihydroxyphenyl, and tetrahydroxyphenyl; and hydroxynaphthyl groups such as hydroxynaphthyl and dihydroxynaphthyl.

[0048] Examples of structural units having an alcoholic hydroxyl group include structural units derived from monomers such as 2-hydroxyethyl (meth)acrylate and 3-(meth)acryloyloxy-4-hydroxytetrahydrofuran, and structural units described in JP-A-2009-276607.

[0049] Examples of structural units having a lactone structure include structural units described in JP 2017-058421 A, US 2010 / 0316954 A, JP 2010-138330 A, US 2005 / 0287473 A, JP 2016-098350 A, and US 2015 / 0323865 A.

[0050] Examples of structural units having a cyclic carbonate structure include structural units described in JP-A-2017-058421, JP-A-2009-223294, and JP-A-2017-044875.

[0051] Examples of structural units having a sultone structure include structural units described in JP-A-2017-058421, JP-A-2014-029518, US 2016 / 0085149, and JP-A-2013-007846.

[0052] Examples of structural units having a fluorine alcohol structure include structural units described in US 2004 / 0106755, US 2003 / 0031952, US 2004 / 0144752, and JP-A 2005-133066.

[0053] The structural units described in the above publications are intended to be as described in this specification. The polymer (A) can have one or more types of structural units (a2). The content 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 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.

[0054] The polymer (A) may contain the structural unit (a2) in the same or different polymer as the polymer containing the structural unit (a1), but it is preferable that the structural units (a1) and (a2) are contained in the same polymer.

[0055] <Structural unit (a3)> The polymer (A) may further have a structural unit (a3) ​​other than the structural units (a1) and (a2).

[0056] Examples of the structural unit (a3) ​​include: Structural units derived from vinyl compounds such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, and 4-methoxystyrene; Structural units derived from aliphatic (meth)acrylate ester compounds, such as 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, and lauroxytripropylene glycol (meth)acrylate; Structural units derived from alicyclic (meth)acrylic acid ester compounds, such as cyclopentyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, and tetrahydropyranyl (meth)acrylate; Structural units derived from aromatic ring-containing (meth)acrylic acid ester compounds such as phenyl (meth)acrylate and phenethyl (meth)acrylate; Structural units derived from unsaturated nitrile compounds such as (meth)acrylonitrile, crotononitrile, maleonitrile, and fumaronitrile; Structural units derived from unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide; Structural units derived from unsaturated imide compounds such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Examples include:

[0057] The polymer (A) can have one or more types of structural units (a3). The content of the structural unit (a3) ​​in the polymer (A) is usually 40 mol % or less. The polymer (A) may contain the structural unit (a3) ​​in the same or different polymer as the polymer containing the structural unit (a1) and / or the structural unit (a2), but it is preferable that the structural units (a1) to (a3) ​​are contained in the same polymer.

[0058] <Method for producing polymer (A)> The polymer (A) can be produced by subjecting monomers corresponding to the respective structural units to a known polymerization method such as ionic polymerization or radical polymerization in an appropriate polymerization solvent. Of these, radical polymerization is preferred.

[0059] Examples of the radical polymerization initiator used in the radical polymerization method include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), and 2,2'-azobis-(2,4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauryl peroxide, and t-butyl peroxide.

[0060] In the polymerization, a molecular weight modifier such as a mercaptan compound or a halogenated hydrocarbon may be used, if necessary.

[0061] <Photoacid generator (B)> The photoacid generator (B) is a compound that generates an acid upon exposure. The action of this acid dissociates the acid-dissociable groups in the polymer (A), generating acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. As a result, the exposed areas of the resin film formed from this composition become readily soluble in an alkaline developer, allowing the formation of a positive resist pattern film. In this way, this composition functions as a chemically amplified positive photosensitive resin composition.

[0062] Examples of the photoacid generator (B) include compounds described in JP 2004-317907 A, JP 2014-157252 A, US 2003 / 0008241 A, JP 2017-102260 A, JP 2016-018075 A, and US 2016 / 0320698 A. These are incorporated herein by reference.

[0063] Specific examples of the photoacid generator (B) include: Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t- Onium salt compounds such as butylphenyl diphenylsulfonium benzenesulfonate, 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-butoxynaphthyl tetrahydrothiophenium bis(trifluoromethanesulfonyl)imide anion, 4,7-di-n-butoxynaphthyl tetrahydrothiophenium bis(nonafluorobutylsulfonyl)imide anion, and 4,7-di-n-butoxynaphthyl tetrahydrothiophenium tris(nonafluorobutylsulfonyl)methide; Halogen-containing compounds such as 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, and naphthyl-bis(trichloromethyl)-s-triazine; Sulfone compounds such as 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis(phenylsulfonyl)methane; sulfonic acid compounds such as benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, and o-nitrobenzyl-p-toluenesulfonate; sulfonimide compounds such as 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)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.1.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)naphthylimide, and N-(10-camphorsulfonyloxy)naphthylimide; diazomethane compounds such as bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl-1,1-dimethylethylsulfonyldiazomethane, and bis(1,1-dimethylethylsulfonyl)diazomethane; Examples include:

[0064] Among these, onium salt compounds and / or sulfonimide compounds are preferred because they are capable of forming a resist pattern film that has excellent resolution and plating solution resistance. The composition may contain one or more photoacid generators (B).

