JP2020136430A - Photosensitive resin composition for forming wiring interlayer insulating layer, wiring layer for semiconductor, and wiring layer laminate for semiconductor using the same - Google Patents

Abstract

To provide a photosensitive resin composition for forming a wiring interlayer insulating layer, which is excellent in compatibility and can be formed into a favorable film, and a wiring layer for a semiconductor and a wiring layer laminate for a semiconductor using the same.SOLUTION: A photosensitive resin composition for forming a wiring interlayer insulating layer includes at least (A) a bismaleimide-containing polymer, (B) a compound having at least one selected from the group consisting of an aromatic ring, a heterocycle, and an alicycle, and having at least one of a methylol group and an alkoxyalkyl group, (C) a nadimide compound, and (D) a photo acid generator, and the (A) has an HLB value of 4.0 to 5.0, the (B) has an HLB value of 4.0 to 10.0, and the (C) has an HLB value of 4.0 to 9.0.SELECTED DRAWING: Figure 2

Description

The present disclosure relates to a photosensitive resin composition for forming a wiring interlayer insulating layer, and a semiconductor wiring layer and a semiconductor wiring layer laminate using the same.

For the purpose of increasing the density and performance of semiconductor packages, a mounting form in which chips having different performances are mixedly mounted in one package has been proposed. In this case, a high-density interconnect technique between chips, which is excellent in terms of cost, is important (see, for example, Patent Document 1).

As a form for mounting a plurality of chips at high density, a packaging technology using an organic substrate having high-density wiring and a fan-out type packaging technology (FO-WLP:) having a through mold via (TMV). Fan Out-Wafer Level Package), packaging technology using silicon or glass interposer, packaging technology using through silicon via (TSV), packaging technology using chips embedded in the substrate for chip-to-chip transmission, etc. Proposed.

In particular, when semiconductor chips are mounted in a semiconductor wiring layer and FO-WLP, a fine wiring layer for conducting the semiconductor chips with each other at a high density is required (see, for example, Patent Document 2). In the wiring layer, for example, fine wiring having a line width and a space width of 5 μm or less is arranged. The wiring is formed, for example, by using the trench method. The trench method is a method of forming a metal layer to be a wiring in a trench (groove) formed by a laser or the like on the surface of an insulating layer (wiring interlayer insulating layer) formed between wiring layers by a plating method or the like.

In the wiring interlayer insulating layer, it is necessary to preferably maintain the insulating property (excellent in insulating reliability). For example, in Patent Document 3, for the purpose of providing a wiring interlayer insulating layer having good insulation reliability, a wiring interlayer insulating layer containing a curable resin and a curing agent and in contact with copper wiring is formed. The resin composition used for the above is disclosed.

Special Table 2012-528770 U.S. Patent Application Publication No. 2011/0221071 International Publication No. 2018/056466

By the way, when forming a wiring interlayer insulating layer, a plurality of components may be mixed to prepare a varnish-like resin composition, and the resin composition may be formed into a film. Therefore, in order to preferably obtain the wiring interlayer insulating layer having the above-mentioned characteristics, it is necessary that the contained components are compatible with each other when the varnish-like resin composition is prepared, and the film is formed. Even after that, it is required that turbidity, phase separation, etc. do not occur.

Therefore, the present invention provides a photosensitive resin composition for forming a wiring interlayer insulating layer, which has excellent compatibility and can form a film well, a wiring layer for a semiconductor, and a wiring layer laminate for a semiconductor using the same. The purpose is to do.

The present invention has at least one selected from the group consisting of [1] (A) bismaleimide-containing polymer and (B) aromatic ring, heterocyclic ring and alicyclic ring, and at least one of a methylol group and an alkoxyalkyl group. A compound having one of them, (C) a nadiimide compound, and (D) a photoacid generator are contained at least, and the HLB value of (A) is 4.0 to 5.0, and the HLB value of (B) is 4. A photosensitive resin composition for forming an interlayer insulating layer for wiring, which has an HLB value of 0 to 10.0 and an HLB value of (C) of 4.0 to 9.0.

Further, in the present invention, the photosensitive resin composition for forming a wiring interlayer insulating layer according to the above [1], wherein the (A) bismaleimide-containing polymer contains at least a resin represented by the following structural formula (I). Is.

In the structural formula (I), Z ¹ and Z ² each independently represent a divalent hydrocarbon group, and R ⁵ represents a tetravalent organic group. n represents an integer of 1-10. When n is 2 or more, a plurality of Z ² may being the same or different.

Further, in the present invention, the relative permittivity of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer according to the above [1] or [2] at 10 GHz is 3.0 or less. The photosensitive resin composition for forming a wiring interlayer insulating layer according to [1] or [2].
Further, in the present invention, the dielectric loss tangent at 10 GHz of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer according to any one of [1] to [3] above is 0.01 or less. The photosensitive resin composition for forming a wiring interlayer insulating layer according to any one of the above [1] to [3].

Further, the present invention is a wiring layer for a semiconductor containing a cured product of the photosensitive resin composition for forming a wiring interlayer insulating layer according to any one of [1] to [4] above.
Further, the present invention is a semiconductor wiring layer laminate including the semiconductor wiring layer described in [6] above [5].

According to the present invention, it is possible to provide a photosensitive resin composition for forming a wiring interlayer insulating layer, which has excellent compatibility and can form a film well. In addition, the cured product obtained from this composition exhibits low dielectric properties and excellent insulation reliability.

It is a schematic cross-sectional view which shows one Embodiment of a semiconductor package. FIG. 5 is a schematic cross-sectional view showing a semiconductor wiring layer laminate included in the semiconductor package of FIG.

The photosensitive resin composition for forming a wiring interlayer insulating layer according to an embodiment has at least one selected from the group consisting of (A) a bismaleimide-containing polymer, (B) an aromatic ring, a heterocyclic ring, and an alicyclic ring. It also contains at least a compound having at least one of a methylol group and an alkoxyalkyl group, (C) a nadiimide compound and (D) a photoacid generator, and has an HLB value of (A) of 4.0 to 5.0. The HLB value of B) is 4.0 to 10.0, and the HLB value of (C) is 4.0 to 9.0. This composition is a curable composition that can be cured by light (and even heat). In this composition, a methylol group-containing compound or an alkoxyalkyl group-containing compound and a nadiimide compound can function as a curing agent.

In the photosensitive resin composition for forming the wiring interlayer insulating layer, the (A) bismaleimide-containing polymer contains at least the resin represented by the following structural formula (I).

In the structural formula (I), Z ¹ and Z ² each independently represent a divalent hydrocarbon group, and R ⁵ represents a tetravalent organic group. n represents an integer of 1-10. When n is 2 or more, a plurality of Z ² may being the same or different.

The tetravalent organic group represented by R ⁵ may be, for example, a hydrocarbon group from the viewpoint of handleability. The hydrocarbon group may have, for example, 1-100, 2-50 or 4-30.

The hydrocarbon group may be substituted, for example, may contain a substituted or unsubstituted siloxane group. Examples of the siloxane group include groups derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and the like.

