Resin composition and wiring layer laminate for semiconductor

Abstract

The invention relates to a resin composition and a semiconductor wiring layer laminate. A resin composition which is used to form a wiring interlayer insulating layer that is in contact with a fine copper wiring having a line width and an interval width of 5 [mu] m or less, contains a curable resin that is a maleimide compound having at least two maleimide groups and a divalent hydrocarbon group, a curing agent, and a coupling agent, does not contain an inorganic filler, and is used to form a wiring interlayer insulating layer that is in contact with the fine copper wiring having a line width and an interval width of 5 [mu] m or less. The maleimide compound is a compound represented by formula (VIII), the elongation at break of a cured product having a thickness of 300 [mu] m, which is obtained by curing the resin composition by heating at 180 DEG C for 2 hours, is 5-200%, and the moisture absorption rate of the cured product of the resin composition after being left to stand in an environment at 130 DEG C and a relative humidity of 85% for 200 hours is 1 mass% or less. The concentration of chloride ions in a cured product of the resin composition is 5 ppm or less.

Description

[0001] This application is a divisional application of Chinese patent application No. 201780059128.7, which entered the Chinese national phase on September 26, 2017, under the PCT / JP2017 / 034778 application date. Technical Field

[0002] This invention relates to resin compositions, wiring stacks for semiconductors, and semiconductor devices. Background Technology

[0003] To achieve high density and high performance in semiconductor packaging, an assembly configuration that integrates chips with different performance characteristics into a single package has been proposed. In this case, cost-effective and high-density interconnect technologies between chips become important (see, for example, Patent Document 1).

[0004] Non-patent literature 1 and non-patent literature 2 describe a type of stacked package (PoP) that connects different packages by layering them on top of each other using flip-chip assembly technology. This PoP is widely used in smartphones, tablet computers, and other similar devices.

[0005] Other forms of packaging for high-density assembly of multiple chips have been proposed, including packaging technologies using organic substrates with high-density wiring, fan-out-wafer level packaging (FO-WLP) with through-mold vias (TMV), packaging technologies using silicon or glass inserters, packaging technologies using through-silicon vias (TSV), and packaging technologies that use embedded chips in a substrate for chip-to-chip transfer.

[0006] Especially when semiconductor chips are mounted on a semiconductor wiring layer and FO-WLP, a fine wiring layer is required to enable high-density interconnection between the semiconductor chips (see, for example, Patent Document 2).

[0007] Existing technical documents

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Publication No. 2012-529770

[0010] Patent Document 2: U.S. Patent Application Publication No. 2011 / 0221071

[0011] Non-patent literature

[0012] Non-patent document 1: Jinseong Kim et al., "Application of Through Mold Via(TMV) as PoP Base Package", Electronic Components and Technology Conference (ECTC), p.1089-1092 (2008)

[0013] Non-patent literature 2: SWYoon et al., "Advanced Low Profile PoP Solution with Embedded Wafer Level PoP (eWLB-PoP) Technology", ECTC, p.1250-1254 (2012). Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] In stacked substrates, wafer-level packaging (WLP), and bottom-mounted fan-out PoP packages, wiring layers (semiconductor wiring layers) are sometimes used to mount multiple semiconductor chips. For example, when fine wirings with linewidths and spacing of less than 5 μm are arranged within this wiring layer, the wirings are formed using a trenching method. The trenching method refers to a method of forming a metal layer, which serves as the wiring, within a trench formed on the surface of an organic insulating layer using a laser or similar method, by a plating method. Therefore, the shape of the wiring formed on the organic insulating layer follows the shape of the trench.

[0016] When forming fine wiring within a wiring layer using the slotting method, copper, for example, with high conductivity, may be used to reduce costs and suppress the increase in wiring resistance. However, when copper wiring is formed, copper may diffuse into the organic insulation layer. In this case, the copper wires may short-circuit with each other due to the diffused copper, posing a problem with the insulation reliability of the wiring layer.

[0017] The object of the present invention is to provide a wiring interlayer insulation layer and a semiconductor device with good insulation reliability, as well as a resin composition suitable for forming the wiring interlayer insulation layer.

[0018] Methods for solving problems

[0019] One aspect of the present invention relates to a resin composition comprising a curable resin and a curing agent, which is used to form an interlayer insulation layer in contact with copper wiring. When the interlayer insulation layer formed by this resin composition is located between adjacent copper wirings, the diffusion of copper from the copper wirings into the wiring laminate can be suppressed. Therefore, short circuits between the copper wirings caused by diffused copper are suppressed, resulting in a significant improvement in the insulation reliability of the wiring laminate.

[0020] The curable resin may have at least two maleimide groups and a divalent hydrocarbon group. The hydrocarbon group may contain a chain-like alkylene group with a main chain having four or more carbon atoms. The hydrocarbon group may have eight or more carbon atoms. The curable resin may contain a divalent organic group having at least two imide bonds. The divalent organic group may be a group represented by the following formula (I).

[0021]

[0022] Where R 1 It represents a tetravalent organic group.

[0023] The hydrocarbon group can be a group represented by the following formula (II).

[0024]

[0025] Where R 2 and R 3 Each independently represents an alkylene group, R 4 and R 5 Alkyl groups are represented independently.

[0026] The curing agent may contain a photoradical polymerization initiator. The resin composition may further contain a compound having a (meth)acryloyl group, and may also contain a coupling agent.

[0027] The resin composition may further contain a thermoplastic resin. The concentration of chloride ions in the cured resin composition may be less than 5 ppm. The elongation at break of the cured resin composition may be 5–200%. The storage modulus of the cured resin composition at 40°C may be 10 MPa–5 GPa. The glass transition temperature of the cured resin composition may be 120–240°C. The dielectric constant of the cured resin composition at 10 GHz may be less than 3.0. The dielectric loss tangent of the cured resin composition at 10 GHz may be less than 0.005. The 5% weight loss temperature of the cured resin composition may be 300°C or higher.

[0028] The cured resin composition has a moisture absorption rate of less than 1% by mass after being placed in an environment of 130°C and 85% relative humidity for 200 hours.

[0029] Another aspect of the present invention relates to a wiring layer stack for semiconductors, comprising: a plurality of wiring layers, the plurality of wiring layers including an organic insulating layer, copper wiring disposed within the organic insulating layer, and a barrier metal film separating the copper wiring and the organic insulating layer; and a wiring layer interlayer insulating layer disposed between the plurality of wiring layers, wherein a portion of the surface of the copper wiring is exposed on one or two main surfaces of the wiring layers, the wiring layer interlayer insulating layer is in contact with the exposed surface of the copper wiring, and the wiring layer interlayer insulating layer is a layer with a moisture absorption rate of less than 1% by mass after being placed in an environment of 130°C and 85% relative humidity for 200 hours.

[0030] The interlayer insulation layer can be a cured product of the above-described resin composition. The organic insulation layer can be a layer formed from a photosensitive insulating resin. The barrier metal film can contain at least one selected from titanium, nickel, palladium, chromium, tantalum, tungsten, and gold. The dielectric constant of the interlayer insulation layer at 10 GHz can be 3.0 or less. The dielectric loss tangent of the interlayer insulation layer at 10 GHz can be 0.005 or less. The 5% weight reduction temperature of the interlayer insulation layer can be 300°C or higher.

[0031] Another aspect of the present invention relates to a semiconductor device comprising: the aforementioned semiconductor wiring layer laminate; and a semiconductor element electrically connected to a copper wiring layer.

[0032] Invention Effects

[0033] According to the present invention, a wiring interlayer insulation layer and a semiconductor device having good insulation reliability can be provided, as well as a resin composition suitable for forming the wiring interlayer insulation layer. Attached Figure Description

[0034] Figure 1 This is a schematic cross-sectional view of a semiconductor device having one embodiment of a semiconductor wiring layer stack.

[0035] Figure 2 This is a schematic cross-sectional view of a semiconductor wiring layer stack according to one embodiment.

[0036] Figure 3 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0037] Figure 4 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0038] Figure 5 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0039] Figure 6 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0040] Figure 7 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0041] Figure 8 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0042] Figure 9 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0043] Figure 10 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0044] Figure 11 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0045] Figure 12 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0046] Figure 13 This diagram illustrates the manufacturing method of a wiring layer laminate for semiconductors.

[0047] Figure 14 (a) is a plan view showing the specimen used for the determination and evaluation. Figure 14 (b) is along Figure 14 (a) Cross-sectional view of line XIVb-XIVb.

[0048] Figure 15 This is a graph showing the results of the high acceleration life test for Example 3 and Comparative Example 2.

[0049] Figure 16 (a) is a general view photograph showing the results of the high-acceleration life test in Example 3. Figure 16 (b) is a panoramic photograph showing the high acceleration life test results of Comparative Example 2. Detailed Implementation

[0050] Hereinafter, this embodiment will be described in detail with reference to the accompanying drawings. In the following description, identical or equivalent parts are indicated by the same symbols, and repeated descriptions are omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right are based on the positional relationships shown in the accompanying drawings. Additionally, the scale of the accompanying drawings is not limited to the scale shown.

[0051] In the description and claims of this specification, the terms "left," "right," "front," "back," "upper," "lower," "above," "below," "first," and "second," etc., are used for illustrative purposes and do not imply that these relative positions are permanent. Furthermore, when viewed in a planar view, "layer" and "film" include not only structures formed entirely but also structures formed partially. Additionally, the term "process" includes not only independent processes but also processes that, when clearly distinguishable from others, achieve the desired purpose of that process. Furthermore, the numerical range indicated by "~" represents a range in which the values ​​described before and after "~" are respectively the minimum and maximum values. Additionally, in the numerical ranges described in stages in this specification, the upper or lower limit of the numerical range of one stage can be replaced by the upper or lower limit of the numerical range of another stage.

[0052] One embodiment of the resin composition comprises a curable resin and a curing agent. The curable resin is a compound that cures using heat or light. That is, the resin composition is a photocurable (photosensitive) resin composition that cures using light, or a thermocurable resin composition that cures using heat. This resin composition can be suitably used to form an interlayer insulation layer in contact with copper wiring. In this specification, copper wiring refers to wiring containing at least copper. Copper wiring can be wiring composed solely of copper, or it can be wiring containing other components besides copper, such as nickel, titanium, palladium, etc.

[0053] In one embodiment (hereinafter referred to as "the first embodiment"), the curable resin is a maleimide compound having at least two maleimide groups and a divalent hydrocarbon group (hereinafter also referred to simply as "maleimide compound").

[0054] Maleimide compounds, for example, have at least two maleimide groups represented by the following formula (III).

[0055]

[0056] Maleimide compounds, for example, are compounds represented by the following formula (IV) (bismaleimide compounds).

[0057]

[0058] In the formula, X is a divalent ligand containing a divalent hydrocarbon group.

[0059] The divalent hydrocarbon group contained in the linker group represented by X can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. The divalent hydrocarbon group can be either chain-like or cyclic, and the chain-like divalent hydrocarbon group can be either straight-chain or branched. The cyclic unsaturated hydrocarbon group can also be an aromatic group. The divalent hydrocarbon group can also contain more than two of the above-mentioned groups.

[0060] From the viewpoint of improving the plasticity of the resin composition and the handling properties (adhesion, cracking, powdering, etc.) and strength of the film made from the resin composition, the divalent hydrocarbon group preferably contains a chain hydrocarbon group, and more preferably contains a chain alkylene group having a main chain having 4 or more carbon atoms.

[0061] Alkyl groups with a main chain having 4 or more carbon atoms are composed of -(CR a R b ) m - indicates (m represents an integer greater than 4, R) a and R b Each alkyl group can be represented independently by a hydrogen atom or an alkyl group with a carbon number less than m. The carbon number (m) of the main chain of the alkylene group is preferably 4 or more, or 6 or more, and more preferably 20 or less, 15 or less, or 10 or less.

[0062] From the viewpoint that it is easy to make the molecular structure of maleimide compounds three-dimensional, thereby increasing the free volume of the polymer and thus reducing density, i.e., reducing dielectric constant, the number of carbons in the divalent hydrocarbon group is preferably 8 or more, 10 or more, or 15 or more, and preferably 300 or less, 250 or less, 200 or less, 100 or less, 70 or less, or 50 or less. From the same viewpoint, the number of carbons in the divalent hydrocarbon group can preferably be 8 to 300, 8 to 250, 8 to 200, or 8 to 100. The divalent hydrocarbon group is preferably a branched alkylene group with 8 to 300, 8 to 250, 8 to 200, or 8 to 100 carbons, more preferably a branched alkylene group with 10 to 70 carbons, and even more preferably a branched alkylene group with 15 to 50 carbons.

[0063] From the viewpoint of more effectively improving high-frequency characteristics and resistance to HAST (Highly Accelerated Temperature and Humidity Stress Test), the divalent hydrocarbon group in one embodiment is a group represented by the following formula (II).

[0064]

[0065] Where R 2 and R 3 Each independently represents an alkylene group, R 4 and R 5 Alkyl groups are represented independently.

[0066] From the perspective of further improving flexibility and ease of synthesis, by R 2 and R 3 The alkylene group represented preferably has 4 to 50 carbon atoms, more preferably 5 to 25, further preferably 6 to 10, and particularly preferably 7 to 10. (From R) 2 and R 3 The alkylene group represented is preferably a chain-like alkylene group having a main chain with 4 or more carbon atoms, as described above.

[0067] From the perspective of further improving flexibility and ease of synthesis, by R 4 The alkyl group represented preferably has 4 to 50 carbon atoms, more preferably 5 to 25, further preferably 6 to 10, and particularly preferably 7 to 10. From the viewpoint of further improving flexibility and ease of synthesis, R 5 The alkylene group represented preferably has 2 to 50 carbon atoms, more preferably 3 to 25, further preferably 4 to 10, and particularly preferably 5 to 8.