[0065] The content of the photoacid generator (B) in the composition is usually 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymer (A). When the content of the photoacid generator (B) is within the above range, a resist pattern film with more excellent resolution tends to be obtained.

[0066] <Surfactant (C)> The surfactant (C) is a fluorine-based or silicon-based surfactant that satisfies the following condition (i):

[0067] 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.

[0068] The upper limit of absorbance in the condition (i) is preferably 0.26 or less, more preferably 0.22 or less, and even more preferably 0.18 or less, and the lower limit is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more.

[0069] When a resin film is formed using this composition containing a hydrophilic surfactant (C) that satisfies condition (i), the surfactant (C) segregates on the surface of the resin film, improving the development solubility of the outermost surface of the resin film, and as a result, it is believed that the above-mentioned T-top shape is improved.

[0070] The content of surfactant (C) in the composition is 0.5 to 6 parts by mass, preferably 0.8 to 5.5, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the polymer (A). The inclusion of surfactant (C) within this range is effective in improving the T-top shape. In conventional photosensitive resin compositions, surfactants are generally used to improve the uniformity (coatability) of the coating film, and in such cases, the content is generally about 0.1% by mass or less. However, in the present invention, the effect of improving the T-top shape has been discovered within a range significantly outside the above range, which is conventional common technical knowledge.

[0071] 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 a fluorine-based surfactant is preferred from the viewpoint of ease of availability, etc. The surfactant (C) may be used alone or in combination of two or more kinds.

[0072] Examples of commercially available surfactants (C) include "Megafac F553," "Megafac F559," "Megafac F477," "Megafac F570," "Megafac F557," and "Megafac F556" (all manufactured by DIC Corporation), "Ftergent 212M" and "Ftergent 602A" (all manufactured by Neos Corporation), and "Polyflow LE-607" (manufactured by Kyoeisha Chemical Co., Ltd.).

[0073] The weight-average molecular weight of the surfactant (C) is preferably 8,000 or more, more preferably 9,000 to 100,000, and even 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 easily on the surface of the resin film.

[0074] <Compound (D)> The compound (D) has at least one selected from a mercapto group, a sulfide bond, and a polysulfide bond. In one embodiment, when a photoacid generator (B) having such a group or bond is used, a compound (D) other than the photoacid generator can be selected and used.

[0075] The total number of mercapto groups, sulfide bonds and polysulfide bonds in compound (D) is not particularly limited, but is usually 1-10, preferably 1-6, and more preferably 2-4.

[0076] Examples of the compound (D) include the compound (D1) shown in formula (D1), the compound (D2) shown in formula (D2), a polymer of the compound (D2), and the compound (D3) shown in formula (D3), which are explained below. The compound (D1) and the compound (D2) are preferred, and the compound (D2) is more preferred, since they can suppress peeling of the resist pattern film from the substrate during plating treatment.

[0077] In one embodiment, compound (D) tends to be highly hydrophobic. The partition coefficient serves as an indicator of 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 a larger value indicates higher hydrophobicity (lipid solubility).

[0078] The composition may contain one or more compounds (D). The content of compound (D) in the composition is, relative to 100 parts by mass of the polymer component containing polymer (A), typically 0.01 parts by mass, preferably 0.05 parts by mass, more preferably 0.1 parts by mass, and particularly preferably 0.2 parts by mass. The content of compound (D) in the composition is typically 10 parts by mass, preferably 3.0 parts by mass, more preferably 2.0 parts by mass, and particularly preferably 1.0 parts by mass. In this embodiment, the positive-tone composition can more effectively exhibit the effects described above. For example, if the content of compound (D) is 0.2 parts by mass or more, a resist pattern film with higher rectangularity tends to be formed. Furthermore, if the content of compound (D) is 2.0 parts by mass or less, the adhesion of the plated object to a substrate having a metal film tends to be higher.

[0079] ≪Compound (D1)≫ The compound (D1) is a compound represented by the formula (D1).

[0080] [ka]

[0081] In formula (D1), R 31 are each independently a monovalent hydrocarbon group, or a group in which at least one hydrogen atom in the monovalent hydrocarbon group has been substituted with a mercapto group (hereinafter also referred to as a "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, at least one R 31 is preferably a group in which at least one hydrogen atom in the monovalent hydrocarbon group has been substituted with a mercapto group.

