阅读说明：本技术 感光性树脂组合物、抗蚀剂图案膜的制造方法、及镀敷造形物的制造方法 (Photosensitive resin composition, method for producing resist pattern film, and method for producing plated article ) 是由 佐野有香 松本朋之 榊原宏和 于 2020-04-13 设计创作，主要内容包括：本发明的课题在于提供一种感光性树脂组合物,用于形成驻波轨迹得到抑制且剖面为矩形的抗蚀剂图案膜。本发明的感光性树脂组合物含有：具有酸解离性基的聚合物(A)；光酸产生剂(B)；具有羟基的氨基甲酸酯(C)；以及溶剂(D),所述溶剂(D)含有：选自丙二醇单甲醚乙酸酯等中的至少一种溶剂(D1)；以及选自二丙二醇二甲醚等中的至少一种溶剂(D2)。(The invention provides a photosensitive resin composition for forming a resist pattern film with suppressed standing wave trajectories and a rectangular cross section. The photosensitive resin composition of the present invention contains: a polymer (A) having an acid-dissociable group; a photoacid generator (B); a carbamate having a hydroxyl group (C); and a solvent (D) containing: at least one solvent (D1) selected from propylene glycol monomethyl ether acetate and the like; and at least one solvent (D2) selected from dipropylene glycol dimethyl ether and the like.)

1. A photosensitive resin composition comprising: a polymer (A) having an acid-dissociable group; a photoacid generator (B); a carbamate having a hydroxyl group (C); and a solvent (D),

the solvent (D) contains:

at least one solvent (D1) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methyl 3-methoxypropionate, and cyclohexanone; and

at least one solvent (D2) selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 1, 4-butanediol diacetate and 1, 3-butanediol diacetate.

2. The photosensitive resin composition according to claim 1, wherein the content of the solvent (D1) is 70 to 99% by mass and the content of the solvent (D2) is 1 to 30% by mass, based on 100% by mass of the solvent (D).

3. The photosensitive resin composition according to claim 1 or 2, wherein the solvent (D1) is propylene glycol monomethyl ether acetate.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the urethane (C) having a hydroxyl group is a urethane having an acid-dissociable group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the urethane having a hydroxyl group (C) in the photosensitive resin composition is 0.1 to 1 part by mass with respect to 100 parts by mass of the solvent (D2).

6. A method for manufacturing a resist pattern film, comprising: a step (1) of forming a resin film of the photosensitive resin composition according to any one of claims 1 to 5 on a metal film of a substrate having the metal film;

a step (2) of exposing at least a part of the resin film; and

and (3) developing the resin film after exposure.

7. A method for producing a plating formation, comprising a step of performing plating treatment using a substrate having a resist pattern film formed by the method for producing a resist pattern film according to claim 6 as a mold.

Technical Field

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

Background

The performance of mobile devices such as smart phones (smartphones) and tablet terminals is enhanced as follows: semiconductor chips having different functions are packaged using high-density packaging technologies such as Fan-Out Wafer Level Package (FO-WLP), Fan-Out Panel Level Package (FO-PLP), Through Silicon Via (TSV), and Silicon interposer (Silicon interposer).

In the packaging technology, wirings and protruding electrodes (bumps) used for electrical connection between semiconductor chips are also high-density. Therefore, a resist pattern film used for forming wiring and bumps is also required to be fine and have high density.

Generally, the wiring and the bump are plating formations, and are manufactured by: a photosensitive resin composition is applied to a metal film of a substrate having the metal film such as a copper film to form a resist coating film, the resist coating film is exposed to light using a mask and developed to form a thick resist pattern film, and the substrate is plated with the thick resist pattern film as a mold (see patent documents 1 to 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2010-008972

Patent document 2: japanese patent laid-open No. 2006-330368

Disclosure of Invention

Problems to be solved by the invention

When the pattern size and the pattern pitch in the resist pattern film are fine and high density, fluctuation (standing wave locus) of the resist pattern film due to standing waves caused by incident light and reflected light from a metal film such as a copper substrate during exposure cannot be ignored.

Further, when the wiring and the bump are made fine and have a high density, the distance to the adjacent wiring or bump becomes short, and the contact area between the wiring or the bump and the metal film such as the copper film becomes small, so that in order to produce a plated article having a rectangular cross section, it is required that the cross section of the resist pattern also be rectangular.

The invention provides a photosensitive resin composition for forming a resist pattern film with suppressed standing wave trajectories and a rectangular cross section, a method for producing a resist pattern film using the photosensitive resin composition, and a method for producing a plating formation product using the resist pattern film.

Means for solving the problems

The present inventors have made diligent studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [7 ].