[0068] From the viewpoint of more effectively improving high-frequency properties and elongation, maleimide compounds preferably have multiple divalent hydrocarbon groups. In this case, the multiple divalent hydrocarbon groups may be the same or different from each other. Maleimide compounds preferably have 2 to 40 divalent hydrocarbon groups, more preferably 2 to 20, and even more preferably 2 to 10.

[0069] Divalent hydrocarbon groups can be, for example, nonylene, decylene, undecylene, dodecylene, tetradecylene, hexadecylene, octadecylene, nonadecanylene, eicosylene, icosylene, icosylene, icosylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, icosylene, nonadecanylene, triacontylene, etc.; benzylene, phenylene, naphthylene, etc.; phenylenemethylene, phenyleneethylene, benzylpropylidene, naphthylmethylene, naphthylethylene, etc.; phenylenedimethylene, phenylenediethylene, etc., etc.

[0070] The linker group represented by X may consist solely of the aforementioned divalent hydrocarbon groups, or it may contain other organic groups in addition to the aforementioned divalent hydrocarbon groups. Other organic groups may be, for example, divalent organic groups having at least two imide bonds.

[0071] A divalent organic group having at least two imide bonds can be, for example, a group represented by the following formula (I).

[0072]

[0073] Where R 1It represents a tetravalent organic group.

[0074] By R 1 The tetravalent organic group represented can be a hydrocarbon group, for example, from an operational handling point of view. The number of carbon atoms in this hydrocarbon group can be, for example, 1 to 100, 2 to 50, or 4 to 30.

[0075] The hydrocarbon group can also be substituted, for example, it can contain substituted or unsubstituted siloxane groups. Examples of siloxane groups include those derived from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc.

[0076] Substituents can be, for example, alkyl, alkenyl, alkynyl, hydroxyl, alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic, substituted heterocyclic, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, substituted aryloxy, halogen atom, haloalkyl, cyano, nitro, nitroso, amino, amide, -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. Acyl, oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide, thioacyl, etc. Here, R... c This indicates a hydrogen atom or an alkyl group. One or more of these substituents can be selected depending on the purpose, application, etc.

[0077] By R 1 The tetravalent organic group can be, for example, a tetravalent residue of an anhydride having two or more anhydride rings in one molecule, that is, a tetravalent group obtained by removing two anhydride groups (-CO(=O)OC(=O)-) from an anhydride. Examples of anhydrides include compounds described later.

[0078] From the perspective of excellent high-frequency characteristics, R 1 The organic group represented is preferably a tetravalent aromatic group, more preferably a residue obtained by removing two anhydride groups from pyromellitic anhydride. A divalent organic group having at least two imide bonds is preferably a group represented by the following formula (V).

[0079]

[0080] From the viewpoint of excellent medium properties, a divalent organic group having at least two imide bonds can be a group represented by the following formula (VI) or (VII).

[0081]

[0082] From the viewpoint of excellent high-frequency properties and good compatibility with other resins when the resin composition further contains other resins (especially high molecular weight thermoplastic elastomer resins), the maleimide compound preferably contains a plurality of divalent organic groups having at least two imide bonds. In this case, the plurality of divalent organic groups may be the same or different from each other. The maleimide compound preferably has 2 to 40, more preferably 2 to 20, and even more preferably 2 to 10 of these divalent organic groups.

[0083] More specifically, in one embodiment, the maleimide compound may be, for example, a compound represented by formula (VIII) below, or a compound represented by formula (IX) below.

[0084]

[0085] In the formula, Z 1 Z 2 and Z 3 Each of the above divalent hydrocarbon groups can be represented independently, R 1 The definition is the same as R1 in equation (I), where n represents an integer from 1 to 10. When n is 2 or more, multiple Z 3 They can be the same or different.

[0086] Maleimide compounds can be purchased and used, for example, from commercially available products. Examples of commercially available products include, for example, maleimide compounds represented by formula (VIII) such as BMI-TMH, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5100, BMI-7000, BMI-7000H (all trade names, manufactured by Yamato Chemical Co., Ltd.), BMI, BMI-70, and BMI-80 (all trade names, manufactured by Ki-Chemical Co., Ltd.). Commercially available products include, for example, maleimide compounds represented by formula (IX), such as BMI-1500, BMI-1700, BMI-3000, BMI-5000 and BMI-9000 (all trade names, manufactured by DesignerMolecules Inc. (DMI)).

[0087] The molecular weight of the maleimide compound is not particularly limited. The weight-average molecular weight (Mw) of the maleimide compound can be 1000 or more, 1500 or more, or 3000 or more, or 30000 or less, 20000 or less, or 15000 or less. From the viewpoint of solubility in solvents and compatibility with monomers, resins, and other components, the weight-average molecular weight (Mw) of the maleimide compound is preferably 1000 to 30000, more preferably 1500 to 20000.

[0088] The weight-average molecular weight (Mw) of maleimide compounds can be determined using gel permeation chromatography (GPC). The determination conditions for GPC are as follows.

[0089] Pump: L-6200 type [Manufactured by Hitachi High-Technologies Co., Ltd.]

[0090] Detector: L-3300 RI [Manufactured by Hitachi High-Technologies Co., Ltd.]

[0091] Column-type heating furnace: L-655A-52 [Manufactured by Hitachi High-Technologies Co., Ltd.]

[0092] Guard column and chromatographic column: TSK Guardcolumn HHR-L + TSKgel G4000HHR + TSKgel G2000HHR [all manufactured by Tosoh Corporation, trade names]

[0093] Column sizes: 6.0×40mm (guard column), 7.8×300mm (column)

[0094] Eluent: Tetrahydrofuran

[0095] Sample concentration: 30 mg / 5 mL

[0096] Injection volume: 20μL

[0097] Measurement temperature: 40℃

[0098] The content of maleimide compounds is based on the total amount of solid components in the resin composition. For example, it can be 50% or more by mass, 65% or more by mass, or 80% or more by mass, or less than 99% by mass, 95% or less by mass, or less than 90% by mass.

[0099] The curing agent of the first embodiment may also contain a photoradical polymerization initiator. That is, in one embodiment, the resin composition contains a maleimide compound and a photoradical polymerization initiator.

[0100] Photoradical polymerization initiators can be, for example, alkyl phenyl ketone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, etc.

[0101] Alkyl phenyl ketone-based photoradical polymerization initiators can be, for example, Irgacure 651, Irgacure 184, DAROCURE 1173, Irgacure 2959, Irgacure 127, DAROCURE MBF, Irgacure 907, Irgacure 369, and Irgacure 379EG, all manufactured by BASF. Acylphosphine oxide-based photoradical polymerization initiators can be, for example, Irgacure 819 and LUCIRIN TPO, both manufactured by BASF.

[0102] The photoradical polymerization initiator can also be other photoradical polymerization initiators such as Irgacure 784, Irgacure OXE01, Irgacure OXE02, and Irgacure 754, which are manufactured by BASF.

[0103] As photoradical polymerization initiators, from the viewpoint of high sensitivity, Irgacure 907, Irgacure 369, Irgacure 379EG, Irgacure OXE01, and Irgacure OXE02 are preferred; from the viewpoint of solvent solubility, Irgacure 907, Irgacure 379EG, and Irgacure OXE02 are more preferred. These photoradical polymerization initiators can be used individually or in combination, depending on the purpose and application.

[0104] From the viewpoint of enabling the curable resin to fully cure, the content of the photoradical polymerization initiator is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the curable resin, and more preferably 1 to 6 parts by mass from the viewpoint that unreacted substances are not easily retained.

[0105] The resin composition of the first embodiment may further contain a compound having a (meth)acrylyl group (hereinafter also referred to as "(meth)acrylyl compound"). That is, in one embodiment, the resin composition contains a maleimide compound, a (meth)acrylyl compound, and a curing agent (photoradical polymerization initiator). Furthermore, the coupling agent having a (meth)acrylyl group described later is not included within the (meth)acrylyl compound.

[0106] (Meth)acryloyl compounds can be, for example, tricyclodecanediethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A (meth)acrylate, dipentaerythritol poly(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, polyethylene glycol di(meth)acrylate, sesquioxane derivatives having (meth)acryloyl groups, etc.

[0107] From the viewpoint of excellent heat resistance, the (meth)acryloyl compound is preferably tricyclodecanediethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A (meth)acrylate, or a sesquioxane derivative having a (meth)acryloyl group. From the viewpoint of excellent compatibility with maleimide compounds, tricyclodecanediethanol di(meth)acrylate is more preferably used.

[0108] When the total amount of maleimide compound and (meth)acryloyl compound is set to 100 parts by mass, the content of (meth)acryloyl compound is preferably 0.1 to 98 parts by mass, more preferably 2 to 50 parts by mass from the viewpoint of obtaining good elongation, and more preferably 5 to 40 parts by mass from the viewpoint of being able to balance high frequency and fine wiring formation.

[0109] The resin composition of the first embodiment may further contain a coupling agent. That is, in one embodiment, the resin composition contains a maleimide compound, a curing agent (photoradical polymerization initiator), and a coupling agent, and in another embodiment, it contains a maleimide compound, a (meth)acryloyl compound, a curing agent (photoradical polymerization initiator), and a coupling agent.

[0110] The coupling agent can be, for example, a silane coupling agent. Silane coupling agents can have, for example, vinyl, epoxy, styrene, acryloyl, methacryloyl, amino, urea, isocyanate, isocyanurate, mercapto, etc.

[0111] Examples of vinyl-containing silane coupling agents include KBM-1003 and KBE-1003 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd. The same applies hereinafter). Examples of epoxy-containing silane coupling agents include KBM-303, 402, 403, KBE-402, 403, X-12-981S, and X-12-984S. Examples of styrene-containing silane coupling agents include KBM-1403. Examples of methacrylyl-containing silane coupling agents include KBM-502, 503, KBE-502, and 503. Examples of acryloyl-containing silane coupling agents include KBM-5103, X-12-1048, and X-12-1050. Examples of silane coupling agents containing amino groups include KBM-602, 603, 903, 573, 575, KBE-903, 9103P, and X-12-972F. Examples of silane coupling agents containing urea groups include KBE-585. Examples of silane coupling agents containing isocyanate groups include KBE-9007 and X-12-1159L. Examples of silane coupling agents containing isocyanurate groups include KBM-9659. Examples of silane coupling agents containing mercapto groups include KBM-802, 803, X-12-1154, and X-12-1156. Depending on the purpose and application, one or more of these agents may be used individually or in combination.

[0112] From the viewpoint of improving adhesion to glass, silica, etc., the content of silane coupling agent is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the curable resin, and more preferably 0.1 to 2 parts by mass from the viewpoint of minimizing the presence of unreacted residues.

[0113] In the resin composition of the first embodiment, in addition to the maleimide compound, a thermosetting resin may be further included as the curing resin. Examples of thermosetting resins include epoxy resins, phenolic resins, cyanate ester resins, isocyanate ester resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, siloxane resins, triazine resins, and melamine resins. One of these resins may be used alone, or two or more may be used in combination. From the viewpoint of heat resistance and electrical insulation, the thermosetting resin is preferably an epoxy resin or a cyanate ester resin.

[0114] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, bisphenol A phenolic varnish type epoxy resin, bisphenol F phenolic varnish type epoxy resin, iridium type epoxy resin, epoxy resin containing a triazine skeleton, epoxy resin containing a fluorene skeleton, biphenyl type epoxy resin, xylene-type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, diglycidyl ether compounds of polycyclic aromatic compounds such as polyfunctional phenols and anthracene, and phosphorus-containing epoxy resins in which phosphorus compounds have been introduced. From the viewpoint of heat resistance and flame retardancy, biphenyl aralkyl type epoxy resin or naphthalene type epoxy resin is preferred. One type can be used alone, or two or more types can be used in combination.

[0115] Examples of cyanate ester resins include bisphenol-type cyanate ester resins such as phenolic varnish-type cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol E-type cyanate ester resins, and tetramethylbisphenol F-type cyanate ester resins, as well as prepolymers obtained by partially triazinizing them. They can be used alone or in combination of two or more. From the viewpoint of heat resistance and flame retardancy, phenolic varnish-type cyanate ester resins are preferred.

[0116] In the resin composition of the first embodiment, in addition to the photoradical polymerization initiator, other curing agents may be included as curing agents. Examples of other curing agents include aromatic amine compounds such as dicyandiamide, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl sulfone, phenylene diamine, and xylene diamine; aliphatic amine compounds such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine; and guanidine compounds such as melamine and benzoguanidine. From the viewpoint of obtaining good reactivity and heat resistance, aromatic amine compounds are preferred as other curing agents.

[0117] When the resin composition contains a cyanate ester resin, the resin composition may further contain, as a curing agent, polyfunctional phenolic compounds such as phenolic resin, cresol phenolic resin, and aminotriazine phenolic resin, as well as acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymers. These may be used alone or in combination of two or more.

[0118] The resin composition of the first embodiment may further contain a thermoplastic elastomer. Examples of thermoplastic elastomers include styrene-based elastomers, olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, siloxane-based elastomers, and their derivatives. Thermoplastic elastomers consist of hard segment components and soft segment components; generally, the former is beneficial for heat resistance and strength, while the latter is beneficial for flexibility and toughness. From the viewpoint of further improving heat resistance and insulation reliability, the thermoplastic elastomer is preferably a styrene-based elastomer, an olefin-based elastomer, a polyamide-based elastomer, or a siloxane-based elastomer. One type may be used alone, or two or more may be used in combination.

[0119] Thermoplastic elastomers with reactive functional groups at the molecular ends or in the molecular chain can be used as thermoplastic elastomers. Examples of reactive functional groups include epoxy, hydroxyl, carboxyl, amino, amide, isocyanate, acryloyl, methacryloyl, and vinyl groups. By having these reactive functional groups at the molecular ends or in the molecular chain, the thermoplastic elastomer improves its compatibility with curable resins, more effectively reducing internal stress during the curing of the resin composition, and consequently significantly reducing substrate warpage. From the viewpoint of adhesion to metals, the reactive functional group is preferably epoxy, hydroxyl, carboxyl, amino, or amide; from the viewpoint of further improving heat resistance and insulation reliability, epoxy, hydroxyl, or amino groups are more preferred.

