JP2019210399A - Resin composition, cured film, method for producing patterned cured film, semiconductor element and electronic device - Google Patents

Abstract

To provide a resin composition that can form a cured film that has excellent storage stability at room temperature and excellent adhesion to copper.SOLUTION: A resin composition contains (A) an alkali-soluble resin, (B) a compound having two or more hydrazide groups, and (C) a heat crosslinker.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a cured film, a method for producing a patterned cured film, a semiconductor element, and an electronic device.

  In recent years, with the high integration and miniaturization of semiconductor elements, insulating layers such as surface protective layers and interlayer insulating layers of semiconductor elements are required to have more excellent electrical characteristics, heat resistance, mechanical characteristics, and the like. . A photosensitive resin composition containing an alkali-soluble resin has been developed as a material for forming an insulating layer having such characteristics (see, for example, Patent Documents 1, 2, and 3). These photosensitive resin compositions are applied onto a substrate and dried to form a resin film, and the resin film is exposed and developed to obtain a patterned resin film (patterned resin film). A patterned cured film (patterned cured film) can be formed by heat curing the patterned resin film, and the patterned cured film can be used as an insulating layer.

JP 2008-309885 A JP 2007-57595 A International Publication No. 2010/073948

  As one form of the semiconductor package substrate, there is a form in which wiring is formed of a metal such as copper on an insulating layer. The insulating layer may be composed of a pattern cured film formed through exposure and development of the resin film, but may be composed of a cured film formed only by heat curing of the resin film. If the cured film of the resin composition used for the insulating layer has insufficient adhesion to copper, peeling may occur between the cured film and the copper wiring. And the disconnection resulting from peeling of copper wiring or a package crack may occur. On the other hand, as a method of improving the adhesiveness with copper, there is a method of adding an adhesion assistant having an amino group to the resin composition. However, the resin composition containing an adhesion assistant having an amino group increases in viscosity when stored at room temperature, and it is difficult to obtain a resin film having a predetermined thickness with the resin composition after storage. Sometimes. Therefore, the resin composition used for forming the insulating layer of the semiconductor element is required to satisfy both adhesion to copper and storage stability at room temperature.

  An object of this invention is to provide the resin composition which can form the cured film which is excellent in the storage stability at room temperature, and excellent in the adhesiveness with respect to copper. Another object of the present invention is to provide a cured film, a semiconductor element and an electronic device produced using the resin composition, and a method for producing a patterned cured film using the resin composition.

  One aspect of the present invention provides a resin composition containing (A) an alkali-soluble resin, (B) a compound having two or more hydrazide groups, and (C) a thermal crosslinking agent.

  (A) The alkali-soluble resin may be a resin having a phenolic hydroxyl group. Further, (C) the thermal crosslinking agent may be a compound having 4 or more alkoxymethyl groups.

  The resin composition according to the present invention may further contain (D) a compound that generates an acid by light, and the compound may be an o-quinonediazide compound. The resin composition according to the present invention may further contain (E) an elastomer, and the elastomer may be an acrylic elastomer.

  This invention provides the cured film containing the hardened | cured material of the resin film which consists of the said resin composition in another side surface. The present invention also provides a semiconductor device comprising the cured film as an interlayer insulating layer or a surface protective layer. The present invention further provides an electronic device comprising the semiconductor element.

  In another aspect, the present invention provides a step of coating and drying the resin composition on a part or the entire surface of a substrate to form a resin film, a step of exposing a part or the entire surface of the resin film, Provided is a method for producing a cured pattern film, comprising: a step of developing a resin film with an alkaline aqueous solution to form a pattern resin film; and a step of heating the pattern resin film.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the cured film which is excellent in the storage stability at room temperature, and is excellent in the adhesiveness with respect to copper can be provided. Moreover, according to this invention, the manufacturing method of the cured film produced using this resin composition, a semiconductor element, an electronic device, and the pattern cured film using this resin composition can be provided.

It is the schematic perspective view and schematic end view explaining one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and schematic end view explaining one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and schematic end view explaining one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and schematic end view explaining one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and schematic end view explaining one Embodiment of the manufacturing process of a semiconductor element. It is a schematic sectional drawing which shows one Embodiment of a semiconductor element. It is a schematic sectional drawing which shows one Embodiment of a semiconductor element.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, and the same applies to other similar expressions such as (meth) acrylate.

[Resin composition]
The resin composition of the present embodiment includes (A) an alkali-soluble resin (hereinafter sometimes referred to as “component (A)”), (B) a compound having two or more hydrazide groups (hereinafter referred to as “(B)”. And (C) a thermal crosslinking agent (hereinafter also referred to as “component (C)”).