[1] A photosensitive resin composition comprising: a polymer (A) having an acid-dissociable group; a photoacid generator (B); a carbamate having a hydroxyl group (C); and a solvent (D),

the solvent (D) contains:

at least one solvent (D1) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methyl 3-methoxypropionate, and cyclohexanone; and

at least one solvent (D2) selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 1, 4-butanediol diacetate and 1, 3-butanediol diacetate.

[2] The photosensitive resin composition according to [1], wherein the content of the solvent (D1) is 70 to 99% by mass and the content of the solvent (D2) is 1 to 30% by mass, based on 100% by mass of the solvent (D).

[3] The photosensitive resin composition according to the item [1] or [2], wherein the solvent (D1) is propylene glycol monomethyl ether acetate.

[4] The photosensitive resin composition according to the above [1] to [3], wherein the carbamate (C) having a hydroxyl group is a carbamate having an acid-dissociable group.

[5] The photosensitive resin composition according to the above [1] to [4], wherein the content of the urethane (C) having a hydroxyl group in the photosensitive resin composition is 0.1 to 1 part by mass with respect to 100 parts by mass of the solvent (D2).

[6] A method for manufacturing a resist pattern film, comprising: a step (1) of forming a resin film of the photosensitive resin composition according to any one of the above [1] to [5] on a metal film of a substrate having the metal film; a step (2) of exposing at least a part of the resin film; and a step (3) of developing the resin film after exposure.

[7] A method for producing a plating formation, comprising a step of performing plating treatment using, as a mold, a substrate having a resist pattern film formed by the method for producing a resist pattern film according to [6 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The photosensitive resin composition of the present invention can form a resist pattern film having a rectangular cross section with suppressed standing wave trajectories.

Drawings

Fig. 1 is a schematic view illustrating measurement of the shape of the resist pattern film of the example.

Fig. 2 is an enlarged portion of the cross section of the resist pattern of the example, which portion is in contact with the substrate, and is a schematic view for explaining measurement of the width of the standing wave locus.

Detailed Description

The components exemplified in the present specification, for example, the components in the photosensitive resin composition or the structural units in the polymer (a), may be contained singly or in two or more kinds unless otherwise mentioned.

[ photosensitive resin composition ]

The photosensitive resin composition of the present invention (hereinafter also referred to as "the present composition") contains: a polymer (a) having an acid-dissociable group (hereinafter also referred to as "polymer (a)"); a photoacid generator (B); carbamate (C) having a hydroxyl group (hereinafter, also referred to as "compound (C)"); and a solvent (D) containing: at least one solvent (D1) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methyl 3-methoxypropionate, and cyclohexanone; and at least one solvent (D2) selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 1, 4-butanediol diacetate, and 1, 3-butanediol diacetate.

< 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 formed 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.

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

The weight average molecular weight (Mw) of the polymer (A) in terms of polystyrene as 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 still more preferably 20,000 to 60,000.

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

The present composition may contain one or two 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% by mass, based on 100% by mass of the solid content of the composition. The solid component means all components except the mixed solvent (D).

The content of the polymer (a) in the present composition is usually 5 to 60% by mass, preferably 10 to 50% by mass. If the thickness is within the above range, a resist pattern film having a rectangular cross section and a thick film suitable for the production of the plating formation can be obtained.

Structural unit (a1)

The polymer (a) usually contains a structural unit (a1) having an acid-dissociable group. Examples of the structural unit (a1) include structural units represented by the formula (a1-10) and structural units represented by the formula (a1-20), and structural units represented by the formula (a1-10) are preferable.

[ solution 1]

The meanings of the symbols in the formulae (a1-10) and (a1-20) are as follows. R¹¹The alkyl group is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group (hereinafter, also referred to as "substituted alkyl group") in which at least one hydrogen atom in the alkyl group is substituted with a halogen atom such as a fluorine atom or a bromine atom, an aryl group such as a phenyl group, or another group such as a hydroxyl group or an alkoxy group.

R¹²A divalent organic group having 1 to 10 carbon atoms. Ar is an arylene group having 6 to 10 carbon atoms. R¹³Is an acid dissociable group.

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

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

Examples of the arylene group having 6 to 10 carbon atoms include: phenylene, methylphenylene, naphthylene. Examples of the acid-dissociable group include the following groups: the polymer (a) is dissociated by the action of an acid to form an acidic functional group such as a carboxyl group and a phenolic hydroxyl group. Specifically, an acid-dissociable group represented by the formula (g1) or a benzyl group is mentioned, and an acid-dissociable group represented by the formula (g1) is preferred.