[0120] From the viewpoint of effectively utilizing the low shrinkage and low thermal expansion of the cured product, the content of thermoplastic elastomer is preferably 0.1 to 50 parts by mass, more preferably 2 to 30 parts by mass, relative to 100 parts by mass of the total solid components in the resin composition.

[0121] In one embodiment (hereinafter also referred to as "the second embodiment"), the resin composition contains a thermoplastic resin in addition to a curable resin and a curing agent. In this case, the curable resin is preferably a thermoplastic resin. That is, the resin composition of the second embodiment contains a thermoplastic resin, a thermoplastic resin, and a curing agent.

[0122] Thermoplastic resins are any resins that can be softened by heating; there are no particular limitations. Thermoplastic resins may have reactive functional groups at the ends of the molecules or in the molecular chains. Examples of reactive functional groups include epoxy, hydroxyl, carboxyl, amino, amide, isocyanate, acryloyl, methacryloyl, vinyl, and maleic anhydride groups.

[0123] From the viewpoint of suppressing moisture absorption and dielectric constant, thermoplastic resins contain, for example, resins with siloxane chains. Examples of thermoplastic resins containing siloxanes include, for instance, acrylic resins containing siloxanes, polyamide resins containing siloxanes, polyimides containing siloxanes, polyurethanes containing siloxanes, siloxane-modified acrylates, siloxane-modified epoxy resins, siloxane resins, or siloxane diamines. From the viewpoint of suppressing gas escaping during heating and improving the heat resistance and adhesion of the interlayer insulation layer, thermoplastic resins with siloxane chains are preferably polyimides (polyimides containing siloxanes).

[0124] Polyimides containing siloxanes can be synthesized, for example, by reacting siloxane diamine with tetracarboxylic dianhydride, or by reacting siloxane diamine with bismaleimide.

[0125] The siloxane diamine preferably contains the structure represented by the following formula (5).

[0126]

[0127] In the formula, Q 4 and Q 9 Each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group that may have substituents, Q 5 Q 6 Q 7 and Q 8 Each of the following can be used to independently represent an alkyl, phenyl, or phenoxy group with 1 to 5 carbon atoms, where d represents an integer from 1 to 5.

[0128] Examples of siloxane diamines with d=1 in formula (5) include 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis(4-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminobutyl)disiloxane, and 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-aminobutyl)disiloxane.

[0129] Examples of siloxane diamines with d=2 in formula (5) include 1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, and 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane. 5-bis(2-aminoethyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis(3-aminopropyl)trisiloxane, etc.

[0130] Commercially available siloxane diamines include, for example, those with amino groups at both ends: "PAM-E" (amino equivalent: 130 g / mol), "KF-8010" (amino equivalent: 430 g / mol), "X-22-161A" (amino equivalent: 800 g / mol), "X-22-161B" (amino equivalent: 1500 g / mol), "KF-8012" (amino equivalent: 2200 g / mol), and "KF-8008" (amino equivalent: 5700 g / mol). The following are examples of siloxane diamines: "X-22-9409" (amino equivalent: 700 g / mol, side-chain phenyl type), "X-22-1660B-3" (amino equivalent: 2200 g / mol, side-chain phenyl type) (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "BY-16-853U" (amino equivalent: 460 g / mol), "BY-16-853" (amino equivalent: 650 g / mol), and "BY-16-853B" (amino equivalent: 2200 g / mol) (manufactured by Toray Dow Corning Co., Ltd.). These siloxane diamines can be used alone or in combination of two or more types. From the viewpoint of reactivity with maleimide groups, at least one of "PAM-E", "KF-8010", "X-22-161A", "X-22-161B", "BY-16-853U", and "BY-16-853" is preferred. From the viewpoint of media properties, at least one of "PAM-E", "KF-8010", "X-22-161A", "BY-16-853U", and "BY-16-853" is more preferred. From the viewpoint of varnish compatibility, at least one of "KF-8010", "X-22-161A", and "BY-16-853" is preferred.

[0131] The content of siloxane in polyimide containing siloxane is not particularly limited, but from the viewpoint of reactivity and compatibility, it is, for example, 5 to 50% by mass relative to the total mass of polyimide; from the viewpoint of heat resistance, it is preferably 5 to 30% by mass; and from the viewpoint of further reducing the moisture absorption rate of the interlayer insulation layer, it is more preferably 10 to 30% by mass.

[0132] There are no particular restrictions on other diamine components used as raw materials for polyimide. Examples include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoro ...phenyldiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, bis(4-amino-3,5-difluoromethane), bis(4-amino-3,5-diisopropylphenyl)methane, bis(4-amino-3,5-difluoromethane), bis(4-amino-3,5-diphenyl)fluoromethane, bis(4-amino-3,5-diphenyl)fluoromethane, bis(4-amino-3,5-diphenyl)fluoromethane, bis(4-amino-3,5-diphenyl)fluoromethane, bis(4-amino-3,5 -Diaminodiphenyldifluoromethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4'- Diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-phenylenebis(1-methylethoxy))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethoxy))bisaniline, 4,4'-(1,4-phenylenebis(1-methylethoxy))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-) (4-aminophenoxy)phenyl)hexafluoropropane, bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid and other aromatic diamines, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, aliphatic ether diamines represented by the following formula (4), aliphatic diamines represented by the following formula (11), diamines having a carboxyl group and / or a hydroxyl group in the molecule, etc.

[0133]

[0134] In the formula, Q 1 Q 2 and Q 3Each of the following can be used to independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer from 2 to 80.

[0135]

[0136] In the formula, c represents an integer from 5 to 20.

[0137] Examples of aliphatic ether diamines represented by formula (4) include aliphatic diamines represented by the following formula and aliphatic ether diamines represented by the following formula (12).

[0138] [Chemical Formula Number 15]

[0139]

[0140] In the formula, n represents an integer greater than or equal to 1.

[0141]

[0142] In the formula, e represents an integer from 0 to 80.

[0143] Specific examples of aliphatic diamines represented by formula (11) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane.

[0144] The diamine components mentioned above can be used alone or in combination of two or more.

[0145] As a raw material for polyimide, tetracarboxylic acid dianhydride can be used, for example. There are no particular limitations on the acid anhydride used; examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfonic acid dianhydride, 3,4,9,10-dinaphthalene-impregnated tetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, and benzene-1,2,3,4-tetracarboxylic acid dianhydride. Acid dianhydride, 3,4,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 3,3,3',4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3 3,4'-Biphenyltetracarboxylic acid dianhydride, 3,4,3',4'-Biphenyltetracarboxylic acid dianhydride, 2,3,2',3'-Biphenyltetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, bis(3,4-dicarboxyphenyl)methylphenylsilane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, 1,4-bis(3,4-dicarboxyphenyl dimethylsilyl)phenyl dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis(triphenylene trioxide), ethylenetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3 5,6,7-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis(oxo-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride, bicyclo-[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-Dicarboxyphenoxy)diphenylsulfide dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenebis(triphenyltrihydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenebis(triphenyltrihydride), 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, and tetracarboxylic acid dianhydrides represented by the following formula (7), etc.

[0146]

[0147] In the formula, a represents an integer from 2 to 20.

[0148] The tetracarboxylic acid dianhydride represented by formula (7) can be synthesized, for example, from trimellitic anhydride monoacyl chloride and the corresponding diol. Specific examples of tetracarboxylic acid dianhydrides represented by formula (7) include 1,2-(ethylene)bis(triphenyltrihydride), 1,3-(trimethylene)bis(triphenyltrihydride), 1,4-(tetramethylene)bis(triphenyltrihydride), 1,5-(pentamethylene)bis(triphenyltrihydride), 1,6-(hexamethylene)bis(triphenyltrihydride), 1,7-(heptamethylene)bis(triphenyltrihydride), 1,8-(octamethylene)bis(triphenyltrihydride), 1,9-(nonamethylene)bis(triphenyltrihydride), 1,10-(decamethylene)bis(triphenyltrihydride), 1,12-(dodecamethylene)bis(triphenyltrihydride), 1,16-(hexadecamethylene)bis(triphenyltrihydride), and 1,18-(octadecamethylene)bis(triphenyltrihydride).

[0149] From the viewpoint of imparting good solubility and moisture resistance to the solvent in the resin composition, the tetracarboxylic dianhydride may contain a tetracarboxylic dianhydride represented by the following formula (6) or (8).

[0150]

[0151] The above-mentioned tetracarboxylic acid dianhydrides can be used alone or in combination of two or more.

[0152] As a raw material for polyimide, bismaleimide can be used, for example. There are no particular limitations on bismaleimide; examples include bis(4-maleimidephenyl)methane, polyphenylmethane maleimide, bis(4-maleimidephenyl) ether, bis(4-maleimidephenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, etc.

[0153] The bismaleimides described above can be used alone or in combination of two or more. From the viewpoint of high reactivity and the ability to further improve media properties and wiring characteristics, the bismaleimide is preferably at least one of bis(4-maleimidephenyl)methane, bis(4-maleimidephenyl)sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, and 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane. From the viewpoint of solubility in solvents, the bismaleimide is preferably at least one of 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis(4-maleimidephenyl)methane, and 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane. From the viewpoint of low cost, the bismaleimide is preferably bis(4-maleimidephenyl)methane. From a wiring perspective, bismaleimide is preferably 2,2-bis(4-(4-maleimide phenoxy)phenyl)propane, or “BMI-3000” (trade name) manufactured by DesignerMolecules Inc.

[0154] The content of thermoplastic resin can be 10% to 70% by mass, based on the mass of the resin composition (excluding fillers).

[0155] Thermosetting resins are any thermosetting resins that can be cured by reacting with a curing agent through heating; there are no particular limitations. Thermosetting resins may have reactive functional groups at the ends of the molecules or in the molecular chains. Examples of reactive functional groups include epoxy, hydroxyl, carboxyl, amino, amide, isocyanate, acryloyl, methacryloyl, vinyl, and maleic anhydride groups.

[0156] The thermosetting resin is preferably a thermosetting elastomer selected from styrene-based elastomers, olefin-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and siloxane-based elastomers. These thermosetting elastomers consist of hard segment components and soft segment components. Generally, the former is beneficial to the resin's heat resistance and strength, while the latter is beneficial to the resin's flexibility and toughness. A single thermosetting elastomer can be used, or two or more can be used in combination. From the viewpoint of further improving the heat resistance and insulation reliability of the interlayer insulation layer, the thermosetting elastomer is preferably at least one of styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, and siloxane-based elastomers; from the viewpoint of the dielectric properties of the interlayer insulation layer, at least one of styrene-based elastomers and olefin-based elastomers is more preferred.

[0157] Thermosetting elastomers may have reactive functional groups at the molecular ends or in the molecular chain. Examples of reactive functional groups include epoxy, hydroxyl, carboxyl, amino, amide, isocyanate, acryloyl, methacryloyl, vinyl, and maleic anhydride groups. From the viewpoint of compatibility and wiring properties, reactive functional groups are preferably epoxy, amino, acryloyl, methacryloyl, vinyl, or maleic anhydride groups, and more preferably epoxy, amino, or maleic anhydride groups.

[0158] Based on the mass of the resin composition (excluding fillers), the content of the thermosetting elastomer is, for example, 10% to 70% by mass, and preferably 20% to 60% by mass from the viewpoint of media properties and varnish compatibility.

[0159] Examples of curing agents include peroxide-based compounds, imidazole compounds and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. From a reactivity point of view, the curing agent is preferably at least one of peroxide-based, phosphorus-based, and imidazole-based compounds, and from the viewpoint of the good self-polymerization of maleimide groups, peroxide-based compounds are more preferred.

[0160] The content of the curing agent can vary depending on the type of catalyst and resin or the intended use of the resin composition. For example, when the curing agent is peroxide-based, the content of the curing agent is preferably 0.1% to 10% by mass based on the mass of the resin composition (excluding fillers), and more preferably 0.5% to 5% by mass, and even more preferably 0.75% to 3% by mass, from the viewpoint of media characteristics and membrane handling.

[0161] The resin composition of the second embodiment may further contain an epoxy resin as a thermosetting resin. The epoxy resin preferably contains at least two epoxy groups within its molecule. From the viewpoint of curing properties and cured product characteristics, the epoxy resin is more preferably a glycidyl ether type epoxy resin of phenol. Examples of such resins include, for instance, bisphenol A type (or AD type, S type, F type) glycidyl ethers, hydrogenated bisphenol A type glycidyl ethers, ethylene oxide adduct type bisphenol A type glycidyl ethers, propylene oxide adduct type bisphenol A type glycidyl ethers, phenolic resin glycidyl ethers, cresol resin glycidyl ethers, bisphenol A resin glycidyl ethers, naphthalene resin glycidyl ethers, trifunctional (or tetrafunctional) glycidyl ethers, dicyclopentadienol resin glycidyl ethers, dimer acid glycidyl esters, trifunctional (or tetrafunctional) glycidylamines, and naphthalene resin glycidylamines. Epoxy resins can be used alone or in combination with two or more types.

[0162] The resin composition of the second embodiment may further contain a (meth)acrylate compound. Examples of (meth)acrylate compounds include, for instance, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol di(methacrylate), triethylene glycol di(methacrylate), tetraethylene glycol di(methacrylate), trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane di(methacrylate), trimethylolpropane tri(methacrylate), 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol di(methacrylate), 1,6-hexanediol di(methacrylate), pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tri(methacrylate), pentaerythritol... Tetra(methacrylate), dipentaerythritol hexaacrylate, dipentaerythritol hexa(methacrylate), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, N-hydroxymethylacrylamide, triacrylate of tri(β-hydroxyethyl)isocyanurate, compounds represented by the following formula (13), urethane acrylates or urethane methacrylates, urea acrylates, isocyanuric acid modified di / triacrylates and methacrylates, etc.