[0082] R 31 The monovalent hydrocarbon group is usually a monovalent hydrocarbon group having a carbon number of 1 to 12. Examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, and an arylalkyl group.

[0083] R 31Examples of the alkyl group include alkyl groups 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. R 31 Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, such as a phenyl group, a methylphenyl group, and a naphthyl group.

[0084] R 31 Examples of the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms, such as a benzyl group and a phenethyl group. Mercapto substituents include, for example, 4-mercaptophenyl groups.

[0085] In the compound (D1), a sulfide bond (when p=1), a polysulfide bond (when p=2 or more), or a mercapto group (R 31 is a mercapto substituent) is bonded to a hydrocarbon structure, which is why compound (D1) is presumed to be highly hydrophobic.

[0086] Examples of the compound (D1) include compounds represented by the following formulas (D1-1) to (D1-3).

[0087] [ka]

[0088] <Compound (D2) and multimers thereof> The compound (D2) is a compound represented by the formula (D2).

[0089] [ka]

[0090] The meanings of the symbols in formula (D2) are as follows: R 32is a divalent hydrocarbon group, preferably an alkanediyl group, an arylene group, or an arylenealkanediyl group, and among these, an alkanediyl group is more preferred because it allows for the production of a plated object in a good condition.

[0091] R 33 is a divalent hydrocarbon group or a group in which at least one -CH2- group (excluding both terminals) in the divalent hydrocarbon group has been substituted with -S- or -O-, and is preferably an alkanediyl group, a group in which at least one -CH2- group (excluding both terminals) in the alkanediyl group has been substituted with -S- or -O- (hereinafter also referred to as a "substituted alkanediyl group"), an arylene group, or an arylenealkanediyl group, and of these, an alkanediyl group is more preferred because it allows for good production of plated objects.

[0092] The number of carbon atoms in the alkanediyl group is usually 1 to 12, preferably 2 to 12. Examples of the alkanediyl group include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl, and dodecane-1,12-diyl; and branched alkanediyl groups such as 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. Of these, linear alkanediyl groups are preferred.

[0093] Examples of the substituted alkanediyl group include a group represented by -CH2-CH2-S-CH2-CH2- and a group represented by -CH2-CH2-O-CH2-CH2-O-CH2-CH2-.

[0094] Examples of the arylene group include arylene groups having 6 to 10 carbon atoms, such as a phenylene group, a methylphenylene group, and a naphthylene group.

[0095] The arylenealkanediyl group is a divalent group in which one or more arylene groups and one or more alkanediyl groups are bonded in any order. Specific examples of each arylene group and alkanediyl group include those listed above.

[0096] R 34 represents a glycoluril ring structure or an isocyanuric ring structure. Although the glycoluril ring structure and the isocyanuric ring structure have a bond that may reduce hydrophobicity, it is presumed that the high structural symmetry does not cause the hydrophobicity of compound (D2) to deteriorate.

[0097] m is 1 or 0. q is an integer from 1 to 4. 34 When R is a glycoluril ring structure, q is an integer of 1 to 4. 34 When is an isocyanuric ring structure, q is an integer of 1 to 3. When q is an integer of 2 or more, -(R 32 -S) m -R 33 The groups represented by -SH may be the same or different.

[0098] In compound (D2), the mercapto group or sulfide bond (when m is 1) is bonded to a hydrocarbon structure or a hydrocarbon structure having -S- or -O- in part, which is presumably why compound (D2) has high hydrophobicity.

[0099] 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 preferred, with the compound (D2-1) being more preferred.

[0100] [ka]

[0101] In formulas (D2-1) and (D2-2), X's are each independently a hydrogen atom or a monovalent group represented by formula (g2). However, in formula (D2-1), at least one X is a monovalent group represented by formula (g2), and preferably, all X's are monovalent groups represented by formula (g2). Furthermore, in formula (D2-2), at least one X is a monovalent group represented by formula (g2), and preferably, all X's are monovalent groups represented by formula (g2).

[0102] [ka]

[0103] In formula (g2), R 32 , R 33 and m are R in formula (D2), respectively. 32 , R 33 and m, and * is a bond to the nitrogen atom in formula (D2-1) or (D2-2).

[0104] Examples of compound (D2-1) include 1,3,4,6-tetrakis[2-mercaptoethyl]glycoluril, 1,3,4,6-tetrakis[3-(2-mercaptoethylsulfanyl)propyl]glycoluril, 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, and 1,3,4,6-tetrakis[3-(6-mercaptohexylsulfanyl)propyl]glycoluril. Examples of suitable glycoluril include glycoluril, 1,3,4,6-tetrakis[3-(8-mercaptooctylsulfanyl)propyl]glycoluril, 1,3,4,6-tetrakis[3-(10-mercaptodecylsulfanyl)propyl]glycoluril, 1,3,4,6-tetrakis[3-(12-mercaptododecylsulfanyl)propyl]glycoluril, 1,3,4,6-tetrakis{3-[2-(2-mercaptoethylsulfanyl)ethylsulfanyl]propyl}glycoluril, and 1,3,4,6-tetrakis(3-{2-[2-(2-mercaptoethoxy)ethoxy]ethylsulfanyl}propyl)glycoluril.