[ solution 2]

In the formula (g1), R^a1～R^a3Each independently represents an alkyl group, an alicyclic hydrocarbon group, or a group obtained by substituting at least one hydrogen atom in the alkyl group or the alicyclic hydrocarbon group with a halogen atom such as a fluorine atom or a bromine atom, an aryl group such as a phenyl group, a hydroxyl group, an alkoxy group, or the like, and R^a1And R^a2Can be bonded to each other and R^a1And R^a2The bonded carbon atoms C together form an alicyclic structure.

As R^a1～R^a3Examples of the alkyl group of (1) include: alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, pentyl, and decyl.

As R^a1～R^a3Examples of the alicyclic hydrocarbon group of (1) include: monocyclic saturated cyclic hydrocarbon groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; monocyclic unsaturated cyclic hydrocarbon groups such as cyclobutenyl, cyclopentenyl and cyclohexenyl; polycyclic saturated cyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, tetracyclododecyl and the like.

As a group consisting of R^a1、R^a2And carbon atom CExamples of the structure include: monocyclic saturated cyclic hydrocarbon structures such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; monocyclic unsaturated cyclic hydrocarbon structures such as cyclobutenyl, cyclopentenyl, cyclohexenyl and the like; polycyclic saturated cyclic hydrocarbon structures such as norbornyl, adamantyl, tricyclodecyl, tetracyclododecyl and the like.

The acid-dissociable group represented by formula (g1) is preferably a group represented by formulae (g11) to (g 15).

[ solution 3]

In the formulae (g11) to (g15), R^a4Each independently represents an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, etc., and n is an integer of 1 to 4. Each of the ring structures in the formulae (g11) to (g14) may have one or more substituents such as alkyl groups having 1 to 10 carbon atoms, halogen atoms such as fluorine atoms and bromine atoms, hydroxyl groups, and alkoxy groups. Denotes a bond.

As the structural unit (a1), in addition to the structural units represented by the formulae (a1-10) and (a1-20), there can be mentioned structural units having an acetal acid-dissociable group as described in Japanese patent laid-open Nos. 2005-208366, 2000-194127, 2002/0110750 and 2006/0210913; a structural unit having a sultone ring described in US2013/0095425 publication; structural units having a crosslinkable acid-dissociable group are disclosed in Japanese patent laid-open Nos. 2000-214587 and 6156481.

The structural units described in the above-mentioned publications are described in the present specification. The polymer (a) may have one or two or more kinds of the structural units (a 1). 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%.

In the present specification, the content ratio of each structural unit in the polymer (a) is defined as the total of all structural units constituting the polymer (a) being 100 mol%The value of (c). The individual structural units are generally derived from individual monomers during the synthesis of the polymer (A). The content ratio of each structural unit is available¹H-Nuclear Magnetic Resonance (NMR) was carried out.

In one embodiment, the polymer (A) preferably has R¹¹A structural unit represented by the formula (a1-10) which is a hydrogen atom, and R¹¹A structural unit represented by the formula (a1-10) which is an alkyl group or a substituted alkyl group having 1 to 10 carbon atoms as a structural unit (a 1). In this form, the composition tends to have a further improved resolution and a further improved resistance to swelling and cracking of the resist pattern film against the plating solution.

Structural unit (a2)

The polymer (a) may further contain 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) having the structural unit (a2) can adjust the lithographic characteristics such as resolution, sensitivity, and depth of focus of a resist pattern formed from the present composition.

Examples of the structural unit (a2) include structural units having at least one group or structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a lactone structure, a cyclic carbonate structure, a sultone structure and a fluoroalcohol structure (with the exception of the structural unit corresponding to the structural unit (a 1)). Among these, a structural unit having a phenolic hydroxyl group is preferable in that a resist pattern film which is strong against pressure from plating when the plating formation product is formed can be formed.

Examples of the structural unit having a carboxyl group include: a unit derived from a monomer 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; and structural units described in Japanese patent laid-open publication No. 2002-341539.

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

Examples of the structural unit having an alcoholic hydroxyl group include: a structural unit derived from a monomer such as 2-hydroxyethyl (meth) acrylate or 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran; and structural units described in Japanese patent laid-open No. 2009-276607.

Examples of the structural unit having a lactone structure include those described in Japanese patent laid-open Nos. 2017-058421, US2010/0316954, 2010-138330, US2005/0287473, 2016-098350 and US 2015/0323865.

Examples of the structural unit having a cyclic carbonate structure include structural units described in Japanese patent laid-open Nos. 2017-058421, 2009-223294 and 2017-044875.

Examples of the structural unit having a sultone structure include those described in Japanese patent laid-open Nos. 2017-058421, 2014-029518, US2016/0085149, and 2013-007846.

Examples of the structural unit having a fluoroalcohol structure include structural units described in Japanese patent laid-open Nos. 2004-083900, 2003-002925, 2004-145048 and 2005-133066.