[0163]

[0164] Where R 41 and R 42 Each of these can be used to independently represent a hydrogen atom or a methyl group, and f and g can be used to independently represent integers greater than 1.

[0165] The resin composition of the second embodiment may also contain an adhesion promoter. Examples of adhesion promoters include silane coupling agents, triazole compounds, or tetraazole compounds.

[0166] As a silane coupling agent, a compound having a nitrogen atom is preferred to improve adhesion to the metal. Examples of silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureopropyltrialkoxysilane, and 3-isocyanatopropyltriethoxysilane. From the viewpoints of effectiveness, heat resistance, and manufacturing cost, the content of the silane coupling agent is preferably 0.1 to 20 parts by weight, based on the total amount of solid components in the resin composition.

[0167] Examples of triazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-tert-octyl] Phenol, 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol, 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol, etc.

[0168] Examples of tetrazolium compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-methyl-5-ethyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-5-mercapto-1H-tetrazole, 2-methoxy-5-(5-trifluoromethyl-1H-tetrazole-1-yl)-benzaldehyde, 4,5-di(5-tetrazole)-[1,2,3]triazole, and 1-methyl-5-benzoyl-1H-tetrazole.

[0169] From the viewpoints of the added effect, heat resistance and manufacturing cost, the content of triazole compounds and tetraazole compounds is preferably 0.1 to 20 parts by mass, respectively, based on the total amount of solid components in the resin composition.

[0170] The aforementioned silane coupling agents, triazole compounds, and tetraazole compounds can be used individually or in combination.

[0171] The resin composition of the second embodiment may further contain an ion-scavenging agent. By adsorbing ionic impurities in the resin composition with an ion-scavenging agent, the insulation reliability of the interlayer insulation layer during moisture absorption can be further improved. Examples of ion-scavenging agents include triazine thiol compounds, phenolic reducing agents, or powdered inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, and tin-based compounds, as well as mixtures thereof. Triazine thiol compounds and phenolic reducing agents are known as anti-copper aging agents used to prevent copper ionization and dissolution.

[0172] Examples of ion scavengers include inorganic ion scavengers (manufactured by Toa Synthetic Co., Ltd., trade names: IXE-300 (antimony-based), IXE-500 (bismuth-based), IXE-600 (antimony and bismuth mixture), IXE-700 (magnesium and aluminum mixture), IXE-800 (zirconium-based), and IXE-1100 (calcium-based)). One of these ion scavengers can be used alone, or two or more can be used in combination. From the viewpoints of effectiveness, heat resistance, and manufacturing cost, the content of the ion scavenger, based on the total amount of solid components in the resin composition, is preferably 0.01 parts by weight to 10 parts by weight.

[0173] The following describes aspects common to both the first and second embodiments. From the viewpoint of imparting low hygroscopicity and low moisture permeability, the resin composition may further contain fillers (fillers). The fillers may be inorganic fillers made of inorganic materials or organic fillers made of organic materials. These fillers are preferably insulating fillers.

[0174] Examples of inorganic fillers include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titanium oxide, glass, iron oxide, and ceramics. Examples of organic fillers include carbon and rubber-based fillers. Fillers of any type and shape can be used without particular restrictions.

[0175] Fillers can be classified and used according to the desired function. For example, inorganic fillers are added to impart thermal conductivity, low thermal expansion, and low moisture absorption to the interlayer insulation of wiring. Organic fillers are added, for example, to impart toughness to the interlayer insulation of wiring. A filler may contain at least one of inorganic and organic fillers; a single filler may be used alone, or two or more may be used in combination. From the viewpoint of imparting the required thermal conductivity, low moisture absorption, and insulation to the interlayer insulation of wiring, inorganic fillers are preferred. From the viewpoint of good dispersibility in resin varnishes and the ability to impart high adhesion upon heating, at least one of silica fillers and alumina fillers is more preferred.

[0176] The average particle size of the filler is, for example, 10 μm or less, and the maximum particle size is, for example, 30 μm or less. Preferably, the average particle size of the filler is 5 μm or less, and the maximum particle size is 20 μm or less. By having an average particle size of 10 μm or less and a maximum particle size of 30 μm or less, the effect of improving the fracture toughness (breakage toughness) of the interlayer insulation can be effectively achieved, and the decrease in the bonding strength and the occurrence of unevenness of the interlayer insulation can be suppressed. In addition, the surface roughening of the interlayer insulation and the decrease in bonding strength can also be suppressed. There are no particular limitations on the lower limit of the average particle size and the lower limit of the maximum particle size of the filler; either can be 0.001 μm or more.

[0177] Methods for determining the average and maximum particle size of fillers include, for example, using a scanning electron microscope (SEM) to measure the particle size of approximately 20 fillers. One SEM-based method involves preparing a sample by heating and curing a resin composition containing fillers (preferably at 150–180°C for 1–10 hours), cutting off the central portion of the sample, and observing the cross-section using SEM. In this case, the probability of fillers with a particle size of 30 μm or less on the cross-section is preferably 80% or more of all fillers.

[0178] The filler content can be appropriately determined based on the desired properties or functions. The filler content, for example, is preferably 1% to 70% by mass, or 2% to 60% by mass, more preferably 5% to 50% by mass, based on the mass of the resin composition. By increasing the filler content, a high elastic modulus of the interlayer insulation can be achieved. This effectively improves cutability (cutting performance by a cutting blade), wire bonding (ultrasonic efficiency), and adhesion strength during heating. From the viewpoint of suppressing the decrease in hot-pressing adhesion, the filler content is preferably below the aforementioned upper limit. The most suitable filler content for achieving a balance of the desired properties can also be determined. The mixing and compounding of the filler can be carried out using a suitable combination of a common mixer, pounder, three-roll mill, ball mill, or other disperser.

[0179] From the viewpoints of maintaining stability, preventing electromigration, and preventing corrosion of metallic conductor circuits, the resin composition may further contain antioxidants. There are no particular limitations on the antioxidants used; examples include benzophenone-based, benzoate-based, hindered amine-based, benzotriazole-based, and phenolic antioxidants. From the viewpoints of effectiveness, heat resistance, and cost, the antioxidant content is preferably 0.01 to 10 parts by weight per 100 parts by weight of the resin component.

[0180] To further promote curing, the resin composition may also contain a catalyst. Examples of catalysts include peroxides, imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. One or more of these can be used alone or in combination. From a reactivity point of view, the catalyst is preferably selected from at least one of peroxides, imidazole compounds, and organophosphorus compounds, and more preferably from the viewpoint of the self-polymerization of maleimide groups and the favorable reaction between maleimide and acryloyl groups.

[0181] The resin composition may further contain flame retardants. There are no particular limitations on the flame retardants, but examples include halogenated flame retardants such as brominated and chlorinated flame retardants, triphenyl phosphate, trimethylbenzyl phosphate, tri(dichloropropyl) phosphate, phosphate ester compounds, phosphorus-based flame retardants such as red phosphorus, nitrogen-based flame retardants such as guanidine aminosulfonate, melamine sulfate, melamine polyphosphate, and melamine cyanurate, phosphazene-based flame retardants such as cyclophosphamide and polyphosphazene, and inorganic flame retardants such as antimony trioxide. One of these flame retardants may be used alone, or two or more may be used in combination.

[0182] The resin composition may also contain a UV absorber. There are no particular limitations on the UV absorber; examples include benzotriazole UV absorbers.

[0183] The resin composition may also contain a fluorescent whitening agent. There are no particular limitations on the fluorescent whitening agent; examples include violet derivatives.

[0184] From an operational and processability point of view, the resin composition is preferably in the form of a film. The resin composition may also be a varnish (liquid) obtained by dissolving or uniformly dispersing the components in a solvent.

[0185] There are no particular limitations on the preparation methods and conditions for varnish. For example, the following methods can be listed: After thoroughly and uniformly stirring and mixing the main components in a specified amount using a mixer, the mixture is then kneaded using a kneading roller, extruder, kneader, roller, or extruder, and the resulting mixture is then cooled and pulverized. There are no particular limitations on the kneading method.

[0186] When the resin composition is a varnish, the solvent can be, for example, an organic solvent. There are no particular limitations on the organic solvent; examples include 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, and limonene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; and nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. One or more of these solvents can be used alone or in combination. From the viewpoint of solubility, toluene, xylene, cyclohexanone, cyclopentanone, limonene, or mesitylene are preferred organic solvents; from the viewpoint of lower toxicity, cyclopentanone, limonene, or mesitylene are more preferred.

[0187] The organic solvent is preferably used, for example, in an amount that brings the solid content of the resin composition in the varnish to 5 to 90% by mass. From the viewpoint of maintaining the workability and coating / coating properties of the varnish well, it is more preferably used in an amount that brings the solid content to 10 to 60% by mass.

[0188] The moisture absorption rate of the cured resin composition after being placed at 130°C and 85% relative humidity for 200 hours is preferably less than 1% by mass.

[0189] The moisture absorption rate of the cured resin composition after being placed at 130°C and 85% relative humidity for 200 hours can be determined according to the following steps: A 10 μm thick curable film of the resin composition is laminated onto a silicon wafer at 100°C, and then cured at 180°C for 2 hours. A sample of the laminate of the silicon wafer and the cured film of the resin composition is placed in a constant temperature and humidity bath (ESPEC EHS-221MD) at 130°C and 85% relative humidity for 200 hours. Then, after the temperature in the constant temperature and humidity bath is lowered to 50°C, the sample is removed, and the cured film is shaved off from the silicon wafer. The weight loss rate of the resulting cured sample due to heating is measured using a differential thermal gravimetric analyzer (Sii-Nanotechnology, trade name "TG / DTA6300") at a heating rate of 10°C / min, a nitrogen flow (400 mL / min), and a temperature range of 25–150°C. Record the rate of mass reduction (ratio of the mass of the cured sample before measurement) when heated to 150°C as the moisture absorption rate (mass%).

[0190] From the viewpoint of insulation reliability, the concentration of chloride ions in the cured resin composition is preferably 5 ppm or less, and more preferably 3 ppm or less from the viewpoint of suppressing discoloration of copper wiring. The concentration of chloride ions can be determined by the following steps: 1 g of the cured sample and 10 g of ultrapure water as the extraction solution are added to a heat-resistant container made of Teflon (registered trademark), and heated at 130°C for 5 hours. Then, after filtering the extraction solution, it is analyzed by ion chromatography. In the obtained chromatogram, the peaks detected within the dissolution time of 0–30 minutes are considered as the total amount of dissolved substances, and the mass of chloride ions in the cured sample is calculated from the peak area of ​​chloride ions around 9.6 minutes. The ratio of the calculated mass of chloride ions to the mass of the cured sample is calculated as the concentration of chloride ions in the cured product (ppm).

[0191] The conditions for ion chromatography here are as follows.

[0192] • Device: Dionex ISC-2000

[0193] • Detector: Conductivity detector

[0194] • Column: AS20 (4mm φ × 200mm)

[0195] Column temperature: 30℃

[0196] • Flow rate: 1.0 ml / min

[0197] Injection volume: 25μl

[0198] • Gradient setting: Set the KOH concentration to 5mM at 0 minutes, 5mM at 5 minutes, 30mM at 15 minutes, and 55mM at 20 minutes.

[0199] From the viewpoint of suppressing crosstalk between wiring layers, the dielectric constant of the interlayer insulation layer (cured resin composition) at 10 GHz is preferably 3.6 or less, 3.2 or less, or 3.0 or less, and more preferably 2.8 or less from the viewpoint of improving the reliability of electrical signals. This dielectric constant can be 1.0 or more. This dielectric constant can be measured using a test piece obtained as follows: the resin composition is cured by heating at 180°C for 2 hours; the resulting cured material with a thickness of 300 μm is cut into pieces 60 mm long and 2 mm wide; and then vacuum-dried at 30°C for 6 hours to obtain the test piece.

[0200] The dielectric loss tangent of the interlayer insulation layer (cured resin composition) at 10 GHz is preferably 0.012 or less, 0.008 or less, or 0.005 or less. This dielectric loss tangent can be 0.0001 or more. This dielectric loss tangent can be calculated from the resonant frequency number and the no-load Q value obtained at 10 GHz. The measurement temperature is 25°C. As the measuring device for the dielectric constant and dielectric loss tangent, a vector network analyzer (manufactured by Keysight Technologies Inc., trade name: E8364B) or a 10 GHz resonator (manufactured by Kanto Electronics Application Development Co., Ltd., trade name: CP531) can be used. As the program, CPMA-V2 can be used.

[0201] From the viewpoint of suppressing cracking during temperature cycling, the glass transition temperature of the cured resin composition is preferably 120°C or higher, and more preferably 140°C or higher from the viewpoint of mitigating stress applied to wiring. From the viewpoint of enabling lamination at low temperatures, the glass transition temperature of the cured resin composition is preferably 240°C or lower, and more preferably 220°C or lower from the viewpoint of suppressing curing shrinkage. The glass transition temperature of the cured resin composition can be 120–240°C, 120–220°C, 140–240°C, or 140–220°C.

[0202] The glass transition temperature of the cured resin composition can be determined using a sample prepared as follows: the resin composition is cured by heating at 180°C for 2 hours, and the resulting cured material with a thickness of 300 μm is cut into samples 30 mm long and 4 mm wide. The measurement is performed using a UBM dynamic viscoelasticity measuring apparatus at a clamping distance of 20 mm, a frequency of 10 Hz, and a heating rate of 5°C / min within a temperature range of 40–260°C. The temperature at which tanδ shows the maximum value is recorded as the glass transition temperature.

[0203] From the viewpoint of reducing warping of the insulation layer between wiring layers, the elongation at break of the cured resin composition is, for example, 5% or more. From the viewpoint of mitigating stress applied to copper wiring, the elongation at break is preferably 10% or more. From the viewpoint of improving the temperature cycling reliability of the wiring layer laminate, the elongation at break is more preferably 15% or more. The elongation at break can be 200% or less. The elongation at break of the cured resin composition can be 5-200%, 10-200%, or 15-200%. The elongation at break can be measured using a sample prepared as follows: the resin composition is cured by heating at 180°C for 2 hours, and the resulting cured material with a thickness of 300 μm is cut into pieces 30 mm long and 5 mm wide to obtain a sample. The elongation at break can be measured using a small benchtop testing machine (manufactured by Shimadzu Corporation, trade name: EZ-S) with the conveying speed set to 5 mm / min.