[0105] 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, and 1,3,5-tris[3-(6-mercaptohexylsulfanyl)propyl]isocyanurate. 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, and 1,3,5-tris(3-{2-[2-(2-mercaptoethoxy)ethoxy]ethylsulfanyl}propyl)isocyanurate.

[0106] 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.

[0107] Compound (D2) may form a multimer. The multimer is obtained by forming a disulfide bond between a plurality of compounds (D2) through coupling of mercapto groups. The multimer is, for example, a dimer to pentamer of compound (D2).

[0108] Compound (D3) The compound (D3) is a compound represented by the formula (D3).

[0109] [ka]

[0110] In formula (D3), R 35 and R 36 R is independently a hydrogen atom or an alkyl group. 37 is a single bond or an alkanediyl group. 38 is an r-valent aliphatic group which may contain atoms other than carbon atoms, and r is an integer of 2 to 10.

[0111] R 35 and R 36 Examples of the alkyl group in R include alkyl groups 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. 35 and R 36 As the group, a combination in which one is a hydrogen atom and the other is an alkyl group is preferred.

[0112] R 37 The number of carbon atoms in the alkanediyl group is usually 1 to 10, preferably 1 to 5. Examples of the alkanediyl group include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and decane-1,10-diyl; and branched alkanediyl groups such as 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. Of these, linear alkanediyl groups are preferred.

[0113] R 38 is an r-valent (2 to 10) aliphatic group which may contain atoms other than carbon atoms. Examples of atoms other than carbon atoms include nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The structure of the aliphatic group may be linear, branched, or cyclic, or may be a combination of these structures.

[0114] Examples of the aliphatic group include an r-valent hydrocarbon group having 2 to 10 carbon atoms, an r-valent oxygen-containing aliphatic group having 2 to 10 carbon atoms, and a trivalent group having an isocyanuric ring structure and having 6 to 10 carbon atoms.

[0115] Examples of the compound (D3) include compounds represented by the following formulas (D3-1) to (D3-4).

[0116] [ka]

[0117] <Novolac resin (E)> The novolac resin (E) may be any resin that is alkali-soluble and can be obtained by a conventional method. The polymer (A) in this composition is hydrophobic, while the surfactant (C) is hydrophilic. The use of the novolac resin (E) in this composition improves the compatibility of the composition when a hydrophilic component and a hydrophobic component are mixed, such as the polymer (A) and surfactant (C), although the reason for this is unclear. Furthermore, because the alkali solubility can be appropriately controlled, rectangular patterns can be obtained by adjusting the mixing ratio with the polymer (A) and the composition of the novolac resin (E), which will be described later.

[0118] The novolak resin (E) can be produced, for example, by condensation polymerization of a phenolic compound with an aldehyde such as formaldehyde, acetaldehyde, or a substituted or unsubstituted benzaldehyde, or by condensation polymerization of a phenolic compound with a substituted or unsubstituted methylol compound, using an acid catalyst.

[0119] Suitable novolak resins (E) include those obtained by the condensation reaction of a phenolic compound such as phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, and the like with an aldehyde compound such as formaldehyde in the presence of an acid or a polyvalent metal ion catalyst.

[0120] 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) may be a blend of two or more types.

[0121] The novolak resin (E) used in the present invention is preferably a cresol-based novolak resin. Cresol novolak resins, which use m-cresol or p-cresol as the phenolic compound and formaldehyde as the aldehyde, are particularly preferred because they are available in a wide variety of types, are easily available, and allow for adjustment of alkali solubility.

[0122] <Quencher> The composition may further contain a quencher. The quencher is a component used, for example, to control the diffusion of the acid generated from the photoacid generator (B) upon exposure in the resin film, thereby improving the resolution of the composition.

[0123] Examples of quenchers include basic compounds and compounds that generate bases, such as those described in JP 2011-029636 A, JP 2014-013381 A, JP 2015-526752 A, JP 2016-099483 A, and JP 2017-037320 A. These are all incorporated herein by reference.

[0124] Examples of quenchers 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; polyamino compounds such as ethylenediamine, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, and polyethyleneimine; amide compounds such as formamide; urea compounds such as urea and methylurea; nitrogen-containing heterocyclic compounds such as imidazole and benzimidazole; and nitrogen-containing compounds having an acid-dissociable group such as N-(t-butoxycarbonyl)piperidine, N-(t-butoxycarbonyl)-4-hydroxypiperidine, N-(t-butoxycarbonyl)imidazole, N-(t-butoxycarbonyl)benzimidazole, and N-(t-butoxycarbonyl)-2-phenylbenzimidazole.