The structural units described in the above-mentioned publications are described in the present specification. The polymer (a) may have one or two or more kinds of the structural units (a 2). 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 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) may have the structural unit (a2) in the same polymer as or different from the polymer having the structural unit (a1), and preferably has the structural units (a1) to (a2) in the same polymer.

Structural unit (a3)

The polymer (a) may further have a structural unit (a3) other than the structural units (a1) to (a 2).

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 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, lauryloxytetraethyleneglycol (meth) acrylate, lauryloxydipropylene glycol (meth) acrylate, lauryloxytripropylene glycol (meth) acrylate, and the like; structural units derived from an alicyclic (meth) acrylate compound such as cyclopentyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, or the like; structural units derived from aromatic ring-containing (meth) acrylate 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.

The polymer (a) may have one or two or more kinds of the structural units (a 3). The content ratio of the structural unit (a3) in the polymer (a) is usually 40 mol% or less. The polymer (a) may have the structural unit (a3) in the same polymer as or different from the polymer having the structural unit (a1) and/or the structural unit (a2), and preferably contains the structural units (a1) to (a3) in the same polymer.

Production method of Polymer (A)

The polymer (a) can be produced into monomers corresponding to the respective structural units by a known polymerization method such as an ionic polymerization method or a radical polymerization method in an appropriate polymerization solvent. Among these, the radical polymerization method is preferable.

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

In the polymerization, a molecular weight modifier such as a thiol compound or a halogen hydrocarbon may be used as necessary.

< photoacid Generator (B) >

The photoacid generator (B) is a compound that generates an acid upon exposure. The acid dissociable groups in the polymer (a) are dissociated by the action of the acid to generate acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. As a result, the exposed portion of the resin film formed from the present composition becomes easily soluble in an alkaline developer, and a positive resist pattern film is formed. Thus, the present composition functions as a chemically amplified positive photosensitive resin composition.

Examples of the photoacid generator (B) include: compounds described in Japanese patent laid-open Nos. 2004-317907, 2014-157252, 2002-268223, 2017-102260, 2016-018075 and 2016-210761761. These are described in the present specification.

Specific examples of the photoacid generator (B) include: iodonium trifluoromethanesulfonate, diphenyliodonium para-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, onium salt compounds such as triphenylsulfonium hexafluorophosphate, 4-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-tert-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, and 4, 7-di-n-butoxynaphthyltetrahydrothiophenium tris (nonafluorobutylsulfonyl) methide; halogen-containing compounds such as 1, 10-dibromo-n-decane, 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-tribenzoylmethyl sulfone, mesitylphenylbenzoyl methyl sulfone, and bis (phenylsulfonyl) methane; sulfonic acid compounds such as benzoin tosylate, pyrogallol tris-trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate and the like; 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, sulfimide compounds such as 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-toluenesulfonyl diazomethane, cyclohexylsulfonyl-1, 1-dimethylethylsulfonyldiamethane and bis (1, 1-dimethylethylsulfonyl) diazomethane.

Among these, onium salt compounds and sulfonimide compounds are preferable because a resist pattern film having excellent resolution and plating solution resistance can be formed. The present composition may contain one or more than two 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, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polymer (a). The content of the photoacid generator (B) in the present composition is usually 0.1 to 6% by mass, preferably 0.5 to 4% by mass.

< Compound (C) >

The compound (C) is a carbamate having a hydroxyl group. The compound (C) is a component that functions as a quencher in the chemically amplified positive photosensitive resin composition. For example, it can be used to control the diffusion of an acid generated from the photoacid generator (B) in the resin film by exposure, and as a result, the resolution of the present composition can be improved.

Since the compound (C) has a hydroxyl group and a urethane structure, its partition coefficient (ClogP) is close to that of the solvent (D2). As a result, since the compound (C) is compatible with the solvent (D2), a resist pattern film having a rectangular cross section can be formed with the stationary wave trajectory suppressed. The partition coefficient of the compound (C) is usually 0.1 to 1.5, preferably 0.3 to 1.4, and more preferably 0.6 to 1.1.