Substituents include, for example, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, alkoxy groups, mercapto groups, cycloalkyl groups, substituted cycloalkyl groups, heterocyclic groups, substituted heterocyclic groups, aryl groups, substituted aryl groups, heteroaryls. Group, substituted heteroaryl group, aryloxy group, substituted aryloxy group, halogen atom, haloalkyl group, cyano group, nitro group, nitroso group, amino group, amide group, -C (O) H, -C (O)- , -S-, -S (O) _2- , -OC (O) -O-, -C (O) -NR ^c , -NR ^c C (O) -N (R ^c ) ₂ , -OC (O) ) -N (R ^c ) ₂ , an acyl group, an oxyacyl group, a carboxyl group, a carbamate group, a sulfonyl group, a sulfonamide group, a sulfryl group and the like may be used. Here, R ^c represents a hydrogen atom or an alkyl group. One type or two or more types of these substituents can be selected according to the purpose, application and the like.

Tetravalent organic group represented by R ^5, for example, tetravalent residue of acid anhydride having two or more anhydride rings per molecule, i.e., an acid anhydride from the acid anhydride group (- It may be a tetravalent group excluding two CO (= O) OC (= O) −). Examples of the acid anhydride include compounds described below.

The organic group represented by R ⁵ is preferably a tetravalent aromatic group, more preferably a residue obtained by removing two acid anhydride groups from pyromellitic anhydride from the viewpoint of excellent high frequency characteristics. The divalent organic group having two imide bonds with R ⁵ is preferably a group represented by the following formula (7).

The divalent organic group having two imide bonds with R ⁵ may be a group represented by the following formula (8) or (9) from the viewpoint of excellent dielectric properties.

The maleimide compound can be used, for example, by purchasing a commercially available product. Examples of commercially available products include SFR2300 (trade name, manufactured by Hitachi Kasei Co., Ltd.), BMI-1500, BMI-1700, BMI-3000, BMI-5000 and BMI-, which are maleimide compounds represented by the formula (I). 9000 (trade name, manufactured by Designer Molecules Inc. (DMI)) and the like can be mentioned.

The HLB value of the maleimide compound is preferably 4.0 or more, and 5.0 or less from the viewpoint of further improving the water resistance of the cured product of the composition.

The term "HLB value" as used herein refers to the organic value (OV) and the inorganic value from the inorganic group table described in "Organic Conceptual Diagram-Basics and Applications-" (published by Sankyo Publishing Co., Ltd. in 1984, by Yoshio Koda). Using the sex value (IV), it can be calculated by the following formula.
HLB value = 10 × (IV) / (OV)
The HLB value (Hydrophilic-Lipophilic Balance) is an index showing the balance between hydrophilicity and lipophilicity, and generally, the larger the HLB value, the higher the hydrophilicity.

The weight average molecular weight Mw of the bismaleimide-containing polymer may be 1000 or more and 1500 or more or 3000 or more, and may be 30,000 or less, 20000 or less or 15000 or less. The weight average molecular weight Mw of the maleimide compound is preferably 1000 to 30,000, more preferably 1500 to 20000, from the viewpoint of solubility in a solvent and compatibility with other components such as a monomer and a resin.

The weight average molecular weight Mw of the bismaleimide-containing polymer can be measured by a gel permeation chromatography (GPC) method. The measurement conditions of GPC are as follows.
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Guard column and column: TSK Guardcolum HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [All manufactured by Tosoh Corporation, product name]
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Measurement temperature: 40 ° C

The content of the bismaleimide-containing polymer may be, for example, 10% by mass or more, 40% by mass or more, or 80% by mass or more, 99% by mass or less, 95% by mass, based on the total amount of solids in the composition. It may be less than or equal to 90% by mass or less.

The photosensitive resin composition for forming an interlayer insulating layer for wiring has at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicyclic as a component (B), and at least a methylol group and an alkoxyalkyl group. Contains a compound having one.
Here, the aromatic ring means a hydrocarbon group having aromaticity (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocycle means a cyclic group having at least one heteroatom such as a nitrogen atom or a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), for example, a pyridine ring, an imidazole ring, a pyrrolidinone ring, and the like. Examples thereof include an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. The alicyclic means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. Can be mentioned.
The alkoxyalkyl group means a group in which an alkyl group is bonded to another alkyl group via an oxygen atom. In the alkoxyalkyl group, the two alkyl groups may be the same as or different from each other, and may be, for example, an alkyl group having 1 to 10 carbon atoms.

From the viewpoint of improving the compatibility of each component in the composition with each other and enabling good film formation, the component (B) is selected from the group consisting of an aromatic ring, a heterocycle and an alicyclic having a specific HLB value. A compound having at least one of these compounds and having at least one of a methylol group and an alkoxyalkyl group is used. The HLB value of the component (B) is 4.0 or more, 4.2 or more, 4.4 or more, 4.6 or more, 4.8 or more, or 5.0 or more. The HLB value of the component (B) is 10.0 or less.

As the component (B), specifically, at least one selected from the group consisting of a compound having a phenolic hydroxyl group and a compound having a hydroxymethylamino group is preferable. The component (B) can be used alone or in combination of two or more.

As the compound having a phenolic hydroxyl group, a conventionally known compound can be used, but the compound represented by the following general formula (12) is preferable from the viewpoint of excellent compatibility of each component with each other.

In the above general formula (12), R ⁶ and R ⁷ independently represent a hydrogen atom or a monovalent organic group, R ⁸ independently represents a monovalent organic group, and a and b respectively. Independently indicates an integer of 1 to 3, and c independently indicates an integer of 0 to 3. Here, as the monovalent organic group, for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group; and a vinyl group and the like having 2 to 10 carbon atoms. Examples thereof include an alkenyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group; and a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are replaced with a halogen atom such as a fluorine atom. When there are a plurality of R ^{6 to} R ⁸ , they may be the same or different from each other.

Further, as the compound having a phenolic hydroxyl group, a compound represented by the following general formula (13) may be used.

In the above general formula (13), Z ⁴ represents a single bond or a divalent organic group, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent organic group, and R ¹¹ and R ¹² are. , Each independently represents a monovalent organic group, d and e each independently represent an integer of 1 to 3, and f and g each independently represent an integer of 0 to 3. Here, as the monovalent organic group, for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group; and a vinyl group and the like having 2 to 10 carbon atoms. Examples thereof include an alkenyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group; and a group in which a part or all of the hydrogen atoms of these hydrocarbon groups are replaced with a halogen atom such as a fluorine atom. When there are a plurality of R ^{9 to} R ¹² , they may be the same or different from each other.

The compound represented by the general formula (13) is preferably a compound represented by the following general formula (14).

In the above general formula (14), Z ⁵ represents a single bond or a divalent organic group, and each of the plurality of Rs independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms). The plurality of Rs may be the same as or different from each other.