[0125] 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, and preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the polymer (A).

[0126] <Other ingredients> The composition may further contain other ingredients. Examples of the other components include surfactants other than the surfactant (C) that act to improve the coatability, defoaming properties, etc. of the photosensitive resin composition; sensitizers that absorb exposure light and improve the acid generation efficiency of the photoacid generator; alkali-soluble resins and low-molecular-weight phenolic compounds that control the dissolution rate of the resin film formed from the photosensitive resin composition in an alkaline developer; ultraviolet absorbers that prevent photoreaction due to the leakage of scattered light into unexposed areas during exposure; thermal polymerization inhibitors that increase the storage stability of the photosensitive resin composition; and other components such as antioxidants, adhesion aids, and inorganic fillers.

[0127] <Organic solvents> The present composition may further contain an organic solvent, which is used, for example, to uniformly mix the components contained in the present composition.

[0128] Examples of organic solvents include alcohol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monoethyl ether, ethyl lactate, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl acetoacetate, ethyl ethoxyacetate, and γ-butyrolactone; ketone solvents such as methyl amyl ketone and cyclohexanone; alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, and dipropylene glycol dimethyl ether; and alkylene glycol monoalkyl ether acetates 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.

[0129] The composition may contain one or more organic solvents. The content of the organic solvent in the present composition is usually 40 to 90 mass %.

[0130] <Production of Photosensitive Resin Composition> The composition can be produced by uniformly mixing the aforementioned components. After uniformly mixing the aforementioned components, the resulting mixture can be filtered to remove any foreign matter.

[0131] [Photosensitive resin composition kit] One embodiment of the present invention is a photosensitive resin composition kit comprising a first part containing a compound (D) and an organic solvent, and a second part containing a polymer (A) having an acid-dissociable group, a photoacid generator (B), and a surfactant (C). The details of each component are as described above.

[0132] The content of 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 further contain the above-mentioned quencher, other components, organic solvent, etc. 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.

[0133] The photosensitive resin composition kit can be used, for example, by applying the first agent onto a metal film of a substrate having the metal film, and then forming a resin film of the second agent on the metal film that has been surface-treated with the first agent. The subsequent steps are the same as steps (2) and (3) described below. It is believed that the effects of the present invention can also be achieved by this method, for the presumed reason described above that a film containing compound (D) is formed on the metal film.

[0134] [Method of manufacturing resist pattern film] The method for producing a resist pattern film of the present invention includes the steps of: (1) forming a resin film of the photosensitive resin composition of the present invention on a metal film of a substrate having the metal film; (2) exposing the resin film to light; and (3) developing the resin film after exposure.

[0135] <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 or uneven, and the shape of the substrate may be circular or square. There is also no limit to the size of the substrate.

[0136] Examples of the metal film include films containing metals such as aluminum, copper, silver, gold, and palladium, as well as alloys of two or more of these metals. A copper film, i.e., a film containing copper and / or a copper alloy, 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 sputtering.

[0137] The resin film is usually formed by applying the present composition onto a metal film of a substrate having the metal film, and examples of the application method of the present composition include spin coating, roll coating, screen printing, and applicator methods, with spin coating and screen printing being preferred.

[0138] After the composition is applied, the applied composition may be subjected to a heat treatment in order to volatilize the organic solvent, etc. The heat treatment conditions 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.

[0139] <Process (2)> In step (2), the resin film formed in step (1) is exposed to light.

[0140] The exposure is usually carried out selectively on the resin film by equal-magnification projection exposure or reduced-magnification projection exposure through a photomask having a predetermined mask pattern. Examples of the exposure light include ultraviolet light or visible light having a wavelength of 150 to 600 nm, preferably 200 to 500 nm. Examples of the light source for the exposure light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and lasers. The exposure dose can be appropriately selected depending on the type of exposure light, the type of photosensitive resin composition, and the thickness of the resin film, and is usually 100 to 20,000 mJ / cm. 2 is.

[0141] After the resin film is exposed to light and before development, the resin film may be subjected to a heat treatment. The heat treatment is usually performed at 70 to 180° C. for 0.5 to 10 minutes. The heat treatment can promote the dissociation reaction of the acid-dissociable group in the polymer (A) with an acid.

[0142] <Process (3)> In step (3), the resin film exposed in step (2) is developed to form a resist pattern film. Development is usually carried out using an alkaline developer. Examples of development methods include showering, spraying, immersion, puddling, and puddling. Development conditions are usually at 10 to 30°C for 1 to 30 minutes.

[0143] The alkaline developer may, for example, be an aqueous solution containing one or more alkaline substances. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, 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 may further contain an organic solvent such as methanol or ethanol and / or a surfactant.

[0144] The resist pattern film formed by development can be washed with water, etc. Thereafter, the resist pattern film can be dried using an air gun or a hot plate.