Examples of the compound (C) include: non-acid-dissociable carbamates such as 1- (methylcarbonyl) -2-piperidinemethanol, 1- (ethylcarbonyl) -2-piperidinemethanol, 1- (methylcarbonyl) -4-hydroxypiperidine, 1- (ethylcarbonyl) -4-hydroxypiperidine, and N- (methylcarbonyl) -D-glucosamine; and 1- (tert-butoxycarbonyl) -2-piperidinemethanol, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, N- (tert-butoxycarbonyl) -L-alanine, 2- (tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, 2- (tert-butoxycarbonylamino) -3-methyl-1-butanol, 2- (tert-butoxycarbonylamino) -3-phenylpropanol, (tert-butoxycarbonylamino) -3-phenyl-1-propanol, 2- (tert-butoxycarbonylamino) -1-propanol, N- (tert-butoxycarbonyl) ethanolamine, N- (tert-butoxycarbonyl) -D-glucosamine, N-acetylsalicylic acid, N-butyloxycarbonyl-3-phenyl-1-propanol, 2-piperidinemethanol, 1- (tert-butoxycarbonylamino) -1-hydroxy-1-N-butyloxycarbonyl-1-methyl-1-propanol, 2-methyl-1-butanol, 2- (tert-butoxycarbonylamino) -3-methyl-1-butanol, 2-methyl-1-butanol, 2-butyloxycarbonyl-butanol, N- (tert-butyloxycarbonyl-1-butanol, N-butyloxycarbonyl-butanol, N-butyloxycarbonyl-1-butanol, N-butyloxycarbonyl-1-butanol, N-butyloxycarbonyl-butanol, N-butyloxycarbonyl-2-1-butanol, N-butyloxycarbonyl-butanol, N-1-butanol, N-butyloxycarbonyl-butanol, N-butyloxycarbonyl-2-butyloxycarbonyl-butanol, N-1-butanol, N-butyloxycarbonyl-butanol, N-2-butyloxycarbonyl-2-1-butyloxycarbonyl-butanol, N-2-butyloxycarbonyl-butanol, N-, Carbamates having an acid-dissociable group (hereinafter, also referred to as "acid-dissociable carbamates") such as 1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, N- (tert-butoxycarbonyl) -L-valinol (valinol), tert-butyl N- (3-hydroxypropyl) carbamate, and tert-butyl N- (2, 3-dihydroxypropyl) carbamate.

Among these, acid-dissociable carbamates are also preferable. In the case of the acid-dissociable urethane, the acid-dissociable group is decomposed by exposure to an acid generated from the photoacid generator (B), whereby the basicity of the compound (C) can be greatly changed after exposure and exposure, and hence the resolution of the photosensitive resin composition can be improved.

The present composition may contain one or more compounds (C). The lower limit of the content of the compound (C) in the present composition is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and the upper limit is usually 10 parts by mass or less, preferably 5 parts by mass or less, relative to 100 parts by mass of the polymer (a). The lower limit of the content of the compound (C) in the present composition relative to the solvent (D2) is usually 0.1 part by mass or more, preferably 0.2 part by mass or more, and the upper limit is usually 1 part by mass or less, preferably 0.8 part by mass or less, and more preferably 0.5 part by mass or less, relative to 100 parts by mass of the solvent (D2).

< solvent (D) >

The solvent (D) contains: at least one solvent (D1) selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methyl 3-methoxypropionate, and cyclohexanone; and at least one solvent (D2) selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 1, 4-butanediol diacetate, and 1, 3-butanediol diacetate.

The lower limit of the content of the solvent (D1) in 100 mass% of the solvent (D) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 85 mass% or more, and the upper limit is preferably 99 mass% or less, more preferably 95 mass% or less, and even more preferably 92 mass% or less.

The lower limit of the content of the solvent (D2) in 100 mass% of the solvent (D) is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 8 mass% or more, and the upper limit is preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less. If the content ratio of the solvent (D1) and the solvent (D2) in the solvent (D) satisfies the above range, a resist pattern film having a rectangular cross section with suppressed standing wave trajectories can be formed.

In the present composition, in order to reduce the standing wave locus of the resist pattern film, an acid generated by exposure is diffused in the resin film. Further, since the acid is easily diffused when the resin film contains a solvent, it is estimated that the standing wave trace of the resist pattern film due to the diffusion of the acid can be efficiently reduced.

The solvent (D1) has a boiling point (normal boiling point) of 120 to 160 ℃ at atmospheric pressure, and most of the solvent volatilizes and hardly remains in the resin film after the photosensitive resin composition is applied to the substrate. On the other hand, since the solvent (D2) has a normal boiling point of over 170 ℃, it does not volatilize and remains in most of the resin film after the photosensitive resin composition is applied to the substrate. From the above, it is presumed that the present composition, by containing the solvent (D2) in the resin film, easily diffuses the acid generated by exposure in the resin film, and as a result, can efficiently reduce the standing wave trace of the resist pattern film.

On the other hand, if the resin film contains a solvent, the low-molecular component may be present in the resin film in a biased manner when the low-molecular component and the solvent are difficult to mix. Since the quencher as a low-molecular component affects the diffusion of the acid, it is presumed that if the quencher is present in a resin film in a biased manner, a resist pattern film having a rectangular cross section cannot be formed.