[0204] From the viewpoint of heat resistance reliability, the 5% weight reduction temperature of the cured resin composition is, for example, 300°C or higher. The 5% weight reduction temperature of the first wiring interlayer insulation layer 17 can be determined as follows: the resin composition is cured by heating at 180°C for 2 hours, and the resulting cured product with a thickness of 300 μm is used as a sample. The temperature is measured using a differential thermal gravimetric analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., trade name: TG / DTA6300) under the conditions of a heating rate of 10°C / min and a nitrogen flow rate of 400 ml / min.

[0205] The storage modulus of the cured resin composition at 40°C can be 10 MPa to 5 GPa.

[0206] Figure 1 This is a schematic cross-sectional view of a semiconductor package having one embodiment of a semiconductor wiring layer stack. The semiconductor wiring layer stack of this application can be suitably used in the package configuration of an inserter that requires the mixing of different types of chips.

[0207] like Figure 1As shown, the semiconductor package 100 is a semiconductor device comprising a substrate 1, a wiring layer stack 10 disposed on the substrate 1, and semiconductor chips 2A and 2B mounted on the wiring layer stack 10. The semiconductor chips 2A and 2B are respectively fixed to the wiring layer stack 10 by corresponding bottom fillers 3A and 3B, and are electrically connected to each other by surface wiring (not shown) disposed within the wiring layer stack 10. Furthermore, the substrate 1 is a sealed body formed by sealing the semiconductor chips 2C and 2D and electrodes 5A and 5B with an insulating material 4. The semiconductor chips 2C and 2D within the substrate 1 can be connected to an external device through electrodes exposed from the insulating material 4. The electrodes 5A and 5B function, for example, as conductive paths for electrically connecting the wiring layer stack 10 to an external device.

[0208] Each semiconductor chip 2A to 2D may be, for example, a graphics processing unit (GPU), a volatile memory such as DRAM (Dynamic Random Access Memory) or SRAM (Static Random Access Memory), a non-volatile memory such as flash memory, an RF chip, a silicon photonics chip, a MEMS (Micro Electro Mechanical Systems), or a sensor chip. Semiconductor chips 2A to 2D may have a TSV (Transient Voltage Slab). Each semiconductor chip 2A to 2D may also be a device obtained by stacking semiconductor elements, for example, a semiconductor element obtained by stacking TSVs. The thickness of semiconductor chips 2A and 2B is, for example, 200 μm or less. From the viewpoint of thinning the semiconductor package 100, the thickness of semiconductor chips 2A and 2B is preferably 100 μm or less. Furthermore, from the viewpoint of operational processability, the thickness of semiconductor chips 2A and 2B is more preferably 30 μm or more. Each semiconductor chip 2A to 2D is electrically connected to any one of the wirings within the wiring layer stack 10.

[0209] The underlayer fillers 3A and 3B are, for example, capillary underlayer fillers (CUF), molding underlayer fillers (MUF), non-conductive pastes (NCP), non-conductive films (NCF), or photosensitive underlayer fillers. The underlayer fillers 3A and 3B are each primarily composed of a liquid-curing resin (e.g., epoxy resin). Additionally, the insulating material 4 is, for example, a curable resin with insulating properties.

[0210] Next, use Figure 2The wiring layer stack 10 of this embodiment will be described in detail. The wiring layer stack 10 is a wiring substrate on which semiconductor elements are mounted. The shape of the wiring layer stack 10 corresponds to the shape of the substrate 11 described later, and can be either a disc (approximately circular when viewed from above) or a panel (approximately rectangular when viewed from above).

[0211] Figure 2 The wiring layer stack 10 shown on the substrate 11 includes: a plurality of wiring layers 41, 42, each comprising organic insulating layers 21, 22, copper wirings 13, 14 embedded in the organic insulating layers 21, 22, and barrier metal films 15, 16 disposed between the copper wirings 13, 14 and the organic insulating layers 21, 22; interlayer insulating layers 17, 18 adjacent to the wiring layers 41, 42; and through wirings 19 penetrating the organic insulating layers 21, 22 and the interlayer insulating layers 17, 18. The organic insulating layers 21, 22 and the interlayer insulating layers 17, 18 are alternately stacked on the substrate 11. A portion of the surface of the copper wirings 13, 14 is exposed on one main surface side of the wiring layers 41, 42, and the interlayer insulating layers 17, 18 are in contact with the exposed surface of the copper wirings 13, 14. Interlayer insulation layers 17 and 18 are cured products of the curable resin composition described in the above embodiments. Organic insulation layers 21 and 22 may be layers formed of photosensitive insulating resin. Copper wiring may also be exposed on both main surfaces of the wiring layers, and the interlayer insulation layers are in contact with the surfaces of the exposed copper wiring.

[0212] The substrate 11 is a support for the wiring layer stack 10. The shape of the substrate 11 in top view is, for example, circular or rectangular. In the case of a circle, the substrate 11 has a diameter of, for example, 200 mm to 450 mm. In the case of a rectangle, one side of the substrate 11 has a diameter of, for example, 300 mm to 700 mm.

[0213] The substrate 11 may be, for example, a silicone resin substrate, a glass substrate, or a peelable copper foil. The substrate 11 may also be, for example, a reinforcement substrate, a wafer-level packaging substrate, a coreless substrate, a substrate manufactured by thermosetting a sealing material, or a substrate with a sealed or embedded chip. When using a silicone resin substrate or a glass substrate as the substrate 11, a temporary fixing layer (not shown) may be provided to temporarily fix the wiring layer stack 10 and the substrate 11. In this case, by removing the temporary fixing layer, the substrate 11 can be easily peeled off from the wiring layer stack 10. The peelable copper foil refers to a stack formed by sequentially overlapping a support, a release layer, and a copper foil. Regarding the peelable copper foil, the support corresponds to the substrate 11, and the copper foil may form part of the through wiring 19.

[0214] 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. The first organic insulating layer 21 has a plurality of grooves 21a (first grooves) with corresponding copper wirings 13 disposed thereon. The fourth organic insulating layer 24 is provided with a plurality of openings corresponding to the grooves 21a. The surface of the third organic insulating layer 23 exposed through these openings forms the bottom surface of the inner surface of the groove 21a. The side surfaces of the grooves 21a are formed by the fourth organic insulating layer 24.

[0215] The thicknesses of the third organic insulating layer 23 and the fourth organic insulating layer 24 are, for example, 0.5 μm to 10 μm. Therefore, the thickness of the first organic insulating layer 21 is, for example, 1 μm to 20 μm. When the thickness of the first organic insulating layer 21 is 1 μm or more, it helps to alleviate stress in the wiring layer laminate 10 and improves the temperature cycling resistance of the wiring layer laminate 10. When the thickness of the first organic insulating layer 21 is 20 μm or less, warping of the wiring layer laminate 10 can be suppressed, for example, preventing the wiring from being easily exposed during grinding of the wiring layer laminate 10. From the viewpoint of forming copper wiring 13 with a width of 3 μm or less by exposure and development, the thickness of the first organic insulating layer 21 is preferably 15 μm or less, more preferably 10 μm or less.

[0216] Multiple slots 21a are provided on the surface of the first organic insulating layer 21 opposite to the substrate 11. In a cross-section along a direction orthogonal to the extending direction of the slot 21a, each slot 21a is approximately rectangular. Therefore, the inner surface of the slot 21a has a side surface and a bottom surface. Furthermore, the multiple slots 21a have a defined linewidth L and a spacing width S. The linewidth L and the spacing width S are, for example, 0.5 μm to 10 μm, preferably 0.5 μm to 5 μm, and more preferably 2 μm to 5 μm. From the viewpoint of achieving high-density transmission in the wiring layer stack 10, the linewidth L is preferably 1 μm to 5 μm. The linewidth L and the spacing width S can be set to be the same or different from each other. The linewidth L is equivalent to the width of the slot 21a in a direction orthogonal to the extending direction of the slot 21a when viewed from above. The spacing width S is equivalent to the distance between adjacent slots 21a. The depth of the groove 21a is equivalent to, for example, the thickness of the fourth organic insulating layer 24.

[0217] The organic insulating layer 22 (second organic insulating layer) is stacked on the first organic insulating layer 21 in such a way that the wiring interlayer insulating layer 17 (first wiring interlayer insulating layer) is sandwiched between it. The second organic insulating layer 22 has a plurality of grooves 22a (second grooves) on which corresponding copper wiring 14 is disposed.

[0218] The thickness of the second organic insulating layer 22 is, for example, 1 μm to 10 μm. When the thickness of the second organic insulating layer 22 is 1 μm or more, it helps to alleviate stress in the wiring layer laminate 10 and improves the temperature cycling resistance of the wiring layer laminate 10. When the thickness of the second organic insulating layer 22 is 10 μm or less, warping of the wiring layer laminate 10 can be suppressed, for example, preventing the wiring from being easily exposed during grinding of the wiring layer laminate 10. A plurality of openings corresponding to the grooves 22a are provided on a portion of the second organic insulating layer 22. The surface of the first wiring interlayer insulation layer 17 exposed through these openings constitutes the bottom surface of the inner surface of the groove 22a. Each side of the groove 22a is formed by the second organic insulating layer 22. In this embodiment, the linewidth and spacing width of the plurality of grooves 22a are consistent with the linewidth L and spacing width S of the groove 21a.

[0219] The first organic insulating layer 21 forming the groove 21a and the second organic insulating layer 22 forming the groove 22a can be cured by heat treatment. The heat treatment is carried out, for example, using an oven. From the viewpoint of reducing residual stress in the wiring layer laminate 10, it is preferable to perform the heat treatment at, for example, below 200°C. From the viewpoint of production efficiency, it is preferable to set the heat treatment time to less than 3 hours.

[0220] As described above, the copper wiring 13 is disposed in the corresponding slot 21a and functions as a conductive path inside the wiring layer stack 10. Therefore, the width of the copper wiring 13 is approximately the same as the line width L of the slot 21a, and the spacing between adjacent copper wiring 13 is approximately the same as the spacing width S of the slot 21a.

[0221] As described above, the copper wiring 14 is disposed within the corresponding slot 22a, serving as a conductive path within the wiring layer stack 10. Therefore, the width of the copper wiring 13 is approximately the same as the line width of the slot 22a, and the spacing between adjacent copper wirings 14 is approximately the same as the spacing width of the slots 22a. The copper wiring 14 contains the same metallic material as the copper wiring 13.

[0222] The first barrier metal film 15 is a metal film disposed in such a way as to separate the copper wiring 13 and the first organic insulating layer 21 (i.e., the inner surface of the trench 21a). The first barrier metal film 15 is a film used to prevent copper from diffusing from the copper wiring 13 to the first organic insulating layer 21, and is formed along the inner surface of the trench 21a. Therefore, the first barrier metal film 15 contains a metallic material (e.g., titanium, chromium, tungsten, palladium, nickel, gold, tantalum, or alloys containing them) that does not readily diffuse into the organic insulating layer. The first barrier metal film 15 may contain one or more metals. From the viewpoint of adhesion to the inner surface of the trench 21a, the first barrier metal film 15 is preferably a titanium film or an alloy film containing titanium. When the first barrier metal film 15 is formed by sputtering, the first barrier metal film 15 is preferably a titanium film, tantalum film, tungsten film, chromium film, or an alloy film containing at least one of titanium, tantalum, tungsten, and chromium.

[0223] 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. From the viewpoint of preventing conduction between the copper wires 13 and suppressing the increase in resistance of the copper wires 13, the thickness of the first barrier metal film 15 is, for example, 0.001 μm to 0.5 μm. From the viewpoint of preventing the diffusion of metal material within the copper wires 13, the thickness of the first barrier metal film 15 is preferably 0.01 μm to 0.5 μm. From the viewpoint of increasing the flatness of the first barrier metal film 15 and the amount of current flowing through the copper wires 13, the thickness of the first barrier metal film 15 is preferably 0.001 μm to 0.3 μm. From the above viewpoints, the thickness of the first barrier metal film 15 is most preferably 0.01 μm to 0.3 μm.

[0224] The second barrier metal film 16 is a metal film provided to separate the copper wiring 14 and the second organic insulating layer 22 (i.e., the inner surface of the trench 22a). The second barrier metal film 16 is a film used to prevent copper from diffusing from the copper wiring 14 to the second organic insulating layer 22, and is formed along the inner surface of the trench 22a. Therefore, like the first barrier metal film 15, the second barrier metal film 16 contains a metallic material that does not easily diffuse into the organic insulating layer. The thickness of the second barrier metal film 16 is the same as that of the first barrier metal film 15, being less than half the width of the trench 22a and less than the depth of the trench 22a. Therefore, the thickness of the second barrier metal film 16 is, for example, 0.001 μm to 0.5 μm, preferably 0.01 μm to 0.5 μm or 0.001 μm to 0.3 μm, and most preferably 0.01 μm to 0.3 μm.

[0225] The first interlayer insulation layer 17 is an insulating film used to prevent copper from diffusing from the copper wiring 13 to the first organic insulating layer 21 and the second organic insulating layer 22. The first interlayer insulation layer 17 is provided between wiring layer 41 (first wiring layer) and wiring layer 42 (second wiring layer) to separate the copper wiring 13 and the second organic insulating layer 22. The first interlayer insulation 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 of making the wiring layer stack 10 thinner, the thickness of the first interlayer insulation layer 17 is, for example, 50 μm or less. From the viewpoint of preventing conductivity between the copper wiring 13, the thickness of the first interlayer insulation layer 17 is, for example, 1 μm or more, preferably 10 μm or more. From the viewpoint of surface smoothness of the first interlayer insulation layer 17, the thickness of the first interlayer insulation layer 17 is preferably 30 μm or less. Details regarding the materials contained in the first wiring interlayer insulation layer 17 and other characteristics of the first wiring interlayer insulation layer 17 will be described later.