The content of the component (B) may be 0.1 part by mass or more, 2 parts by mass or more, or 5 parts by mass or more, and 98 parts by mass or less, when the bismaleimide-containing polymer is 100 parts by mass. , 50 parts by mass or less, or 40 parts by mass or less, and is particularly preferably 20 parts by mass to 40 parts by mass from the viewpoint of being able to form a wiring interlayer insulating layer having both low dielectric properties and high heat resistance. ..

The photosensitive resin composition for forming the wiring interlayer insulating layer contains one kind or two or more kinds of nadiimide compounds as the component (C). The nadiimide compound is a compound having a group represented by the following formula (15).

In formula (15), R ¹¹ represents an allyl group and m represents 0 or 1.

The nadiimide compound may have one group represented by the formula (15), may have two or more, and preferably has two. The nadiimide compound is preferably a compound represented by the following formula (16).

In formula (16), R ¹¹ and m are independently synonymous with R ¹¹ and m in formula (15), respectively, and R ¹² represents a divalent organic group.

The divalent organic group represented by R ¹² may have an aromatic hydrocarbon group (aromatic ring). The aromatic hydrocarbon group (aromatic ring) may be a benzene residue, a toluene residue, a xylene residue, a naphthalene residue or the like. The divalent organic group may have a linear, branched or cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a linear, branched or cyclic alkyl group. The divalent organic group may have both the above-mentioned aromatic hydrocarbon group (aromatic ring) and aliphatic hydrocarbon group.

The divalent organic group represented by R ¹² may be a divalent hydrocarbon group containing only a carbon atom and a hydrogen atom, and is a divalent organic group containing other atoms in addition to the carbon atom and the hydrogen atom. It may be, preferably a divalent hydrocarbon group.

The divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group, or may be a divalent aliphatic hydrocarbon group having the following structure.

In the formula, n is an integer of 1-10.

The divalent hydrocarbon group is preferably a divalent hydrocarbon group having an aromatic hydrocarbon group (aromatic ring), and more preferably a divalent hydrocarbon group having any of the following structures. Is.

The divalent organic group containing other atoms may contain one or more atoms such as nitrogen atom, oxygen atom, sulfur atom and fluorine atom in addition to carbon atom and hydrogen atom. The divalent organic group containing other atoms is preferably a divalent hydrocarbon group having any of the following structures.

The nadiimide compound is preferably a bisallyl nadiimide compound represented by the following formula (17) (a compound in which m is 1 in the formula (16)).

In equation (17), R ¹² is synonymous with R ¹² in equation (16).

The nadiimide compound is more preferably a bisallyl nadiimide compound in which R ¹² in the formula (17) is a divalent hydrocarbon group having an aromatic hydrocarbon group (aromatic ring), and more preferably the following formula. A wiring interlayer insulating layer which is a bisallyl nadiimide compound represented by (17-1) or (17-2), has excellent UV curability and compatibility with a maleimide compound, and exhibits low dielectric properties is more preferable. From the viewpoint of being able to form, a bisallyl nadiimide compound represented by the following formula (17-1) is more preferable.

The HLB value of the nadiimide compound is 4.0 or more, 5.0 or more, or 6.0 or more, and from the viewpoint of further improving compatibility (particularly compatibility with maleimide-containing polymer), 9.0 or less, 8 It is 0.0 or less, or 7.0 or less.

The content of the (C) nadiimide compound has at least one selected from the group consisting of (A) bismaleimide-containing polymer, (B) aromatic ring, heterocyclic ring and alicyclic ring, and has a methylol group and an alkoxyalkyl group. When the total amount of the compound having at least one of the above is 100 parts by mass, it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and preferably 90 parts by mass from the viewpoint of sufficiently improving the heat resistance. Hereinafter, it is more preferably 50 parts by mass or less.

The photosensitive resin composition for forming the wiring interlayer insulating layer contains a photoacid generator as the component (D). The photoacid generator is not particularly limited as long as it is a compound that generates an acid by irradiation with active light or the like. Examples of the component (D) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds and the like. Above all, from the viewpoint of excellent availability, the component (D) is preferably at least one selected from the group consisting of onium salt compounds and sulfonimide compounds. In particular, when a solvent is used, the component (D) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.

Examples of the onium salt compound include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutane sulfonate, diphenyliodonium heptadecafluorooctane sulfonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoro. Diaryliodonium salts such as phosphate, diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tris [(trifluoromethyl) sulfonyl] metanide; triaryl; Examples include sulfonium salts. Of these, a sulfonium salt is preferable from the viewpoint of further improving sensitivity and thermal stability, and a triarylsulfonium salt is more preferable from the viewpoint of further improving thermal stability. The onium salt compound may be used alone or in combination of two or more.

Examples of the triarylsulfonium salt include a compound represented by the following general formula (b1), a compound represented by the following general formula (b2), a compound represented by the following general formula (b3), and the following general formula. At least one cation selected from the group consisting of the compound represented by (b4), a tetraphenylborate skeleton, an alkyl sulfonate skeleton having 1 to 20 carbon atoms, a phenyl sulfonate skeleton, a 10-campar sulfonate skeleton, and 1 to 1 carbon atoms. Examples thereof include a sulfonium salt having an anion having at least one skeleton selected from the group consisting of 20 trisalkylsulfonylmethanide skeletons, tetrafluoroborate skeletons, hexafluoroantimonate skeletons and hexafluorophosphate skeletons.

The hydrogen atoms of the phenyl groups of the general formulas (b1) to (b4) are hydroxyl groups, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, alkylcarbonyl groups having 2 to 12 carbon atoms, and carbons. It may be substituted with at least one selected from the group consisting of the number 2 to 12 alkoxycarbonyl groups, and when there are a plurality of substituents, they may be the same or different from each other.

The hydrogen atom of the phenyl group of the tetraphenylborate skeleton includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms, and when there are a plurality of substituents, they are the same as each other. May be different.

The hydrogen atom of the alkylsulfonate skeleton is at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted, and when there are a plurality of substituents, they may be the same or different from each other.

The hydrogen atom of the phenyl group of the phenylsulfonate skeleton is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon. It may be substituted with at least one selected from the group consisting of an alkylcarbonyl group having 2 to 12 atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms, and when there are a plurality of substituents, they are the same as each other. May be different.

The hydrogen atom of the trisalkylsulfonylmethanide skeleton is at least selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted with one kind, and when there are a plurality of substituents, they may be the same or different from each other.

The fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms. When there are a plurality of substituents, they may be the same or different from each other.

The sulfonium salt used as the photoacid generator of the component (D) has [4- (4-biphenylylthio) phenyl] -4-biphenylyl as a cation from the viewpoint of further excellent sensitivity, resolution and insulating property. Phenylsulfonium, (2-methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium, Selected from the group consisting of (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylyl sulfonium and tris [4- (4-acetylphenyl sulfanyl) phenyl] sulfonium. It is preferably a compound having at least one kind.

The sulfonium salt used as the component (D) is trifluoromethanesulfonate, nonafluorobutane sulfonate, hexafluoroantimonate, tris [(trifluoromethyl) sulfonyl] metanide, 10-camparsulfonate, tris (pentafluoroethyl) as anions. It is preferably a compound having at least one selected from the group consisting of trifluorophosphate and tetrakis (pentafluorophenyl) borate.