In general, since the compatibility between substances is improved when the partition coefficients are approximated, it is presumed that the presence of the deviation of the quencher in the resin film can be eliminated by approximating the partition coefficient of the solvent remaining in the resin film (the solvent (D2) in the present composition) to the partition coefficient of the quencher in the present composition, and as a result, a resist pattern film having a rectangular cross section can be formed. The solvent (D2) has a partition coefficient of 0.3 to 1.2, which is similar to that of the compound (C) as a quencher. From the above, it is presumed that the present composition can eliminate the presence of the compound (C) bias in the resin film by containing the solvent (D2) and the compound (C), and can form a resist pattern film having a rectangular cross section.

The partition coefficient can be calculated by measuring the concentration ratio (partition coefficient) of the compound in each liquid layer when the compound is dissolved in a mixed solution of water and 1-octanol. The higher the concentration of the compound in 1-octanol relative to the concentration of the compound in water, the more hydrophobic (fat-soluble) the value. The distribution coefficient can also be determined by the Professional chemical mapping software (Chem Draw Professional) 17.1.

The solvent (D) may contain a solvent other than the solvent (D1) and the solvent (D2) (hereinafter, referred to as "solvent (D3)"). Examples of the solvent (D3) include: alcohol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol and diethylene glycol monoethyl ether; ester solvents such as ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl acetoacetate, ethyl ethoxyacetate, and γ -butyrolactone; ketone solvents such as methyl amyl ketone; alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol di-n-propyl ether; and alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. The solvent (D3) may be used singly or in combination of two or more.

The content of the solvent (D3) in 100% by mass of the solvent (D) is usually less than 30% by mass, preferably less than 20% by mass, and more preferably 0% by mass.

The solid content concentration of the present composition is usually 5% by mass or more, preferably 10% by mass to 50% by mass. Within the above range, a resist pattern film having a rectangular cross section can be formed with a thickness most suitable for the production of a plating formation such as a wiring or a bump, with suppressed standing wave trajectories.

< other ingredients >

The present compositions may further contain other ingredients. Examples of the other components include: a quencher other than the compound (C); a surfactant which exhibits an effect of improving the coatability, defoaming property, etc. of the photosensitive resin composition; a sensitizer which absorbs exposure light to improve the acid generation efficiency of the photoacid generator; an alkali-soluble resin or a low-molecular-weight phenol compound for controlling the dissolution rate of a resin film formed from the photosensitive resin composition with respect to an alkaline developer; an ultraviolet absorber for preventing photoreaction caused by refraction of scattered light at the time of exposure back to an unexposed portion; a thermal polymerization inhibitor for improving the storage stability of the photosensitive resin composition; a mercapto compound that improves the adhesion between the resist pattern film and the metal film of the substrate; an imidazole compound; and an adhesion promoter such as a silane coupling agent, an antioxidant, and an inorganic filler.

< production of photosensitive resin composition >

The present composition can be produced by uniformly mixing the above-mentioned components. In order to remove foreign substances, the above components may be uniformly mixed, and the resulting mixture may be filtered with a filter such as a membrane filter or a capsule cartridge filter.

[ method for producing resist Pattern film ]

The method for manufacturing a resist pattern film of the present invention includes: a step (1) of forming a resin film of the photosensitive resin composition of the present invention on a metal film of a substrate having the metal film; a step (2) of exposing at least a part of the resin film; and a step (3) of developing the resin film after exposure.

< step (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 a flat plate shape or a convex-concave shape, and the shape of the substrate may be a circular shape or a square shape. In addition, the size of the substrate is not limited.

Examples of the metal film include a film containing a metal such as aluminum, copper, silver, gold, and palladium, and an alloy containing two or more of the metals, and a copper film, that is, a film containing copper and/or a copper alloy is preferable. The thickness of the metal film is usuallyPreferably, it isA metal film is typically disposed on a surface of the substrate. The metal film can be formed by a sputtering method or the like.

The resin film is formed by coating the composition on a metal film of a substrate having the metal film. Examples of the coating method of the present composition include: among these methods, spin coating, roll coating, screen printing and applicator (applicator) methods are preferable.

After the application of the present composition, the applied present composition may be subjected to a heat treatment for the purpose of, for example, volatilizing the solvent (D). The heat treatment is usually carried out at 50 to 200 ℃ for 0.5 to 20 minutes. The thickness of the resin film is usually 0.1 to 80 μm, preferably 0.5 to 50 μm, and more preferably 1 to 10 μm.