[0226] The second interlayer insulation layer 18 is an insulating film used to prevent copper from diffusing from the copper wiring 14 to the second organic insulating layer 22. The second interlayer insulation layer 18 is 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, and is disposed on the second wiring layer 42. The second interlayer insulation layer 18 contains the same material as the first interlayer insulation layer 17 and has the same properties as the first interlayer insulation layer 17.

[0227] Through-hole wiring 19 is a wiring embedded in the through-hole 31 of through-hole wiring layers 41, 42 and the insulation layers 17, 18 between wiring layers, and functions as a connection terminal to external devices.

[0228] Below, refer to Figures 3 to 10 The manufacturing method of the wiring layer laminate 10 according to this embodiment will be described. The wiring layer laminate 10 formed by the following manufacturing method is particularly suitable, for example, in configurations requiring miniaturization and multiple pins. Furthermore, Figure 4 (b) is Figure 4 (a) Enlarged view of the main part. Similarly, Figure 5 (b) Figure 6 (b) Figure 7 (b) Figure 8 (b) Figure 9 (b) Figure 10 (b) Figure 11 (b) and Figure 12 (b) are enlarged views of the main parts of the corresponding figures.

[0229] First, as step 1, such as Figure 3As shown in (a), a bottom 19a of a through-wire is formed on the substrate 11. The bottom 19a of the through-wire is formed by patterning a metal film formed on the substrate 11. In step 1, the metal film is formed by, for example, a physical vapor deposition (PVD) method such as coating, vacuum evaporation or sputtering, a printing or spraying method using metal paste, or various plating methods. In this embodiment, copper foil is used as the metal film.

[0230] When a temporary fixing layer (not shown) is provided between the substrate 11 and the bottom 19a of the through wiring, the temporary fixing layer contains a resin such as polyimide, polybenzoxazole, a resin containing non-polar components such as silicon or fluorine, a resin containing components that can expand or foam by heating or UV (ultraviolet light), a resin containing components that can undergo crosslinking by heating or UV, or a resin that can generate heat by light irradiation. Examples of methods for forming the temporary fixing layer include spin coating, spray coating, or lamination. From the viewpoint of achieving a high degree of balance between processability and carrier peelability, the temporary fixing layer is preferably easy to peel off by external stimuli such as light or heat. From the viewpoint that the temporary fixing layer can be peeled off so as not to remain on the semiconductor wiring layer laminate 10 manufactured subsequently, the temporary fixing layer most preferably contains a resin that can expand in volume by heat treatment.

[0231] When a temporary fixing layer is provided between the substrate 11 and the bottom 19a of the through wiring, the bottom 19a of the through wiring can also be formed of a peelable copper foil. In this case, the substrate 11 is equivalent to a support for the peelable copper foil, and the temporary fixing layer is equivalent to a release layer for the peelable copper foil.

[0232] Next, as step 2, such as Figure 3 As shown in (b), a third organic insulating layer 23 is formed on the substrate 11 in such a way that it covers the bottom 19a of the through wiring. In step 2, for example, the third organic insulating layer 23 can be formed by attaching a film of photosensitive insulating resin to the substrate 11. As needed, the film of photosensitive insulating resin is subjected to exposure treatment, development treatment, curing treatment, etc.

[0233] Then, as in step 3, such as Figure 3 As shown in (c), the first organic insulating layer 21 is formed by forming a fourth organic insulating layer 24 on the third organic insulating layer 23. In step 3, similar to step 2, the fourth organic insulating layer can be formed by attaching a film containing a photosensitive insulating resin to the third organic insulating layer 23. As needed, the film containing the photosensitive insulating resin undergoes exposure treatment, development treatment, curing treatment, etc.

[0234] Then, as in step 4, such as Figure 4As shown in (a) and (b), a plurality of grooves 21a are formed on the first organic insulating layer 21. In step 4, the plurality of grooves 21a are formed by, for example, laser ablation, photolithography, or imprinting. From the viewpoint of miniaturization of the grooves 21a and formation cost, photolithography is preferred. For example, the plurality of grooves 21a can be formed by exposing and developing the photosensitive insulating resin used to form the fourth organic insulating layer 24.

[0235] As a method for exposing the photosensitive insulating resin using the above-described photolithography method, known methods such as projection exposure, contact exposure, and direct tracing exposure can be used. Additionally, to develop the photosensitive insulating resin, alkaline aqueous solutions such as sodium carbonate or tetramethylammonium hydroxide (TMAH) can also be used.

[0236] In step 4 above, after forming multiple grooves 21a, the first organic insulating layer 21 can be further cured by heating. In this case, for example, the heating temperature is set to 100 to 200°C and the heating time is set to 30 minutes to 3 hours to cure the first organic insulating layer 21 by heating.

[0237] Then, as in step 5, such as Figure 5 As shown in (a) and (b), a first barrier metal film 15 is formed on the first organic insulating layer 21 to cover the inner surface of the groove 21a. In step 5, the first barrier metal film 15 is formed by, for example, coating, PVD, printing or spraying using metal paste, or various plating methods. When using a coating method, a palladium or nickel complex is coated on the first organic insulating layer 21 and then heated to form the first barrier metal film 15. When using a metal paste, a paste containing metal particles such as nickel and palladium is coated on the first organic insulating layer 21 and then sintered to form the first barrier metal film 15. In this embodiment, the first barrier metal film 15 is formed by sputtering, which is a type of PVD method.

[0238] Then, as in step 6, such as Figure 6 As shown in (a) and (b), a copper layer 13A for forming copper wiring is formed on the first barrier metal film 15 by filling the trench 21a. In step 6, the copper layer 13A is formed by, for example, using a metal paste method or a plating method with the first barrier metal film 15 as a seed layer. The thickness of the copper layer 13A is preferably, for example, 0.5 to 3 times the thickness of the first organic insulating layer 21. When the thickness of the copper layer 13A is 0.5 times or more, it is preferable to suppress the increase of surface roughness of the copper wiring 13 formed in subsequent processes. In addition, when the thickness of the copper layer 13A is 3 times or less, it is preferable to suppress the warping of the copper layer 13A and to ensure good adhesion to the first organic insulating layer 21.

[0239] Then, as in step 7, such as Figure 7 As shown in (a) and (b), the copper layer 13A is thinned to expose the first organic insulating layer 21. In step 7, the portion of the copper layer 13A other than the groove 21a and the portion of the first barrier metal film 15 that is not covered by the groove 21a are removed by mechanical or chemical methods. Thus, while exposing the first organic insulating layer 21, the copper layer 13A is thinned to form a copper wiring 13 embedded in the groove 21a. This thinning process can also be a planarization process of the surface where the first organic insulating layer 21 and the copper wiring 13 are combined. In this case, the target portions of the copper layer 13A and the first barrier metal film 15 are removed by CMP or rapid cutting, while the surface of the first organic insulating layer 21 is ground or spun to achieve planarization.

[0240] In step 7, when using CMP, the slurry used can be, for example, an alumina-based slurry commonly used for resin polishing, a slurry containing hydrogen peroxide and silica used for polishing the first barrier metal film 15, and a slurry containing hydrogen peroxide and ammonium persulfate used for polishing the copper layer 13A. From the viewpoint of reducing costs while suppressing the expansion of surface roughness, it is preferable to use an alumina-based slurry to polish the first organic insulating layer 21, the first barrier metal film 15, and the copper layer 13A. Using CMP tends to increase costs. Furthermore, when simultaneously planarizing the first organic insulating layer 21, the first barrier metal film 15, and the copper layer 13A (copper wiring 13), concavity occurs on the copper wiring 13 due to differences in polishing speed, resulting in a tendency for the flatness of the surface where the first organic insulating layer 21 and the copper wiring 13 are joined to be significantly compromised. Therefore, it is more preferable to use a rapid cutting method of a leveling machine to grind the first organic insulating layer 21, the first barrier metal film 15, and the copper layer 13A (copper wiring 13).

[0241] Then, as in step 8, such as Figure 8 As shown in (a) and (b), a first wiring interlayer insulation layer 17 is formed to cover the copper wiring 13 within the groove 21a. In step 8, the first wiring interlayer insulation layer 17 is formed by, for example, spin coating, spray coating, bar coating, curtain coating, printing, or lamination.

[0242] From the viewpoint of ease of handling, it is preferable to use a film-like resin composition to form the first wiring interlayer insulation layer 17. Furthermore, from the viewpoint of uniform film thickness of the first wiring interlayer insulation layer 17 and its ability to handle large-scale applications, it is preferable to use a lamination method to form the first wiring interlayer insulation layer 17. When using a lamination method to form the first wiring interlayer insulation layer 17, the film-like resin composition is adhered to the first organic insulating layer 21, similar to steps 2 and 3. In this case, from the viewpoint of reducing residual stress, it is preferable to set the temperature to 150°C or lower, and from the viewpoint of suppressing voids, it is preferable to set the temperature to 60°C or higher.

[0243] In step 8, preferably, the first interlayer insulation layer 17 is formed not only on the copper wiring 13 but also on the portion of the first barrier metal film 15 that contacts the side of the groove 21a. In this case, a portion of the copper wiring 13 (the side and bottom surfaces of the copper wiring 13 opposite to the inner surface of the groove 21a) is covered by the first barrier metal film 15, and the remaining portion of the copper wiring 13 (the upper surface of the copper wiring 13) is covered by the first interlayer insulation layer 17. The copper wiring 13 is covered without gaps by the first barrier metal film 15 and the first interlayer insulation layer 17.

[0244] Next, as in step 9, as... Figure 9 As shown in (a) and (b), a second organic insulating layer 22 with grooves 22a is formed on the first interlayer insulating layer 17. In step 9, firstly, as in step 3, a film of photosensitive insulating resin is attached to the first interlayer insulating layer 17. Then, a plurality of grooves 22a are formed on the attached film of photosensitive insulating resin. In step 9, the grooves 22a are formed in the same manner as the grooves 21a described in step 4. In step 9, from the viewpoint of preventing the diffusion of copper constituting the copper wiring 13, it is preferable not to perform a development process on the second organic insulating layer 22.

[0245] Then, as in step 10, as Figure 10 As shown in (a) and (b), a second barrier metal film 16 and a copper layer 14A for forming copper wiring are sequentially formed on the second organic insulating layer. In step 10, the second barrier metal film 16 is first formed on the second organic insulating layer 22 in the same manner as in step 5, so as to cover the inner surface of the trench 22a. Then, the copper layer 14A is formed on the second barrier metal film 16 in the same manner as in step 6, so as to fill the trench 22a.

[0246] Then, as in step 11, as Figure 11As shown in (a) and (b), the copper layer 14A is thinned to expose the second organic insulating layer 22. In step 11, the portion of the copper layer 14A other than the groove 22a and the portion of the second barrier metal film 16 that is not covered by the groove 22a are removed by mechanical or chemical methods, using the same method as in step 7. Thus, the copper layer 14A is thinned while exposing the second organic insulating layer 22, forming a copper wiring 14 embedded in the groove 22a.

[0247] Then, as in step 12, as Figure 12 As shown in (a) and (b), a second wiring interlayer insulation layer 18 is formed to cover the copper wiring 14 within the groove 22a. In step 12, the second wiring interlayer insulation layer 18 is formed on the second organic insulating layer 22 using the same method as in step 8. In step 12, it is preferable that the second wiring interlayer insulation layer 18 is formed not only on the copper wiring 14 but also on the portion of the second barrier metal film 16 that contacts the side of the groove 22a. In this case, the side and bottom surfaces of the copper wiring 14 are covered by the second barrier metal film 16, and the upper surface of the copper wiring 14 is covered by the second wiring interlayer insulation layer 18. The copper wiring 14 is covered without gaps by the second barrier metal film 16 and the second wiring interlayer insulation layer 18.

[0248] Then, as in step 13, as Figure 13 As shown in (a), a via 31 is formed that penetrates the first organic insulating layer 21, the first wiring interlayer insulating layer 17, the second organic insulating layer 22, and the second wiring interlayer insulating layer 18. As a method for forming the via 31, a laser is used, for example. Examples of lasers include carbon dioxide lasers, UV lasers, YAG lasers, and excimer lasers. Preferably, after the via 31 is formed, the interior of the via 31 is cleaned using a known method such as a decontamination treatment.

[0249] Then, as in step 14, as Figure 13 As shown in (b), a metal material is filled into the via 31 to form a conductive portion 19b within the via, thereby forming a through wiring 19 having a bottom 19a and a conductive portion 19b within the via. In step 14, the conductive portion 19b within the via is formed using, for example, PVD or various plating methods. Examples of metal materials include copper, nickel, and tin. After the above steps, a... Figure 2 The wiring layer stack 10 is shown. If a temporary fixing layer is provided, the wiring layer stack 10 can also be peeled off from the substrate 11.

[0250] In the wiring layer laminate 10 manufactured by the above-described manufacturing method, after being placed in an environment of 130°C and 85% relative humidity for 2 hours, the moisture absorption rate of the interlayer insulation layer is less than 1% by mass, resulting in extremely low moisture content in the interlayer insulation layer. Therefore, the diffusion of copper into the interlayer insulation layer caused by the reaction between water and copper within the interlayer insulation layer can be effectively suppressed. As a result, the insulation properties of the interlayer insulation layer can be well maintained, short circuits between copper wires can be suppressed, and thus the insulation reliability of the wiring layer laminate 10 can be significantly improved.

[0251] By mounting multiple semiconductor chips on the wiring layer stack 10 in this embodiment, a semiconductor device formed by integrating semiconductor chips can be provided efficiently.

[0252] This application is not limited to the above-described embodiments, and appropriate modifications can be made without departing from its spirit. For example, a resin layer containing a photosensitive insulating resin, a wiring interlayer insulation layer, or an assembly material may also be formed between the first organic insulating layer 21 and the substrate 1.