Specific examples of the sulfonium salt include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylyl sulfonium nonafluorobutane sulfonate, [4- (4-biphenylylthio). Phenyl] -4-biphenylylphenyl sulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenyl sulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. The sulfonium salt can be used alone or in combination of two or more.

Specific examples of the sulfoneimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- (trifluoromethylsulfonyloxy). Oxy) Bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- Examples thereof include naphthalimide and N- (10-campharsulfonyloxy) -1,8-naphthalimide. The sulfoneimide compound can be used alone or in combination of two or more.

The photoacid generator of the component (D) can be used alone or in combination of two or more.
The content of the component (D) has at least one selected from the group consisting of (A) bismaleimide-containing polyma, (B) aromatic ring, heterocycle and alicyclic ring, and has a methylol group and an alkoxyalkyl group. When the total of the compound having at least one and the (C) nadiimide compound is 100 parts by mass, it may be preferably 0.1 part by mass or more and 10 parts by mass from the viewpoint of sufficiently curing the composition. It may be less than a part, and more preferably 1 part by mass or more, and 6 parts by mass or less from the viewpoint that the unreacted substance is less likely to remain.

The photosensitive resin composition for forming the wiring interlayer insulating layer may further contain a coupling agent. The coupling agent may be, for example, a silane coupling agent. The silane coupling agent may have, for example, a vinyl group, an epoxy group, a styryl group, an acryloyl group, a methacryloyl group, an amino group, a ureido group, an isocyanate group, an isocyanurate group, a mercapto group and the like.

Examples of the silane coupling agent having a vinyl group include KBM-1003 and KBE-1003 (trade names, all manufactured by Shin-Etsu Chemical Co., Ltd., the same shall apply hereinafter). Examples of the silane coupling agent having an epoxy group include KBM-303, 402, 403, KBE-402, 403, X-12-981S, X-12-984S and the like. Examples of the silane coupling agent having a styryl group include KBM-1403 and the like. Examples of the silane coupling agent having a methacryloyl group include KBM-502,503 and KBE-502,503. Examples of the silane coupling agent having an acryloyl group include KBM-5103, X-12-1048, X-12-1050 and the like. Examples of the silane coupling agent having an amino group include KBM-602,603,903,573,575, KBE-903,9103P, X-12-972F and the like. Examples of the silane coupling agent having a ureido group include KBE-585 and the like. Examples of the silane coupling agent having an isocyanate group include KBE-9007 and X-12-1159L. Examples of the silane coupling agent having an isocyanurate group include KBM-9569 and the like. Examples of the silane coupling agent having a mercapto group include KBM-802,803, X-12-1154, and X-12-1156. These may be used alone or in combination of two or more, depending on the purpose, application and the like.

The content of the silane coupling agent has at least one selected from the group consisting of (A) bismaleimide-containing polyma, (B) aromatic ring, heterocyclic ring and alicyclic ring, and has a methylol group and an alkoxyalkyl group. When the total of the compound having at least one and the (C) nadiimide compound is 100 parts by mass, it may be preferably 0.01 parts by mass or more from the viewpoint of improving the adhesion to glass, silica and the like. It may be 5 parts by mass or less, and more preferably 0.1 part by mass or more and 2 parts by mass or less from the viewpoint that unreacted substances are less likely to remain.

The photosensitive resin composition for forming an interlayer insulating layer for wiring has at least one selected from the group consisting of (B) aromatic rings, heterocycles and alicyclics as a curing agent, and has a methylol group and an alkoxyalkyl group. In addition to the compound having at least one, the (C) nadiimide compound and the photoacid generator, other curing agents may be further contained. Examples of other curing agents include dicyandiamide, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenylsulfone, phenylenediamine, xylene diamine and the like. Examples thereof include aromatic amine compounds, aliphatic amine compounds such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine, and guanamine compounds such as melamine and benzoguanamine. The other curing agent is preferably an aromatic amine compound from the viewpoint of obtaining good reactivity and heat resistance.

The photosensitive resin composition for forming the wiring interlayer insulating layer may further contain a catalyst in order to further accelerate the curing. Examples of the catalyst include peroxides, imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines and quaternary ammonium salts. These may be used alone or in combination of two or more.

The photosensitive resin composition for forming the wiring interlayer insulating layer may further contain a flame retardant. The flame retardant is not particularly limited, but is a halogen-containing flame retardant such as a brominated flame retardant or a chlorine flame retardant, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compound, red phosphorus, etc. Phosphate flame retardants, guanidine sulfamate, melamine sulfate, melamine polyphosphate, nitrogen flame retardants such as melamine cyanurate, phosphazene flame retardants such as cyclophosphazene and polyphosphazene, inorganic flame retardants such as antimony trioxide, etc. Can be mentioned. One type of these flame retardants may be used alone, or two or more types may be used in combination.

The photosensitive resin composition for forming the wiring interlayer insulating layer may further contain an ultraviolet absorber. The ultraviolet absorber is not particularly limited, and examples thereof include a benzotriazole-based ultraviolet absorber.

The photosensitive resin composition for forming the wiring interlayer insulating layer may further contain a fluorescent whitening agent. The fluorescent whitening agent is not particularly limited, and examples thereof include a stilbene derivative.

The photosensitive resin composition for forming the wiring interlayer insulating layer is preferably in the form of a film from the viewpoint of handleability. The photosensitive resin composition for forming the wiring interlayer insulating layer may be a varnish (liquid) in which each component is dissolved or uniformly dispersed in a solvent.

The means for preparing the varnish, the conditions and the like are not particularly limited. For example, after sufficiently uniformly stirring and mixing each principal component in a predetermined blending amount with a mixer or the like, kneading is performed using a mixing roll, an extruder, a kneader, a roll, an extruder or the like, and the obtained kneaded product is further cooled. And a method of crushing. The kneading method is not particularly limited.

When the photosensitive resin composition for forming the wiring interlayer insulating layer is a varnish, the solvent may be, for example, an organic solvent. The organic solvent is not particularly limited, and for example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone; Aromatic hydrocarbons such as toluene, xylene, mesitylene, limonene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- It may be nitrogen-containing such as 2-pyrrolidone. One of these may be used alone, or two or more thereof may be mixed and used. The organic solvent is preferably toluene, xylene, cyclohexanone, cyclopentanone, limonene or mesitylene in terms of solubility, and more preferably cyclopentanone, limonene or mesitylene in terms of low toxicity.

For example, the organic solvent is preferably used in an amount such that the solid content of the composition in the varnish is 5 to 90% by mass, and is said to be applicable from the viewpoint of maintaining good handleability and coating / coating property of the varnish. It is more preferable to use it in an amount such that the solid content is 10 to 60% by mass.

The cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer has a hygroscopicity of preferably 1% by mass or less after being placed in an atmosphere of 130 ° C. and a relative humidity of 85% for 200 hours. The hygroscopicity of the cured composition after being placed in an environment of 130 ° C. and 85% relative humidity for 200 hours can be measured by the method described in Examples.

The relative permittivity of the wiring interlayer insulating layer (cured product of the composition) at 10 GHz should be 3.6 or less, 3.2 or less, or 3.0 or less in that crosstalk between wiring layers can be suppressed. It is preferable, and more preferably 2.8 or less in that the reliability of the electric signal can be improved. The relative permittivity may be 1.0 or more. The dielectric loss tangent of the wiring interlayer insulating layer (cured product of the composition) at 10 GHz is preferably 0.012 or less, more preferably 0.01 or less, still more preferably 0.008 or less, and extremely preferably 0.005 or less. Yes, for example 0.0001 or more. The relative permittivity and the dielectric loss tangent can be measured by the method described in Examples.

The glass transition temperature of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer is preferably 120 ° C. or higher from the viewpoint of suppressing cracks during the temperature cycle, and 140 ° C. from the viewpoint of relaxing the stress on the wiring. The above is more preferable. The glass transition temperature of the cured product of the composition is preferably 240 ° C. or lower in terms of enabling lamination at a low temperature, and more preferably 220 ° C. or lower in terms of suppressing curing shrinkage. The glass transition temperature of the cured product of the composition can be measured by the method described in Examples.

The elongation at break of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer is preferably 5% or more from the viewpoint of reducing the warp of the wiring interlayer insulating layer, and from the viewpoint of relaxing the stress on the copper wiring. It is more preferably 10% or more, and further preferably 15% or more from the viewpoint of improving the temperature cycle reliability of the wiring layer laminate. The elongation at break may be 200% or less. The elongation at break can be measured by the method described in Examples.

The 5% weight reduction temperature of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer is, for example, 300 ° C. or higher from the viewpoint of heat resistance reliability. The 5% weight loss temperature of the cured product of the composition is a differential thermogravimetric simultaneous measurement device (Hitachi, Ltd.) using a cured product with a thickness of 300 μm obtained by curing the composition at 180 ° C. for 2 hours as a sample. It can be measured under the conditions of a heating rate of 10 ° C./min and a nitrogen flow of 400 mL / min using Hitachi High-Tech Science Corporation, trade name: TG / DTA6300).

The storage elastic modulus of the cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer at 40 ° C. may be 10 MPa to 5 GPa.

Since the photosensitive resin composition for forming a wiring interlayer insulating layer described above can form a wiring interlayer insulating layer having low dielectric properties and excellent insulation reliability, it is possible to form a wiring interlayer insulating layer of a semiconductor package and a wiring layer for a semiconductor. It is preferably used for laminates.

FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor package, and FIG. 2 is a schematic cross-sectional view showing a wiring layer laminate (wiring layer laminate for semiconductor) included in the semiconductor package of FIG. As shown in FIG. 1, the semiconductor package 100 includes a substrate 1, a wiring layer laminate 10 provided on the substrate 1, and semiconductor chips 2A and 2B mounted on the wiring layer laminate 10.

The substrate 1 is a sealed body formed by sealing the semiconductor chips 2C and 2D and the electrodes 5A and 5B with the insulating material 4. The semiconductor chips 2C and 2D in the substrate 1 can be connected to an external device via electrodes exposed from the insulating material 4. The electrodes 5A and 5B function as, for example, a conductive path for electrically connecting the wiring layer laminate 10 and the external device to each other. The semiconductor chips 2A and 2B are fixed on the wiring layer laminate 10 by the corresponding underfills 3A and 3B, respectively, and are electrically connected to each other via surface wiring (not shown) provided in the wiring layer laminate 10. Has been done. Each of the semiconductor chips 2A to 2D is electrically connected to any of the wirings in the wiring layer laminate 10.

Each of the semiconductor chips 2A to 2D is, for example, a volatile memory such as a graphic processing unit (GPU), a DRAM (Dynamic Random Access Memory) or a SRAM (Static Random Access Memory), and a non-volatile memory such as a flash memory. , RF chip, silicon photonics chip, MEMS (Micro Electro Mechanical Systems), sensor chip, etc. The thickness of the semiconductor chips 2A and 2B may be, for example, 30 μm or more and 200 μm or less.

The underfills 3A and 3B are, for example, capillary underfill (CUF), mold underfill (MUF), paste underfill (NCP), film underfill (NCF), or photosensitive underfill. The underfills 3A and 3B are each composed of a liquid curable resin (for example, an epoxy resin) as a main component. The insulating material 4 is, for example, a curable resin having an insulating property.

As shown in FIG. 2, the wiring layer laminate 10 includes the organic insulating layers 21 and 22, the copper wirings 13 and 14 embedded in the organic insulating layers 21 and 22, and the copper wirings 13 and 14 and the organic insulating layer 21. A plurality of wiring layers 41 and 42 including barrier metal films 15 and 16 provided between the wiring layers 41 and 22, wiring interlayer insulating layers 17 and 18 adjacent to the wiring layers 41 and 42, and organic insulating layers 21 and 22. , And a through wiring 19 penetrating the wiring interlayer insulating layers 17 and 18 (each of these layers is also collectively referred to as a wiring layer). The organic insulating layers 21 and 22 and the wiring interlayer insulating layers 17 and 18 are alternately laminated on the substrate 11. A part of the surface of the copper wirings 13 and 14 is exposed on one main surface side of the wiring layers 41 and 42, and the wiring interlayer insulating layers 17 and 18 are in contact with the surface of the exposed copper wirings 13 and 14. The wiring interlayer insulating layers 17 and 18 are cured products of the above-mentioned photosensitive resin composition for forming a wiring interlayer insulating layer. The organic insulating layers 21 and 22 can also be layers formed from a cured product of the photosensitive resin composition for forming the wiring interlayer insulating layer. The copper wiring may be exposed on both main surface sides of the wiring layer, and the wiring interlayer insulating layer may be in contact with the surface of the exposed copper wiring.

The substrate 11 is a support that supports the wiring layer laminate 10. The shape of the substrate 11 in a plan view is, for example, a circular shape or a rectangular shape. In the case of a circular shape, the substrate 11 has a diameter of, for example, 200 to 450 mm. In the case of a rectangular shape, one side of the substrate 11 is, for example, 300 to 700 mm.

The substrate 11 may be, for example, a silicon substrate, a glass substrate, or a peelable copper foil.
When a silicon substrate, a glass substrate, or the like is used as the substrate 11, a temporary fixing layer (not shown) for temporarily fixing the wiring layer laminate 10 and the substrate 11 may be provided. In this case, the substrate 11 can be easily peeled off from the wiring layer laminate 10 by removing the temporary fixing layer. The peelable copper foil is a laminated body in which a support, a peeling layer, and a copper foil are sequentially stacked. In the peelable copper foil, the support corresponds to the substrate 11, and the copper foil can form a part of the through wiring 19.