< step (2) >

In the step (2), at least a part of the resin film formed in the step (1) is exposed to light. The exposure is usually performed selectively on the resin film by reducing the projection exposure through a photomask (photomask) having a predetermined mask pattern. Examples of the exposure light include ultraviolet rays or visible rays having a wavelength of 150nm to 600nm, preferably 200nm to 500 nm. Examples of the light source of the exposure light include: low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, laser. The exposure amount can be suitably selected depending on the kind of exposure light, the kind of the present composition and the thickness of the resin film, and is usually 100mJ/cm²～20,000mJ/cm²。

The resin film may be subjected to a heat treatment after exposure to light and before development. The heat treatment is performed under conditions of, usually, 70 to 180 ℃ for 0.5 to 10 minutes, preferably 75 to 160 ℃ for 0.8 to 7 minutes, and more preferably 80 to 140 ℃ for 1.0 to 5 minutes.

The acid generated by the photoacid generator (B) is diffused in the resin film by the heat treatment, whereby the standing wave effect generated in the resin film can be reduced.

< step (3) >

In step (3), the resin film exposed in step (2) is developed to form a resist pattern film. Development is generally carried out using an alkaline developer. Examples of the developing method include: spraying, dipping, liquid-filling, and spinning immersion (puddle). The developing conditions are usually 10 to 30 ℃ for 1 to 30 minutes.

The alkaline developer includes, for example, an aqueous solution containing one or two or more alkaline substances. Examples of the basic 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, piperidine and the like. 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.

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

As described above, a resist pattern film as a mold for forming a plating formation can be formed on the metal film of the substrate, and a substrate for plating having the resist pattern film on the metal film can be obtained. The thickness of the resist pattern film is usually 0.1 to 80 μm, preferably 0.5 to 50 μm, and more preferably 1.0 to 10 μm.

The shape of the opening of the resist pattern film can be selected according to the type of the plating formation. When the plating formation object is a wiring, the shape of the opening of the resist pattern film viewed from above is linear, and when the plating formation object is a bump, the shape of the opening of the resist pattern film viewed from above is square.

When the opening of the resist pattern film is linear in shape as viewed from above, the line width of the resist pattern film is usually 0.1 to 50 μm, preferably 0.3 to 10 μm. Within the above range, the effect of the method for producing a resist pattern film of the present invention is more remarkable.

The standing wave locus of the resist pattern film can be confirmed by observing the cross section of the resist pattern film with an electron microscope. When the opening of the resist pattern film is linear in shape as viewed from above, the width (W4) of the standing wave trajectory is usually less than 40nm, preferably less than 20 nm.

[ method for producing plated article ]

The method for producing a plating formation product of the present invention includes a step (4) of performing plating treatment using a substrate having a resist pattern film produced by the method for producing a resist pattern film of the present invention as a mold.

< step (4) >

Examples of the plating treatment include wet plating treatments such as electrolytic plating treatment, electroless plating treatment, and melt plating treatment, and dry plating treatments such as chemical vapor deposition and sputtering. In the case of forming a wiring or a connection terminal in wafer-level processing, it is generally performed by electrolytic plating treatment.

Before the electrolytic plating treatment, pretreatment such as ashing (ashing), flux (flux) treatment, desmear (desmear) treatment, and the like may be performed to improve the affinity between the inner wall surface of the resist pattern and the plating solution.

In the case of the electrolytic plating treatment, a layer formed on the inner wall of the resist pattern by sputtering or electroless plating treatment may be used as the seed layer, and in the case of using a substrate having a metal film on the surface thereof, the metal film may be used as the seed layer. The barrier layer may also be formed prior to forming the seed layer, which may also be used as a barrier layer.

Examples of the plating solution used in the electrolytic plating treatment include: a copper plating solution containing copper sulfate, copper pyrophosphate, or the like; gold plating solution treatment containing gold potassium cyanide; and a nickel plating solution containing nickel sulfate or nickel carbonate.

The conditions for the electrolytic plating treatment may be appropriately selected depending on the kind of the plating solution, and for example, in the case of the electrolytic plating treatment containing copper sulfate, the temperature is usually 10 to 90 ℃ and the current density is usually 0.1A/dm²～100A/dm². As for the plating treatment, different plating treatments may be sequentially performed. For example, the solder copper pillar bump can be formed by first performing a copper plating process, then performing a nickel plating process, and then performing a molten solder plating process.

The thickness of the plated formation varies depending on the application, and is usually 5 to 80 μm in the case of a bump and 0.1 to 10 μm in the case of a wiring, for example.

< other steps >

In the method for producing a plated shaped article of the present invention, as another step, a step of removing the resist pattern film after the step (4) (hereinafter, also referred to as "step (5)") can be mentioned. The step (5) is performed, for example, by a resist stripping solution containing tetramethylammonium hydroxide, dimethyl sulfoxide, water and/or N, N-dimethylformamide.

Further, the method for producing a plating formation of the present invention may comprise the steps of: the metal film other than the region where the plating formation is formed is removed by, for example, wet etching.