[0145] In this manner, a resist pattern film that serves as a mold for forming a plated product can be formed on the metal film of the substrate while suppressing the formation of a T-top shape, thereby obtaining a plating substrate having a resist pattern film (mold) on the metal film. The thickness of the resist pattern film is usually 1 to 100 μm, preferably 5 to 80 μm. The shape of the openings in the resist pattern film can be selected according to the type of plated product. When the plated product is a wiring, the pattern shape is, for example, a line-and-space pattern, and when the plated product is a bump, the shape of the openings is, for example, a cubic hole pattern.

[0146] By using a plating substrate having a mold that suppresses the formation of a T-top shape, it is possible to manufacture a plated object with the designed pattern dimensions.

[0147] [Method of manufacturing plated objects] The method for producing a plated object of the present invention includes a step (5) of plating a substrate having a metal film on which a resist pattern film produced by the method for producing a resist pattern film of the present invention is formed, using the resist pattern film as a mold. The method for producing a plated object of the present invention may further include a step (4) of performing a plasma treatment with an oxygen-containing gas after the step (3) and before the step (5).

[0148] <Process (4)> By carrying out a plasma treatment with an oxygen-containing gas (surface treatment of the plating substrate) in step (4), the affinity between the metal film surface and the plating solution can be increased.

[0149] In step (4), for example, a plating substrate having a resist pattern film on a metal film is placed in a vacuum chamber, and oxygen plasma is emitted to perform surface treatment of the plating substrate. Plasma treatment conditions are typically a power output of 50 to 300 W, a flow rate of an oxygen-containing gas of 20 to 150 mL, an internal pressure of the chamber of 10 to 30 Pa, and a treatment time of 0.5 to 30 minutes. The oxygen-containing gas may contain, in addition to oxygen, one or more gases selected from, for example, hydrogen, argon, and tetrafluoromethane. The plating substrate surface-treated by the plasma treatment can be washed with water or the like.

[0150] <Process (5)> In step (5), the resist pattern film is used as a mold to form a plated object in the openings defined by the resist pattern film (portions removed by development) by plating.

[0151] Examples of plated products include bumps and wiring. Plated products are made of conductors such as copper, gold, and nickel. The thickness of the plated product varies depending on its application, but for example, in the case of bumps, it is usually 5 to 100 μm, preferably 10 to 80 μm, and more preferably 20 to 60 μm, and in the case of wiring, it is usually 1 to 30 μm, preferably 3 to 20 μm, and more preferably 5 to 15 μm.

[0152] The plating process may be, for example, a plating solution process using a plating solution. Examples of plating solutions include copper plating solutions, gold plating solutions, nickel plating solutions, and solder plating solutions. Specific examples include copper plating solutions containing copper sulfate or copper pyrophosphate, gold plating solutions containing potassium gold cyanide, and nickel plating solutions containing nickel sulfate or nickel carbonate. Among these, copper plating solutions are preferred. Plating solutions typically contain water and a hydrophilic solvent such as alcohol.

[0153] Specific examples of plating treatments include wet plating treatments such as electrolytic plating, electroless plating, and hot-dip plating. When bumps or wiring are formed in wafer-level processing, electrolytic plating is usually used.

[0154] In the case of electrolytic plating, a plating film formed on the inner wall of a resist pattern film by sputtering or electroless plating can be used as a seed layer, or the metal film on the substrate can be used as a seed layer. Also, a barrier layer can be formed before forming the seed layer, and the seed layer can be used as a barrier layer.

[0155] The conditions for the electrolytic plating treatment can be appropriately selected depending on the type of plating solution, etc. In the case of a 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 In the case of a 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.

[0156] The plating process can be performed by sequentially plating different materials, for example, by first plating copper, then plating nickel, and then plating with molten solder to form a copper solder pillar bump.

[0157] <Other processes> The method for producing a plated product of the present invention can further include a step of removing the resist pattern film after step (5). This step is specifically a step of stripping and removing the remaining resist pattern film, for example, by immersing the substrate having the resist pattern film and the plated product in a stripping solution. The temperature of the stripping solution and the immersion time are usually 20 to 80°C and 1 to 10 minutes.

[0158] The stripping solution may be, for example, a stripping solution containing at least one selected from tetramethylammonium hydroxide, dimethyl sulfoxide, and N,N-dimethylformamide.

[0159] The method for manufacturing a plated object of the present invention may further include a step of removing the metal film in an area other than the area where the plated object is formed by, for example, wet etching. [Example]

[0160] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0161] <Polymer weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer and surfactant was measured by gel permeation chromatography under the following conditions. GPC equipment: Tosoh Corporation, equipment name "HLC-8220-GPC" Column: Tosoh Corporation columns TSK-M and TSK2500 connected in series Solvent: Tetrahydrofuran ·Temperature: 40℃ Detection method: Refractive index method Standard material: Polystyrene

[0162] <Absorbance> A 0.1% by mass aqueous solution of the surfactant was prepared and placed in a quartz cell with an optical path length of 10 mm. The absorbance was measured at an optical path length of 10 mm and a wavelength of 300 nm using a UV-Vis-NIR spectrophotometer ("UV-Vis-NIR Spectrophotometer V-7300" manufactured by JASCO Corporation).