The organic insulating layer 21 (first organic insulating layer) includes a third organic insulating layer 23 located on the substrate 11 side and a fourth organic insulating layer 24 located on the second organic insulating layer 22 side. I'm out. The first organic insulating layer 21 has a plurality of groove portions 21a (first groove portions) in which the corresponding copper wiring 13 is arranged. The fourth organic insulating layer 24 is provided with a plurality of openings corresponding to the groove 21a.
The surface of the third organic insulating layer 23 exposed by these openings constitutes the bottom surface of the inner surface of the groove 21a. The side surface of the groove 21a is composed of a fourth organic insulating layer 24.

The thickness of the third organic insulating layer 23 and the fourth organic insulating layer 24 may be, for example, 0.5 to 10 μm, respectively. The thickness of the first organic insulating layer 21 may be, for example, 1 to 20 μm.

The plurality of groove portions 21a are provided on the surface of the first organic insulating layer 21 opposite to the substrate 11. In the cross section along the direction orthogonal to the extending direction of the groove portion 21a, each of the groove portions 21a has a substantially rectangular shape. The inner surface of the groove portion 21a has a side surface and a bottom surface. The plurality of groove portions 21a have a predetermined line width L and a space width S. The line width L and the space width S may be independently, for example, 0.5 to 10 μm. The line width L corresponds to the width of the groove portion 21a in the direction orthogonal to the extending direction of the groove portion 21a in a plan view. The space width S corresponds to the distance between adjacent groove portions 21a. The depth of the groove 21a corresponds to, for example, the thickness of the fourth organic insulating layer 24.

The organic insulating layer 22 (second organic insulating layer) is laminated on the first organic insulating layer 21 with the wiring interlayer insulating layer 17 (first wiring interlayer insulating layer) interposed therebetween. The second organic insulating layer 22 has a plurality of groove portions 22a (second groove portions) in which the corresponding copper wiring 14 is arranged.

The thickness of the second organic insulating layer 22 may be, for example, 1 to 10 μm. A plurality of openings corresponding to the groove 22a are provided in a part of the second organic insulating layer 22. The surface of the first wiring interlayer insulating layer 17 exposed by these openings constitutes the bottom surface of the inner surface of the groove 22a. Each side surface of the groove portion 22a is composed of a second organic insulating layer 22. The line width and the space width of the plurality of groove portions 22a coincide with the line width L and the space width S of the groove portions 21a.

The copper wiring 13 is provided in the corresponding groove portion 21a as described above, and functions as a conductive path inside the wiring layer laminate 10. The width of the copper wiring 13 is substantially the same as the line width L of the groove portion 21a, and the distance between the adjacent copper wirings 13 is substantially the same as the space width S of the groove portion 21a. The copper wiring 14 is provided in the corresponding groove portion 22a as described above, and functions as a conductive path inside the wiring layer laminate 10. Therefore, the width of the copper wiring 14 is substantially the same as the line width of the groove 22a, and the distance between the adjacent copper wirings 14 is substantially the same as the space width of the groove 22a. The copper wiring 14 contains the same metal material as the copper wiring 13.

The barrier metal film 15 (first barrier metal film) is a metal film provided so as to partition the copper wiring 13 and the first organic insulating layer 21 (that is, the inner surface of the groove portion 21a). The first barrier metal film 15 is a film for preventing the diffusion of copper from the copper wiring 13 to the first organic insulating layer 21, and is formed along the inner surface of the groove portion 21a. Therefore, the first barrier metal film 15 contains a metal material (for example, titanium, chromium, tungsten, palladium, nickel, gold, tantalum, or an alloy containing these) that is difficult to diffuse into the organic insulating layer.

The thickness of the first barrier metal film 15 is less than half the width of the groove 21a and less than the depth of the groove 21a. The thickness of the first barrier metal film 15 may be, for example, 0.001 to 0.5 μm from the viewpoint of preventing continuity between the copper wirings 13 and suppressing an increase in the resistance of the copper wirings 13.

The second barrier metal film 16 is a metal film provided so as to partition the copper wiring 14 and the second organic insulating layer 22 (that is, the inner surface of the groove portion 22a). The second barrier metal film 16 is a film for preventing the diffusion of copper from the copper wiring 14 to the second organic insulating layer 22, and is formed along the inner surface of the groove portion 22a. Therefore, the second barrier metal film 16 contains a metal material that does not easily diffuse into the organic insulating layer, like the first barrier metal film 15. The thickness of the second barrier metal film 16 is less than half the width of the groove 22a and less than the depth of the groove 22a, as in the case of the first barrier metal film 15, for example, at 0.001 to 0.5 μm. It may be there.

The first wiring interlayer insulating layer 17 is an insulating film for preventing the diffusion of copper from the copper wiring 13 to the first organic insulating layer 21 and the second organic insulating layer 22. The first wiring interlayer insulating layer 17 partitions the copper wiring 13 and the second organic insulating layer 22 between the wiring layer 41 (first wiring layer) and the wiring layer 42 (second wiring layer). It is provided as follows. The first wiring interlayer insulating layer 17 is in contact with the surface of the copper wiring 13 exposed on the main surface of the first wiring layer 41 opposite to the substrate 11. From the viewpoint that the wiring layer laminate 10 can be made thin, the thickness of the first wiring interlayer insulating layer 17 may be, for example, 50 μm or less.

The second wiring interlayer insulating layer 18 is an insulating film for preventing the diffusion of copper from the copper wiring 14 to the second organic insulating layer 22. The second wiring interlayer insulating layer 18 is provided on the second wiring layer 42 while being in contact with the surface of the copper wiring 14 exposed on the main surface of the second wiring layer 42 opposite to the substrate 11. .. The second wiring interlayer insulating layer 18 contains the same material as the first wiring interlayer insulating layer 17, and has the same characteristics as the first wiring interlayer insulating layer 17.

The through wiring 19 is wiring embedded in the wiring layers 41 and 42 and the via 31 penetrating the wiring interlayer insulating layers 17 and 18, and functions as a connection terminal to an external device.

As described above, the copper wiring in the semiconductor package may be formed by the trench method, or in another embodiment, it may be formed by SAP (Semi Additive Process). In any case, the above-mentioned photosensitive resin composition for forming a wiring interlayer insulating layer is suitably used for forming a wiring layer for a semiconductor.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the examples and comparative examples, the following components were used.
(A): Maleimide compound represented by the following formula as a bismaleimide-containing polymer (mixture of n = 1 to 10, weight average molecular weight: 1500 to 20000, HLB value: 4.4, manufactured by Hitachi Kasei Co., Ltd., trade name: SFR2300)