[0253] On the first wiring interlayer insulation layer 17, instead of the second organic insulation layer 22 and copper wiring 14, a resin layer containing photosensitive insulating resin, a wiring interlayer insulation layer, assembly material, and a bottom filler can be formed, or copper wiring or bumps can be formed. Furthermore, vias for embedding metal materials connecting the copper wiring 13 and 14 can also be provided on the first wiring interlayer insulation layer 17.

[0254] The second wiring interlayer insulation layer 18 may also be formed with a resin layer containing photosensitive insulating resin, a wiring interlayer insulation layer, assembly material, a bottom filler, etc., and copper wiring or bumps may also be formed. In addition, vias for embedding metal materials for connecting copper wiring 14 and semiconductor chips may also be provided on the second wiring interlayer insulation layer 18.

[0255] Example

[0256] The invention will be described in more detail through the following examples, but the invention is not limited to these examples.

[0257] (Example 1)

[0258] Production as described below Figure 14The test samples shown in (a) and (b) are for evaluation. First, a photosensitive insulating resin film 52 with a thickness of 3 μm is attached to a silicon wafer 51 with a thickness of 150 mm. The photosensitive insulating resin film 52 is formed as follows. First, cresol phenolic varnish resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: TR-4020G, 100 parts by weight), 1,3,4,6-tetra(methoxymethyl)glycidyl urea (30 parts by weight), trimethylolpropane triglycidyl ether (40 parts by weight), triarylsulfone salt (manufactured by San-Apro Co., Ltd., trade name: CPI-310B, 8 parts by weight) and methyl ethyl ketone (100 parts by weight) are combined to obtain the photosensitive insulating resin. Then, the obtained photosensitive insulating resin was coated onto a polyethylene terephthalate film (manufactured by Teijindupont Film Co., Ltd., trade name: A-53), and dried in an oven at 90°C for 10 minutes to obtain a photosensitive insulating resin film 52 with a thickness of 3μm.

[0259] Then, the photosensitive insulating resin film 52 attached to the silicon wafer 51 is subjected to exposure, heat treatment, development, and thermal curing in sequence. Next, a photosensitive insulating resin film 53 with a thickness of 3 μm, formed in the same manner as the film 52, is attached to the photosensitive insulating resin film 52. Then, the attached photosensitive insulating resin film 53 is exposed through a photomask, followed by heat treatment, development, and thermal curing in sequence. This patterning of the photosensitive insulating resin film 53 forms first groove portions 53a and second groove portions 53b in a comb-like, interlocking manner; a first connecting portion 53c connecting the first groove portions 53a to each other; and a second connecting portion 53d connecting the second groove portions 53b to each other. The width of the first groove portion 53a and the width of the second groove portion 53b are each set to 5 μm. These widths correspond to the linewidth L of the wiring described later. In addition, the distance (spacing S) between adjacent first groove 53a and second groove 53b is set to 5μm, and the length of each groove is set to 1mm.

[0260] Then, a titanium-containing barrier metal film 54 with a thickness of 0.05 μm is formed on the photosensitive insulating resin film 53 by sputtering. Next, using the barrier metal film 54 as a seed layer, a copper layer is formed by electroplating to fill the first groove 53a, the second groove 53b, the first connecting portion 53c, and the second connecting portion 53d. Then, a portion of the copper layer and the portion of the barrier metal film 54 that does not cover the inner surfaces of the first groove 53a, the second groove 53b, the first connecting portion 53c, and the second connecting portion 53d are ground away using a rapid cutting method on a planer. This forms the first wiring 55a embedded in the first groove 53a, the second wiring 55b embedded in the second groove 53b, the first connecting wiring 55c embedded in the first connecting portion 53c, and the second connecting wiring 55d embedded in the second connecting portion 53d. As a leveling machine, an automatic leveling machine (manufactured by Disco Co., Ltd., trade name "DAS8930") is used. Furthermore, for grinding based on the rapid cutting method, the conveyor speed is set to 1 mm / s and the shaft speed is set to 2000 min / min. -1 .

[0261] Then, a curable film with a thickness of 10 μm is applied in such a way that at least a portion of the first connecting wire 55c and a portion of the second connecting wire 55d are exposed, and the curable film is thermally cured to form an interlayer insulation layer 57. The curable film is applied in such a way that at least the first connecting wire 55a and the second connecting wire 55b are embedded. Material A, as described below, is used as the curable film.

[0262] <Material A>

[0263] First, to synthesize a thermoplastic resin with siloxane chains, 25g of "BMI-3000" (manufactured by DesignerMolecules Inc., trade name), 25g of 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane (manufactured by Yamato Kasei Corporation, trade name: BMI-4000), and 150g of toluene were added to a flask and stirred for 20 minutes. Then, 16.4g of siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-8010) was added to the same flask, and the mixture was heated to 130°C using an oil bath. The mixture was stirred for 3 hours from the start of reflux to allow the reaction to proceed, and then cooled to room temperature by air cooling to form a solid thermoplastic resin with siloxane chains. Then, 50g of a thermosetting elastomer (manufactured by Asahi Kasei Corporation, trade name: Tuftec M1911) dissolved in toluene (based on solids), 50g of the aforementioned thermoplastic resin with siloxane chains (based on solids), and 2g of a curing agent (manufactured by Nippon Oil Co., Ltd., trade name: Perhexyne 25B) were mixed. The mixture was stirred for 30 minutes to uniformly disperse the compound, thereby forming a varnish of a resin composition for forming an interlayer insulation layer with a non-volatile content adjusted to 20%. The obtained varnish of the resin composition was applied to a demolded PET film (thickness: 38μm, trade name: NR-1) using a benchtop coater. The thickness of the coating was adjusted using a coater to achieve a dry thickness of 10μm. The coating of the resin composition was then dried at 130°C for 10 minutes to form a cured film (material A) on the PET film. Then, the PET film is removed, and the cured film (material A) is used to form the wiring interlayer insulation layer 57. The wiring interlayer insulation layer 57 (cured material A) of Example 1 has a moisture absorption rate of less than 1.0% by mass, a chloride ion concentration of less than 3 ppm, an elongation at break of 150%, and a storage modulus of 60 MPa at 40°C.

[0264] Then return Figure 14 A photosensitive insulating resin film 58, with a thickness of 3 μm, is attached to the interlayer insulation layer 57, forming a similar structure to the photosensitive insulating resin film 52. Then, the photosensitive insulating resin film undergoes exposure, development, and thermal curing treatments. This results in the formation of... Figure 14 The test specimen 50 shown in (a) and (b) is used for evaluation. In this test specimen 50, the first wirings 55a are interconnected with each other via first connecting wirings 55c, and the first wirings 55a are covered by a barrier metal film 54 and an interlayer insulation layer 57. Additionally, the second wirings 55b are interconnected with each other via second connecting wirings 55d, and the second wirings 55b are also covered by a barrier metal film 54 and an interlayer insulation layer 57.

[0265] To confirm the insulation reliability of the test specimen 50 used for evaluation as described above, a Highly Accelerated Stress Test (HAST) was performed as described below. In this test, a voltage of 3.3V was applied to the first connection wiring 55c and the second connection wiring 55d under conditions of 85% humidity and 130°C, and the circuit was left to stand for a specified time. The change in insulation between the first wiring 55a and the second wiring 55b over time was then measured. In this test, if the resistance value between the first wiring 55a and the second wiring 55b is 1 × 10⁻⁶ after 200 hours from the start of the test... 6 If the value is above Ω, it is recorded as evaluation A. If it is below 1×10 Ω 200 hours after the start of the experiment, it is considered an evaluation A. 6 Ω is denoted as evaluation B. The results of the high acceleration life test in Example 1 are shown in Table 1 below.

[0266] (Example 2)

[0267] Except that the linewidth L and the spacing S were set to 3 μm, the test specimen 50 for measurement and evaluation was formed in the same manner as in Example 1, and the high acceleration lifetime test described above was performed. The results of the high acceleration lifetime test in Example 2 are shown in Table 1 below.

[0268] (Example 3)

[0269] Except that the linewidth L and the spacing S were set to 2 μm, the test specimen 50 for measurement and evaluation was formed in the same manner as in Example 1, and the high acceleration lifetime test described above was performed. The results of the high acceleration lifetime test in Example 3 are shown in Table 1 below.

[0270] (Example 4)

[0271] Material B was used as the curable film for forming the interlayer insulation layer 57 of the wiring. Otherwise, a test specimen 50 for evaluation was formed in the same manner as in Example 2, and the high-acceleration life test described above was performed on the test specimen 50. The results of the high-acceleration life test of Example 4 are shown in Table 1 below.

[0272] <Material B>

[0273] First, to synthesize a thermoplastic resin with siloxane chains, 8.17 g of 1,4-butanediol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: B-12) as a diamine, 21.65 g of polyoxypropylene diamine (manufactured by BASF JAPAN Co., Ltd., trade name: D-400), and 8.6 g of siloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-8010) as a siloxane diamine, and 250 g of NMP (N-methyl-2-pyrrolidone) as a solvent were added to a 500 ml flask equipped with a stirrer, thermometer, and nitrogen purging device (nitrogen inlet tube). The mixture was stirred to dissolve the diamine in the solvent. Then, a reflux condenser with a moisture receiver was installed on the flask, and the temperature was raised to 180°C while blowing nitrogen gas. The temperature was maintained at 180°C for 5 hours to remove water while reacting. The solution obtained as described above was cooled to room temperature. Then, 50g of polybutadiene resin (manufactured by CRAY VALLEY, trade name: Ricon130MA8) dissolved in NMP (based on solids), 50g of the aforementioned thermoplastic resin with siloxane chains (based on solids), 2g of curing agent (manufactured by Nippon Oil Co., Ltd., trade name: Perhexyne25B), and 1g of G8009L (manufactured by Daiichi Kogyo Co., Ltd., trade name) were mixed and stirred for 30 minutes to uniformly disperse, forming a varnish of the resin composition for forming an interlayer insulation layer of wiring. The obtained varnish of the resin composition was applied to a demolded PET film (thickness of 38μm, trade name: NR-1) using a benchtop coater. The film thickness of the resin composition coating was adjusted using a coater to achieve a dry thickness of 10μm. Then, the resin composition coating was heated at 120°C for 20 minutes to dry, thereby forming a cured film (material B) on the PET film. Then, the PET film is removed, and the cured film (material B) is used to form the wiring interlayer insulation layer 57. The wiring interlayer insulation layer 57 (cured material B) of Example 4 has a moisture absorption rate of less than 1.0% by mass, a chloride ion concentration of less than 3 ppm, an elongation at break of 70%, and a storage modulus of 180 MPa at 40°C.

[0274] (Example 5)

[0275] Except that the linewidth L and the spacing S were set to 2 μm, the test specimen 50 for measurement and evaluation was formed in the same manner as in Example 4, and the high acceleration lifetime test described above was performed. The results of the high acceleration lifetime test in Example 5 are shown in Table 1 below.

[0276] (Example 6)

[0277] Material C was used as the curable film for forming the interlayer insulation layer 57 of the wiring. Otherwise, the test specimen 50 for evaluation was formed in the same manner as in Example 2. The high-acceleration lifetime test described above was performed on the test specimen 50 for evaluation. The results of the high-acceleration lifetime test of Example 6 are shown in Table 1 below.

[0278] <Material C>

[0279] First, to synthesize the thermoplastic resin, 10.3 g of 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4.1 g of 1,4-butanediol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: B-12), and 101 g of NMP were added to a flask equipped with a stirrer, thermometer, and nitrogen purging device. Then, 20.5 g of 1,2-(ethylidene)bis(triphenyltriglyceridyl anhydride) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Next, a reflux condenser with a moisture receiver was installed on the flask, and the temperature was raised to 180°C while purging with nitrogen. The temperature was maintained at 180°C for 5 hours to remove water during the reaction. The solution obtained as described above was then cooled to room temperature. Then, 50g of polybutadiene resin (manufactured by CRAY VALLEY, trade name: Ricon130MA8) dissolved in NMP (based on solids), 50g of the above-mentioned thermoplastic resin (based on solids), 2g of curing agent (manufactured by Nippon Yu Co., Ltd., trade name: Perhexyne25B), 10g of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000H) dissolved in NMP (based on solids), 1g of G8009L (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., trade name), and 70g of silica slurry (manufactured by Admatechs, trade name: SC2050-KNK) (based on solids) were mixed and stirred for 30 minutes to uniformly disperse, forming a varnish of the resin composition for forming an interlayer insulation layer of wiring. The obtained varnish of the resin composition was applied to a demolded PET film (38μm thick, trade name: NR-1) using a benchtop coater. The film thickness of the resin composition coating was adjusted using a coater to achieve a dry thickness of 10 μm. The coating was then dried at 120°C for 20 minutes to form a cured film (material C) on the PET film. The PET film was then removed, and the cured film (material C) was used to form the interlayer insulation layer 57. The interlayer insulation layer 57 (cured material C) of Example 6 had a moisture absorption rate of 1.0% by mass or less, a chloride ion concentration of 5 ppm or less, an elongation at break of 3%, and a storage modulus of 11 GPa at 40°C.

[0280] (Comparative Example 1)

[0281] Except for using material D to form the interlayer insulation layer 57, the test sample 50 for measurement and evaluation is formed in the same manner as in Example 1. However, the attached material D is exposed to a high-precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1172-B-∞) at an exposure dose of 500 mJ / cm. 2 After exposure treatment, a thermosetting treatment was performed. The high acceleration lifetime test described above was conducted on the test specimen 50 used for evaluation. The results of the high acceleration lifetime test of Comparative Example 1 are shown in Table 1 below.

[0282] <Material D>

[0283] Material D is a 10 μm thick film formed from the same photosensitive insulating resin as photosensitive insulating resin film 52. The cured material D has a moisture absorption rate of 2.0% by mass and a chloride ion concentration of 8.6 ppm.