[0163] [Synthesis Examples 1 and 2] Polymers (A-1) to (A-3) having the structural units and their content ratios shown in Table 1 were produced by radical polymerization using 2,2'-azobis(methyl isobutyrate) as a radical polymerization initiator. 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), and (a4-1). The numerical values ​​in columns a1-1 to a4-1 in Table 1 are in mol %. The content ratio of each structural unit is 1 1H-NMR was used to measure the

[0164] [ka]

[0165] [Table 1]

[0166] <Production of Photosensitive Resin Composition> [Examples 1A to 11A, Comparative Examples 1A to 3A] Preparation of photosensitive resin compositions The photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A were produced by uniformly mixing the types and amounts of each component shown in Table 3 below. Details of each component other than the polymer component are as follows. The units of values ​​in Table 3 are parts by mass. B1: A compound represented by the following formula (B1): B2: A compound represented by the following formula (B2): B3: A compound represented by the following formula (B3):

[0167] [ka]

[0168] C1: Fluorine-based surfactant "Megafac F553" (DIC Corporation) C2: Fluorine-based surfactant "Ftergent 602A" (manufactured by Neos Co., Ltd.) C3: Fluorine-based surfactant "Megafac F559" (DIC Corporation) C4: Fluorine-based surfactant "Megafac F477" (DIC Corporation) C5: Fluorine-based surfactant "Ftergent 212M" (manufactured by Neos Co., Ltd.) C6: Fluorine-based surfactant "Megafac F-570" (DIC Corporation) C7: Fluorine-based surfactant "Megafac F-563" (DIC Corporation) The absorbance and weight average molecular weight of the surfactants (C1) to (C7) under the condition (i) are shown in Table 2 below.

[0169] [Table 2]

[0170] D1: Karenz MT (registered trademark) PE1 manufactured by Showa Denko K.K. D2: Karenz MT (registered trademark) NR1 manufactured by Showa Denko K.K.

[0171] E1: Cresol novolac resin (m-cresol:p-cresol = 6:4 (molar ratio), polystyrene equivalent weight average molecular weight = 12,000) E2: Cresol novolac resin (m-cresol:p-cresol = 4:6 (molar ratio), polystyrene equivalent weight average molecular weight = 5,000)

[0172] S1: Propylene glycol monomethyl ether acetate S2: 3-Methoxybutyl acetate S3: γ-butyrolactone

[0173] [Table 3]

[0174] <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 patterned substrates were prepared according to the methods described in Conditions 1 and 2 below, and the T-top shapes of the resist pattern films were evaluated using the evaluation methods and criteria described below.

[0175] Condition 1 (board production without settling time) The photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A were applied to the copper sputtered film of a silicon wafer substrate using a spin coater and heated on a hot plate at 120°C for 60 seconds to form a 6 μm-thick coating film. The coating film was exposed through a pattern mask using a stepper (Nikon Corporation, model "NSR-i10D"). 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% by mass aqueous solution of tetramethylammonium hydroxide for 180 seconds for development. The substrate was then rinsed with running water and blasted with nitrogen to form a resist pattern film (line width: 2 μm, line width / space width = 1 / 1) of Examples 1B to 11B and Comparative Examples 1B to 3B on the copper sputtered film of the substrate. The substrate with the resist pattern film thus formed is referred to as "patterned substrate-1." Under these conditions, the time required from exposure to post-exposure heating is within 30 minutes.

[0176] Condition 2 (substrate preparation with 24 hours of exposure) The photosensitive resin compositions of Examples 1A to 11A and Comparative Examples 1A to 3A were applied to the copper sputtered film of a silicon wafer substrate using a spin coater and heated on a hot plate at 120°C for 60 seconds to form a 6 μm-thick coating film. The coating film was exposed through a pattern mask using a stepper (Nikon Corporation, model "NSR-i10D"). The exposed coating film was exposed for 24 hours in an environment contaminated with 5 ppb of atmospheric amine, then heated at 90°C for 60 seconds and subsequently immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 180 seconds for development. The substrate was then rinsed with running water and blasted with nitrogen to form a resist pattern film (line width: 2 μm, line width / space width = 1 / 1) of Examples 1B to 11B and Comparative Examples 1B to 3B on the copper sputtered film of the substrate. The substrate with the resist pattern film thus formed is referred to as "patterned substrate-2."