(A-1): Chemically modified saturated thermoplastic elastomer (HLB value: 0.55, manufactured by Asahi Kasei Corporation, trade name: Tough Tech M1911)
(A-2): Non-denatured saturated thermoplastic elastomer (HLB value: 0.60, manufactured by Asahi Kasei Corporation, trade name: Tough Tech H1041)
(B-1): 4- (1,1- (dimethylethyl) -2,6-bis (methoxymethyl) phenol (HLB value: 5.9, manufactured by Honshu Chemical Industry Co., Ltd., trade name: DMOM-PTBT)
(B-2): 2-Hydroxy-5- (1,1,3,3-tetramethylbutyl) -1,3-benzenedimethanol (HLB value: 9.8, manufactured by Honshu Chemical Industry Co., Ltd., trade name) : DML-POP)
(B-3): 3,3,5,5-tetrakis (methoxymethyl)-[1,1-biphenyl] -4,4-diol (HLB value: 7.8, manufactured by Honshu Chemical Industry Co., Ltd., trade name) : TMOM-BP)
(B-1): 2,2-bis (4-hydroxy-3,5-dihydroxy-methylphenyl) propane (HLB value: 16.6, manufactured by Asahi Organic Materials Co., Ltd., trade name: TM-BIP-A)
(B-2): Ditrimethylolpropane (HLB value: 17.5, manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: DI-TMP)
(B-3): Bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane (HLB value: 12.7, manufactured by Asahi Organic Materials Co., Ltd., trade name: DM-BIPC-F)
(C): Nadiimide compound represented by the following formula (3-1) (HLB value: 6.5, manufactured by Maruzen Petrochemical Co., Ltd., trade name: BANI-X)

(D): Photoacid generator (triarylsulfonium salt type, manufactured by San-Apro Co., Ltd., trade name: CPI-310B)

<Preparation of photosensitive resin varnish for forming wiring interlayer insulation layer>
Example 1
40 parts by mass of the above (A) as the component (A), 30 parts by mass of the above (B-1) as the component (B), 30 parts by mass of the above BANI-X as the component (C), and the above as the component (D). (D) was stirred and mixed in 5 parts by mass and 50 mL flasks, respectively, to obtain a photosensitive resin varnish for forming a wiring interlayer insulating layer.

Examples 2 and 3 and Comparative Examples 1 to 5
A resin varnish was obtained in the same manner as in Example 1 according to the compounding ratio (parts by mass) shown in Table 1.

<Evaluation of varnish compatibility>
After allowing the resin varnish to stand for 1 hour, the compatibility of the varnish was visually evaluated according to the following criteria. A had good compatibility.
A: There was no turbidity, phase separation, or precipitation.
B; Turbidity, phase separation, or precipitation occurred.

<Appearance evaluation after film formation>
The above resin varnish was spin-coated, dried and exposed on a peelable copper foil under the following conditions in order. Then, the appearance of the cured film was visually observed, and the one without turbidity and phase separation was evaluated as A, and the others were evaluated as B.

<Preparation of cured film>
The resin varnish produced above was spin-coated on a peelable copper foil under the same conditions as above, and then dried, exposed, and baked after exposure to form a resin film. By stacking this a plurality of times, a resin film having a thickness of 30 to 100 μm was obtained. Then, it was cured at 220 ° C. for 2 hours. Subsequently, the support copper foil (attached to the release layer) of the peelable copper foil was peeled off, and the remaining copper foil was dissolved and removed with ammonium persulfate to obtain an evaluation sample.
The conditions for spin coating, drying, exposure, and post-exposure baking were as follows.
-Spin coating conditions Step. 1: 400 rpm (rpm) / 5 seconds Step. 2: 800 rpm (rpm) / 30 seconds SLOPE: 5 seconds, drying conditions 90 ° C, 5 minutes 120 ° C, 5 minutes, exposure conditions Exposure: 200 mJ / cm ²
Broadband exposure / post-exposure bake 90 ° C, 5 minutes

<Evaluation of dielectric properties>
The dielectric properties (relative permittivity Dk and dielectric loss tangent Df) were measured by the SPDR method using an evaluation sample cut out to a predetermined size. An SPDR dielectric resonator manufactured by Agilent Technologies was used for the SPDR method, a vector network analyzer E8364B manufactured by Agilent Technologies was used for the measuring instrument, and CPMA-V2 was used for the measuring program. The conditions were a frequency of 10 GHz and a measurement temperature of 25 ° C.

<Evaluation of insulation reliability (b-HAST (Highly Accelerated Stress Test) resistance)>
The above varnish is applied by spin coating on the comb-shaped wiring produced by SAP (Semi Additive Process) or the trench method, and then dried, exposed and PEB (baked after exposure) for evaluation. A sample was prepared. The conditions for spin coating, drying, exposure, and post-exposure baking were the same as the conditions for the above-mentioned sample for evaluating dielectric properties (preparation of a cured film). Under the conditions of humidity of 85% and 130 ° C., the prepared comb-shaped wiring was allowed to stand with a voltage of 3.3 V applied. The resistance value between the anode and the cathode was measured at each scheduled time, and the resistance value was 1 × 10 ⁶ Ω or more for 300 hours or more. “A” (insulation reliability (b-HAST resistance)) ), And those that did not were evaluated as "B" (without insulation reliability (b-HAST resistance)).

<Measurement of glass transition temperature>
An evaluation sample prepared in the same manner as the sample for evaluating the dielectric property (preparation of the cured film) was cut out to a size of 8 mm × 30 mm. For this sample, a DMA (dynamic viscoelasticity measurement) device (manufactured by UBM Co., Ltd., trade name: Rheogel-E4000) was used, the distance between chucks was 20 mm, the frequency was 10 Hz, the temperature rise rate was 10 ° C./min, and the temperature range was -30. The temperature at which tan δ showed the maximum value measured by the tensile method under the condition of about 300 ° C. was recorded as the glass transition temperature (° C.).

<Measurement of coefficient of linear expansion>
An evaluation sample prepared in the same manner as the sample for evaluating dielectric properties (preparation of a cured film) was cut into a size of 4 mm × 30 mm, and a TMA (thermomechanical analysis) device (manufactured by Seiko Instruments Co., Ltd., trade name:) TMA / SS6000), with a load of 10 mN and the following temperature conditions, the coefficient of linear expansion α1 ( ^10-6 / K) at 50 to 70 ° C and the coefficient of linear expansion α2 (10) at 200 to 220 ° C by the tensile method. ^-6 / K) was measured.
・ Temperature condition 30 ℃ → 200 ℃ (heating rate 10 ℃ / min)
200 ° C → 30 ° C (temperature drop rate 20 ° C / min)
30 ° C → 260 ° C (heating rate 5 ° C / min)
260 ° C → 30 ° C (temperature drop rate 20 ° C / min)

<Sputter resistance>
The above varnish was applied by spin coating on a silicon wafer (6 inch diameter, thickness 400 μm) and dried by heating at 90 ° C. for 3 minutes to form a resin film on the silicon wafer. Exposure was performed at 1000 mJ / cm ² using a high-precision parallel exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name: EXM-1172-B-∞). Further, after additional heating was performed under the condition of 100 ° C./1 minute, further heating was performed at 220 ° C./2 hours to obtain a sample.
A titanium film of 50 nm was formed by sputtering on the resin film of the obtained sample, and then a copper film of 150 nm was formed by sputtering. After cooling, the sample was taken out and the presence or absence of cracks or wrinkles in the sputtered film was observed with a microscope. Those in which cracks or wrinkles were desired to be observed in the sputtered film were evaluated as "A" (with sputter resistance), and those in which cracks or wrinkles were observed were evaluated as "B" (without sputter resistance).