Examples

The present invention will be described more specifically with reference to 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 was measured by gel permeation chromatography under the following conditions.

GPC apparatus: manufactured by Tosoh corporation, Inc., under the name "HLC-8220-GPC"

Column: connecting in series TSK-M and TSK2500 columns manufactured by Tosoh corporation

Vehicle: tetrahydrofuran (THF)

Temperature: 40 deg.C

The detection method: refractive index method

Standard substance: polystyrene

< production of photosensitive resin composition >

[ example 1A ]

The photosensitive resin composition of example 1A was prepared by uniformly mixing 100 parts by mass of a polymer (a-1) (Mw 11,000) having a monomer-derived structural unit represented by the following formula (a-1), 1 part by mass of a photoacid generator (B-1) represented by the following formula (B-1), 0.34 part by mass of a quencher (C-1) represented by the following formula (C-1), and 0.1 part by mass of a surfactant (E1) (trade name "NBX-15", manufactured by nios (Neos) incorporated) in co., ltd.) in a mixed solvent having the components and their content ratios shown in the following table 1 so that the solid content concentration became 15 mass%.

Examples 2A to 5A and comparative examples 1A to 4A

Photosensitive resin compositions of examples 2A to 5A and comparative examples 1A to 4A were produced in the same manner as in example 1A, except that components having the components shown in table 1 below and their contents were used in example 1A.

The details of each component shown in table 1 are as follows.

[ solution 4]

The subscript between parentheses in the formula (A-1) represents the content ratio (mol%) of each structural unit.

[ solution 5]

[ solution 6]

[ solution 7]

The partition coefficients of the quencher (C-1) and the quencher (C-2) were 0.781 and 4.876, respectively.

The partition coefficients of the quencher (C-3) and the quencher (C-4) were 1.310 and 2.887, respectively.

Solvent (D1-1): propylene glycol monomethyl ether acetate (partition coefficient: 0.5992, normal boiling point: 146 ℃)

Solvent (D2-1): 3-Methoxybutyl acetate (partition coefficient 0.9320, normal boiling point 172 ℃)

Solvent (D2-2): dipropylene glycol methyl ether acetate (partition coefficient: 0.7326, normal boiling point: 209 ℃ C.)

Solvent (D3-1): gamma-butyrolactone (partition coefficient-0.803, standard boiling point-204 deg.C)

The distribution coefficient is a value obtained by Professional chemical mapping software (Chem Draw Professional)17.1 manufactured by Perkin Elmer (Perkin Elmer).

< production of resist Pattern film >

[ example 1B ]

The photosensitive resin composition of example 1A was spin-coated on a copper sputtered film of a silicon wafer substrate including the copper sputtered film using a coater developer (product name "MARK) -8" manufactured by Tokyo Electron (Tokyo Electron) corporation, and then heated at 110 ℃ for 60 seconds to form a resin film. The resin film was exposed to light using a stepper (stepper) (model "NSR-i 10D", manufactured by Nikon corporation) through a pattern mask. The exposed coating film was heated at 90 ℃ for 60 seconds, and then immersed in a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 90 seconds and developed. Then, flowing water cleaning was performed, and nitrogen gas was blown to form the resist pattern film of example 1B (a resist pattern film that becomes a1 line/1 space, and the thickness of the resist pattern film is 1.5 μm) on the copper sputtering film of the substrate.

The shape of the cross section of the resist pattern film of example 1B was observed with an electron microscope. The shape of the resist pattern film and the standing wave locus were evaluated by the following methods and criteria. The results of measurement and evaluation are shown in table 2.

Shape of resist Pattern film

As shown in FIG. 1, the widths of the spaces formed by the resist pattern films were measured at heights of 0 μm, 0.75 μm and 1.5 μm from the substrate (W1-W3). Further, W2/W1 and W3/W1 were calculated, and the rectangularity of the pattern was evaluated according to the following criteria.

(evaluation criteria for rectangularity)

O: 0.95 or more and 1.05 or less

And (delta): more than 1.05 and not more than 1.15

X: over 1.15

Stationary wave trace

As shown in fig. 2, the width of the standing wave locus (W4) was measured.

Examples 2B to 5B and comparative examples 1B to 4B

Resist pattern films of examples 2B to 5B and comparative examples 1B to 4B were formed and evaluated in the same manner as in example 1B, except that the photosensitive resin composition shown in table 2 was used in example 1B instead of the photosensitive resin composition of example 1A. The evaluation results are shown in table 2.

[ Table 2]

TABLE 2

Description of the symbols

10. 100, and (2) a step of: substrate

11: copper sputtering film

12: silicon wafer

20. 200: resist pattern film

300: standing wave trace