[0284] (Comparative Example 2)

[0285] Except that the line width L and the spacing width S were set to 2 μm, the test specimen 50 for measurement and evaluation was formed in the same manner as in Comparative Example 1, and the high acceleration life test described above was performed. The results of the high acceleration life test of Comparative Example 2 are shown in Table 1 below.

[0286] (Comparative Example 3)

[0287] Interlayer insulation 57 of the wiring was formed using material E, with the line width L and spacing S set to 3 μm. Otherwise, a test specimen 50 for evaluation was formed in the same manner as in Comparative Example 1. The high-acceleration life test described above was performed on the test specimen 50 for evaluation. The results of the high-acceleration life test for Comparative Example 3 are shown in Table 1 below.

[0288] <Material E>

[0289] Material E uses FZ-2700GA (manufactured by Hitachi Chemicals Co., Ltd., trade name). The cured product of material E has a moisture absorption rate of 1.3% by mass and a chloride ion concentration of 6.3 ppm.

[0290] (Comparative Example 4)

[0291] Material F was used as the curable film for forming the interlayer insulation layer 57 of the wiring. The line width L and spacing width S were set to 3 μm. Otherwise, the test specimen 50 for evaluation was formed in the same manner as in Comparative Example 1. The high acceleration life test described above was performed on the test specimen 50 for evaluation. The results of the high acceleration life test of Comparative Example 4 are shown in Table 1 below.

[0292] <Material F>

[0293] First, to synthesize the thermoplastic resin, 2.16 g of 5,5'-methylenebis(o-aminobenzoic acid), 15.13 g of aliphatic ether diamine (manufactured by BASF JAPAN Co., Ltd., trade name: D-400), 1.63 g of 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LP-7100), and 115 g of NMP were added to the flask. Then, 16.51 g of oxydiphthalic anhydride (ODPA) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Next, while purging nitrogen into the flask, the temperature was raised to 180°C and maintained at 180°C for 5 hours to remove water during the reaction. The solution obtained as described above was then cooled to room temperature. Then, 30g of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000H) dissolved in NMP (based on solids), 50g of the aforementioned thermoplastic resin (based on solids), and 1g of 2P4MHZ (manufactured by Shikoku Kasei Corporation, trade name) as a curing agent were mixed and stirred for 30 minutes to uniformly disperse, forming a varnish of the resin composition. The obtained varnish of the resin composition was applied to a demolded PET film (thickness: 38μm, trade name: NR-1) using a benchtop coater. The coating of the resin composition was adjusted using a coater to achieve a thickness of 10μm after drying. Then, the coating of the resin composition was dried at 120°C for 20 minutes to form a cured film (material F) on the PET film. Then, the PET film was removed, and the cured film (material F) was used to form an interlayer insulation layer for wiring. The moisture absorption rate of the interlayer insulation layer (cured form of material F) in Comparative Example 4 was 1.2% by mass, and the chloride ion concentration was less than 5 ppm.

[0294] Table 1

[0295]

[0296] In Table 1 above, cases where the moisture absorption rate of the interlayer insulation layer 57 is less than 1.0% by mass are denoted as "Y", and cases where the moisture absorption rate of the interlayer insulation layer 57 exceeds 1.0% by mass are denoted as "N". Table 1 shows that the results of the high-acceleration life tests for Examples 1-6 are all rated A, while the results of the high-acceleration life tests for Comparative Examples 1-4 are all rated B. These results indicate that the insulation reliability of the evaluation sample 50 varies significantly depending on the presence or absence of the interlayer insulation layer 57 with a moisture absorption rate of less than 1.0% by mass.

[0297] Figure 15 This is a graph showing the results of the high-acceleration lifetime test for Example 3 and Comparative Example 2. Figure 13In the diagram, the horizontal axis represents time, and the vertical axis represents the resistance value between the first wiring 55a and the second wiring 55b. Figure 15 In the figures, data 61 is the test result of Example 3, and data 62 is the test result of Comparative Example 2.

[0298] like Figure 15 As shown in Example 3, even after 300 hours from the start of the test, the resistance between the first wiring 55a and the second wiring 55b remained at 1×10⁻⁶. 7 Ω or higher. On the other hand, in Comparative Example 2, the resistance value decreased sharply around 20 hours after the start of the experiment, becoming below 1 × 10 Ω. 7 Ω.

[0299] Figure 16 (a) is a graph obtained by observing the test sample 50 of Example 3 after the above-mentioned high acceleration life test. Figure 16 (b) is a graph obtained by observing the test specimen 50 used in the evaluation of Comparative Example 2 after the above-mentioned high acceleration life test. Figure 16 As shown in (b), in Comparative Example 2, it was confirmed that at least the first wiring 55a and the second wiring 55b were corroded for some reason. On the other hand, as Figure 16 As shown in (b), in Example 3, no obvious corrosion was found in the wiring, etc.

[0300] (Examples 7-13)

[0301] According to the composition shown in Table 1, stir the following components at 25°C for more than 30 minutes, and then filter them through a #200 nylon sieve (pore size: 75μm) to obtain the resin composition (varnish).

[0302] (A-1) Composition: Maleimide compounds represented by the following formula (a mixture of n = 1 to 10, weight-average molecular weight: approximately 15,000 to 20,000)

[0303] [Chemical Formula No. 21]

[0304]

[0305] (A-2) Components: A mixture of maleimide compounds represented by the following formula

[0306] [Chemical Formula No. 22]

[0307]

[0308] [Chemical Formula No. 23]

[0309]

[0310] (B) Ingredients: Compounds containing (meth)acryloyl groups (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name: A-DCP)

[0311] (C) Ingredients: Photoradical polymerization initiator (manufactured by BASF, trade name: Irgacure 907)

[0312] (D-1) Ingredient: Silane coupling agent with epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-984S)

[0313] (D-2) Ingredient: Silane coupling agent with epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)

[0314] The resin compositions (varnishes) of each embodiment were evaluated as follows. The results are shown in Table 2.

[0315] <Evaluation of dielectric properties (dielectric constant: Dk, dielectric loss tangent: Df)>

[0316] In the evaluation of the dielectric properties, a benchtop coater was used to apply varnish to copper foil to achieve a dried thickness of 50 μm, and then dried to obtain a resin film (semi-cured). The resulting resin film (semi-cured) was then irradiated with 2000 mJ / cm². 2 UV radiation. A resin film is similarly formed and laminated on the prepared resin film, resulting in a resin film thickness of 300 μm. Then, the copper foil serving as the support is removed by physical peeling or etching to obtain the resin film for evaluation.

[0317] Then, the resin film was cut into test pieces 60 mm long, 2 mm wide, and 0.3 mm thick, and the dielectric properties were determined using the void resonator perturbation method. The measuring instrument used was an Agilent Technologies E8364B vector network analyzer, and the void resonator used was a CP531 (10 GHz with resonator) manufactured by Kanto Electronics Application Development Co., Ltd. The measurement program used was CPMA-V2. The conditions were set as follows: frequency 10 GHz, measurement temperature 25 °C.

[0318] <Determination of moisture absorption rate>

[0319] A varnish was applied to a wafer (6 inches in diameter, 400 μm thick) using a spin coater and dried at 90°C for 5 minutes to form a resin layer. The varnish was applied at 2000 mJ / cm². 2After curing by exposure, the sample was prepared by heating at 180°C for 1 hour. The sample was then placed in a constant temperature and humidity bath (Espec Co., Ltd., trade name: EHS-221MD) at a relative humidity of 85% and a temperature set at 130°C for 200 hours. Then, the temperature and humidity bath was cooled to 50°C, the sample was removed, and a portion of the resin was shaved off from the silicon wafer. The shaved resin was measured using a differential thermal gravimetric analyzer (Hitachi High-Tech Science Co., Ltd., trade name: TG / DTA6300) at a heating rate of 10°C / min, a nitrogen flow rate of 400 mL / min, and a temperature range of 25°C to 150°C. The weight loss rate at 150°C was calculated as the moisture absorption rate.

[0320] <Determination of Elongation>

[0321] The resin film, prepared using the same method as described above, was cut into samples with a length of 30 mm and a width of 5 mm. The elongation at break of the samples was measured using a small benchtop testing machine (manufactured by Shimadzu Corporation, trade name: EZ-S) at a conveying speed of 5 mm / min.

[0322] <Evaluation of the Formative Characteristics of Micro-wiring>

[0323] A varnish was applied to a 6-inch diameter, 400μm thick wafer using a spin coater and dried at 90°C for 5 minutes to form a resin film on the silicon wafer. The spin coating conditions were then adjusted to achieve a 5μm thick resin film after drying. Negative pattern masks with linewidth / spacing (L / S (μm / μm)) of 200 / 200, 100 / 100, 80 / 80, 60 / 60, 50 / 50, 40 / 40, 30 / 30, 20 / 20, 10 / 10, 7 / 7, 5 / 5, 4 / 4, 3 / 3 and via diameters of 50, 40, 30, 20, 10, 7, 5, 4, 3μm were then applied using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd., trade name: EXM-1172-B-∞) at 1000mJ / cm². 2 The sample was then exposed to the next exposure. Further heating was then applied at 100°C for 1 minute to obtain the sample. The obtained sample was then immersed in cyclopentanone at room temperature with shaking for 60 seconds, rinsed with cyclopentanone, and then immersed in isopropanol at room temperature for 5 seconds. Finally, compressed air was used to evaporate the isopropanol.

[0324] Micro-wire formation was assessed using a metal microscope to check for resin film peeling from the wafer, resin film cracks, the presence or absence of cracks (roughness) at the pattern ends, and the presence or absence of residue at the bottom of the pattern after resin development. The minimum L / S and via diameter for which the above defects could not be identified are shown in Table 2.

[0325] <b-HAST Tolerance>

[0326] Form a pattern in the same manner as the high-acceleration life test described above. Then, perform plating such as electroless copper plating or electroplating, and planarize the surface by CMP. In addition, adjust the mask size so that the L / S (μm / μm) is 3 / 3 or 5 / 5.

[0327] Then, spin-coat varnish on the obtained wiring and dry it at 90 °C for 5 minutes. During spin coating, paste polyimide tape on the 55c and 55d parts of the wiring to prevent the resin from being coated, and peel off the polyimide tape after UV curing. Adjust the spin coating conditions so that the film thickness of the resin film is 5 μm. After irradiating UV under the condition of 1000 mJ / cm 2 irradiate UV, heat the resin film at 180 °C for 1 hour to cure it. In addition, there is a resin layer made by the same method as that for forming the pattern between the silicon wafer (diameter 6 inches, thickness 400 μm) as the substrate and the wiring layer.

[0328] Apply a voltage of 3.3 V to the first connecting wiring 55c and the second connecting wiring 55d of the obtained wiring under the conditions of 85% humidity and 130 °C, and leave it for a specified time. Thus, measure the change in the insulation between the first wiring 55a and the second wiring 55b over time. In this test, a resistance value between the first wiring 55a and the second wiring 55b of 1 × 10 6 Ω or more for 300 hours or more is evaluated as "A" (having b-HAST tolerance), and those not meeting the above conditions are evaluated as "B" (without b-HAST tolerance).

[0329] Table 2

[0330]

[0331] Symbol Explanation

[0332] 1 Substrate, 2A - 2D Semiconductor chips, 3A, 3B Underfill, 4 Insulating material, 10 Semiconductor wiring layer laminate, 11 Substrate, 13 Copper wiring, 13A Copper layer, 14 Copper wiring, 14A Copper layer, 15, 16 Barrier metal film, 17, 18 Wiring layer insulation layer, 21 Organic insulation layer, 21a Groove part, 22 Organic insulation layer, 22a Groove part, 100 Semiconductor package, L Line width, S Spacing width.

Claims

1. A resin composition comprising a curable resin, a curing agent, and a coupling agent, but without inorganic fillers, used to form an interlayer insulation layer for contacting fine copper wiring having a linewidth and spacing width of less than 5 μm. The curable resin is a maleimide compound having at least two maleimide groups and a divalent hydrocarbon group. The maleimide compound is a compound represented by the following formula (VIII). In the formula, Z 1 This indicates the presence of a divalent hydrocarbon group with a main chain having four or more carbon atoms. The elongation at break of the cured material with a thickness of 300 μm obtained by curing the resin composition at 180°C for 2 hours was 5–200%. The cured resin composition, after being placed at 130°C and 85% relative humidity for 200 hours, has a moisture absorption rate of less than 1% by mass. The concentration of chloride ions in the cured resin composition is less than 5 ppm.

2. The resin composition according to claim 1, wherein, The hydrocarbon group has 8 or more carbon atoms.

3. The resin composition according to claim 1 or 2, wherein, The curing agent contains a photoradical polymerization initiator.

4. The resin composition according to claim 1 or 2, further comprising a compound having a (meth)acryloyl group.

5. The resin composition according to claim 1 or 2, further comprising a thermoplastic resin.

6. The resin composition according to claim 1 or 2, wherein, The glass transition temperature of the cured material with a thickness of 300 μm obtained by curing the resin composition by heating at 180°C for 2 hours is 120–240°C.

7. The resin composition according to claim 1 or 2, wherein, The cured product with a thickness of 300 μm obtained by curing the resin composition by heating at 180°C for 2 hours has a dielectric constant of less than 3.0 at 10 GHz.

8. The resin composition according to claim 1 or 2, wherein, The resin composition was cured at 180°C for 2 hours to obtain a cured product with a thickness of 300 μm. The 5% weight reduction temperature was above 300°C.

9. A semiconductor wiring layer laminate, comprising: Multiple wiring layers, each comprising an organic insulating layer, copper wiring disposed within the organic insulating layer, and a barrier metal film separating the copper wiring from the organic insulating layer; and Interlayer insulation layer disposed between the plurality of wiring layers in, A portion of the surface of the copper wiring is exposed on one or both main surfaces of the wiring layer, and the interlayer insulation layer is in contact with the exposed surface of the copper wiring. The interlayer insulation layer of the wiring is a cured product of the resin composition according to claim 1 or 2.

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