[0177] <Evaluation methods and criteria> The T-top shapes of the resist pattern films obtained for the patterned substrates 1 and 2 prepared using each photosensitive resin composition were observed under an electron microscope. As shown in Figure 1, the pattern width when the resist pattern was observed from directly above under an electron microscope was defined as W1, and the pattern width connecting points 3a and 3b where the T-top shape end (protrusion) intersects with the pattern sidewall extending perpendicular to the substrate when the cross section of the resist pattern was observed under an electron microscope was defined as W2. The sum of the T-top widths (W1 - W2) was calculated, and the ratio of this to the pattern width W2 ((W1 - W2) / W2 × 100 = Wt (%)) was calculated. The Wt of patterned substrate 1 was defined as Wt1, and the Wt of patterned substrate 2 was defined as Wt2. The shape of the pattern sidewall is not limited to a shape extending straight vertically from the patterned substrate as shown in Figure 1, but may also be a shape extending vertically from the patterned substrate in a barrel-like bulge as shown in Figure 2, a shape extending vertically from the patterned substrate in a tapered shape as shown in Figure 3, or a shape extending vertically from the patterned substrate in an inverted tapered shape as shown in Figure 4. For each photosensitive resin composition, Wt2 - Wt1 was calculated and evaluated according to the following criteria. The evaluation results are shown in Table 4.

[0178] ◎: (Wt2 - Wt1) is 0% or more and less than 10%. ○: (Wt2-Wt1) is 10% or more and less than 20%. △: (Wt2-Wt1) is 20% or more and less than 30%. ×: (Wt2-Wt1) is 30% or more.

[0179] For each photosensitive resin composition, Wt1 hardly exhibited a T-top shape due to the influence of environmental amines, but it is believed that the larger (Wt2 - Wt1) was, the more likely it was that a T-top shape was due to the influence of environmental amines.

[0180] The state of the interface between the resist pattern film and the sputtered copper film of the resulting patterned substrate-1 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.

[0181] ◎: No peeling of the pattern including the isolated wiring part in the 2 μm LS pattern. ◯: No pattern peeling except for isolated wiring areas in the 2 μm LS pattern. ×: Pattern peeling was observed occasionally in the 2 μm LS pattern.

[0182] <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 plated objects. Except for Example 11C, as a pretreatment for the electrolytic plating, treatment with oxygen plasma (power 100 W, oxygen flow rate 100 mL, treatment time 60 seconds) was performed, followed by water rinsing.

[0183] The pretreated patterned substrate-1 (an untreated patterned substrate in Example 11C) was immersed in 1 L of copper plating solution (product name "MICROFAB SC-40", manufactured by MacDermid Performance Solutions Japan Co., Ltd.) at a plating bath temperature of 25°C and a current density of 8.5 A / dm 2 The temperature was set at 100°C, and electrolytic plating was carried out for 2 minutes and 10 seconds to produce a plated object.

[0184] The state of the plated object thus produced was observed under an electron microscope and evaluated according to the following criteria. The evaluation results are shown in Table 4 below.

[0185] ◯: No plating peeling occurred and a rectangular shape was obtained. ×: Plating peeled off, or pattern peeling occurred, and therefore a rectangular shape was not obtained.

[0186] [Table 4] [Explanation of symbols]

[0187] 1. Substrate 2. Pattern 3a, 3b: The intersection point between the T-top shape and the pattern sidewall extending perpendicular to the substrate when the cross section of the resist pattern is observed with an electron microscope. W1: Pattern width when observing the resist pattern from directly above using an electron microscope W2: The width of the pattern connecting 3a and 3b when the cross section of the resist pattern is observed with an electron microscope.

Claims

1. A process (1) of forming a resin film of a photosensitive resin composition on a metal film of a substrate having the metal film, the resin film comprising a polymer (A) having an acid-dissociable group, a photoacid generator (B), and a surfactant (C), wherein the surfactant (C) is a fluorine-based surfactant that satisfies the following condition (i) and is contained in an amount of 0.5 to 6 parts by mass per 100 parts by mass of the polymer (A); a step (2) of exposing the resin film to light; (3) a step of developing the resin film after exposure; A method for producing a plated object, comprising the step (5) of performing plating treatment using a resist pattern film produced by the method for producing a resist pattern film comprising the steps of: Condition (i): The absorbance of a 0.1% by mass aqueous solution of the surfactant at a wavelength of 300 nm with an optical path length of 10 mm measured using an ultraviolet-visible-near infrared spectrophotometer is 0.30 or less.

2. 2. The method for producing a plated object according to claim 1, wherein the surfactant (C) has a weight average molecular weight of 8,000 or more.

3. A method for producing a plated object described in claim 1 or 2, wherein the photosensitive resin composition 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. A method for manufacturing a plated object described in any one of claims 1 to 3, wherein the photosensitive resin composition further contains a novolac resin (E).

5. The method for producing a plated object according to any one of claims 1 to 4, further comprising a step (4) of performing a plasma treatment with an oxygen-containing gas before the step (5).

Images