<Measurement of hygroscopicity>
The above varnish was applied to a wafer (6 inch diameter, thickness 400 μm) using a spin coater, and dried at 90 ° C./3 minutes to form a resin layer. A sample was prepared by exposing and curing at 1000 mJ / cm ² and then heating at 220 ° C./2 hours. This sample was allowed to stand for 200 hours in a constant temperature and humidity chamber (manufactured by ESPEC CORPORATION, trade name: EHS-221MD) set at a relative humidity of 85% and 130 ° C. Then, after the temperature inside the constant temperature and humidity chamber was lowered to 50 ° C., a sample was taken out and a part of the resin was scraped off from the silicon wafer. Using a differential thermogravimetric simultaneous measuring device (manufactured by Hitachi High-Tech Science Corporation, trade name: TG / DTA6300), a part of the scraped resin was heated at 10 ° C / min, nitrogen flow: 400 mL / min, Temperature range: Measured under the condition of 25 to 150 ° C. On the other hand, the similarly prepared sample was dried at 130 ° C. for 2 hours, and TG-DTA was measured by the same method. The difference in the weight loss rate at 150 ° C. was calculated as the hygroscopicity.

<Measurement of elongation>
The above varnish was spin-coated on a peelable core and dried. The next exposure was performed through a mask having a length of 30 mm and a width of 5 mm. The obtained sample was developed and then cured at 220 ° C. for 2 hours. After that, a resin film was obtained by etching the copper foil portion in the same manner as described above. The obtained sample was measured for breaking elongation when measured with a small tabletop tester (manufactured by Shimadzu Corporation, trade name: EZ-S) at a feed rate of 5 mm / min. Since the resin film produced by this method has smooth edges, a higher elongation rate can be obtained as compared with a sample cut out using a cutting tool such as a cutter.

<Evaluation of fine wiring formability>
A varnish was applied by spin coating on a silicon wafer (6 inch diameter, thickness 400 μm) and dried by heating at 90 ° C. for 3 minutes to form a resin film on the silicon wafer. At that time, the spin coating conditions were adjusted so that the film thickness of the resin after drying was 5 μm. Next, Line / Space (L / S (μm / μm)) is 200/200, 100/100, 80/80, 60/60, 50/50, 40/40, 30/30, 20/20, 10 A pattern mask for negative molds with via diameters of 50, 40, 30, 20, 10, 7, 5, 4, 3 μm at / 10, 7/7, 5/5, 4/4, and 3/3 is placed. Exposure was performed at 1000 mJ / cm ² using a high-precision parallel exposure machine (manufactured by ORC Manufacturing Co., Ltd., trade name: EXM-1172-B-∞). Further, additional heating was performed under the condition of 100 ° C./1/1 minute to obtain a sample. The obtained sample was immersed in cyclopentanone at room temperature (25 ° C.) for 60 seconds while shaking, then rinsed with cyclopentanone and then immersed in isopropyl alcohol at room temperature (25 ° C.) for 5 seconds. After that, isopropyl alcohol was volatilized by spraying compressed air.
The fine wiring formability was confirmed by a metallurgical microscope to see if the resin film was peeled off from the wafer, the resin film was cracked, the edge of the pattern was rough, and the bottom of the pattern was developed with resin. The minimum L / S and via diameter for which these defects could not be confirmed were defined as microfabrication.

The evaluation results of each characteristic described above are shown in Tables 1 and 2.

In the photosensitive resin composition for forming the wiring interlayer insulating layer of the present invention of Examples 1 to 3, the HLB of the components (A) to (C) is within the specified range, so that the compatibility of the varnish is good, and the film is formed. Later observation of the appearance of the cured film also showed a good appearance with no turbidity or phase separation. The obtained cured film has excellent dielectric properties and excellent insulation reliability. In addition, it has a high glass transition temperature, good heat resistance, spatter resistance, low hygroscopicity, excellent elongation, and excellent fine wiring formability.
On the other hand, in Comparative Examples 1 to 3 in which the HLB of the component (B) is larger than the specified range, and Comparative Examples 4 and 5 in which the HLB of the component (A) is smaller than the specified range and the HLB of the component (B) is larger than the specified range, the varnish is used. The compatibility of the cured film was poor, and turbidity and phase separation were observed in the appearance observation of the cured film after film formation.
By setting the HLB of the components (A) to (C) within the specified range, it is possible to provide a photosensitive resin composition for forming a wiring interlayer insulating layer, which has excellent compatibility and can form a film well, and use this. It is possible to provide a semiconductor wiring layer and a semiconductor wiring layer laminate having an insulating layer having excellent dielectric properties, heat resistant properties, insulating properties, and mechanical properties.

1 ... Substrate, 2A to 2D ... Semiconductor chip, 3A, 3B ... Underfill, 4 ... Insulating material, 10 ... Wiring layer laminate, 11 ... Substrate, 13 ... Copper wiring, 14 ... Copper wiring, 15, 16 ... Barrier metal Film, 17, 18 ... Wiring interlayer insulating layer, 21 ... Organic insulating layer, 21a ... Groove, 22 ... Organic insulating layer, 22a ... Groove, 100 ... Semiconductor package, L ... Line width, S ... Space width.

Claims (6)

A compound having at least one selected from the group consisting of (A) a bismaleimide-containing polymer, (B) an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having at least one of a methylol group and an alkoxyalkyl group, (C). It contains at least a nadiimide compound and (D) photoacid generator, and has an HLB value of (A) of 4.0 to 5.0, an HLB value of (B) of 4.0 to 10.0, and (C. ) Is a photosensitive resin composition for forming an interlayer insulating layer for wiring, which has an HLB value of 4.0 to 9.0. The photosensitive resin composition for forming a wiring interlayer insulating layer according to claim 1, wherein the (A) bismaleimide-containing polymer contains at least a resin represented by the following structural formula (I).

In the structural formula (I), Z ¹ and Z ² each independently represent a divalent hydrocarbon group, and R ⁵ represents a tetravalent organic group. n represents an integer of 1-10. When n is 2 or more, a plurality of Z ² may being the same or different. The wiring according to claim 1 or 2, wherein the cured product of the photosensitive resin composition for forming an interlayer insulating layer has a relative permittivity of 3.0 or less at 10 GHz. A photosensitive resin composition for forming an interlayer insulating layer. Any one of claims 1 to 3, wherein the cured product of the photosensitive resin composition for forming a wiring interlayer insulating layer according to any one of claims 1 to 3 has a dielectric loss tangent of 0.01 or less at 10 GHz. The photosensitive resin composition for forming a wiring interlayer insulating layer according to the above item. A wiring layer for a semiconductor containing a cured product of the photosensitive resin composition for forming a wiring interlayer insulating layer according to any one of claims 1 to 4. A semiconductor wiring layer laminate including the semiconductor wiring layer according to claim 5.