<(A) component>
The component (A) is a resin that is soluble in an alkaline aqueous solution. The alkaline aqueous solution is an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. Whether the component (A) is soluble in an alkaline aqueous solution can be confirmed, for example, as follows.

  A varnish obtained by dissolving the component (A) in an arbitrary solvent is formed by spin coating on a substrate such as a silicon wafer to form a coating film having a thickness of about 5 μm. This is immersed in either a TMAH aqueous solution, a metal hydroxide aqueous solution or an organic amine aqueous solution at 20 to 25 ° C. As a result, when the coating film can be dissolved uniformly, the component (A) can be regarded as soluble in an alkaline aqueous solution.

  From the viewpoint of solubility in an alkaline aqueous solution, the component (A) is preferably a resin having a phenolic hydroxyl group. Examples of the resin having a phenolic hydroxyl group include polyhydroxystyrene, a hydroxystyrene resin such as a copolymer containing hydroxystyrene as a monomer unit, a polybenzoxazole precursor such as a phenol resin and poly (hydroxyamide), a poly (hydroxyamide), and a poly ( Hydroxyphenylene) ether, and polynaphthol. The component (A) may be composed of only one of these resins, or may be composed of two or more.

  Among these, the component (A) preferably contains a hydroxystyrene-based resin because of its excellent electrical characteristics (insulating properties) and small volume shrinkage during curing.

The hydroxystyrene-based resin can have a structural unit represented by the following general formula (1).

In Formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, a Represents an integer of 0 to 3, and b represents an integer of 1 to 3. The sum of a and b is 5 or less.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. . These alkyl groups may be linear or branched. Examples of the aryl group having 6 to 10 carbon atoms represented by R ² include a phenyl group and a naphthyl group. Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ¹ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group, and a deoxy group. It is done. These alkoxy groups may be linear or branched.

  The hydroxystyrene-based resin can be obtained by polymerizing a monomer or the like that gives the structural unit represented by the general formula (1). Monomers that give the structural unit represented by the general formula (1) include, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenyl. Phenol is mentioned. These monomers can be used alone or in combination of two or more.

  The hydroxystyrene-based resin is not limited by its production method. For example, a monomer having a hydroxyl group protected by protecting the hydroxyl group of the monomer giving the structural unit represented by the general formula (1) with a t-butyl group, an acetyl group or the like. And a monomer having a hydroxyl group protected therein to obtain a polymer, and the obtained polymer is further converted by a known method (such as deprotection under an acid catalyst to convert to a hydroxystyrene-based structural unit). It can be obtained by deprotection.

  The hydroxystyrene-based resin may be a polymer or copolymer consisting only of a monomer that gives the structural unit represented by the general formula (1), and a monomer that gives the structural unit represented by the general formula (1) It may be a copolymer with other monomers. The proportion of the structural unit represented by the general formula (1) is preferably 10 to 100 mol%, more preferably 20 to 97 mol%, based on 100 mol% of the component (A), from the viewpoint of solubility in an aqueous alkali solution. 30 to 95 mol% is more preferable, and 50 to 95 mol% is particularly preferable.

  When the hydroxystyrene resin is a copolymer of a monomer that gives the structural unit represented by the general formula (1) and another monomer, the hydroxystyrene resin is represented by the following general formula (2). It may have a structural unit.

In Formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, c Represents an integer of 0 to 3.

An alkyl group having 1 to 10 carbon atoms represented by R ^4, the aryl group or an alkoxy group having 1 to 10 carbon atoms having from 6 to 10 carbon atoms, can be exemplified the same as ^{R 2,} respectively.

  The alkali-soluble resin having the structural unit represented by the general formula (2) can be obtained by using a monomer that provides the structural unit represented by the general formula (2). Examples of the monomer that gives the structural unit represented by the general formula (2) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, and m-methoxystyrene. And aromatic vinyl compounds such as p-methoxystyrene. These monomers can be used alone or in combination of two or more.

  When the hydroxystyrene-based resin is an alkali-soluble resin having a structural unit represented by the general formula (2), from the viewpoint of water absorption of the cured film, the proportion of the structural unit represented by the general formula (2) is (A 1) -90 mol% is preferable with respect to 100 mol% of component, 3-80 mol% is more preferable, 5-70 mol% is still more preferable, 5-50 mol% is especially preferable.

  When the hydroxystyrene resin is a copolymer of a monomer that gives the structural unit represented by the general formula (1) and another monomer, the hydroxystyrene resin has a structure based on a (meth) acrylic ester. You may have a unit. The (meth) acrylic acid ester may be a compound having an alkyl group or a hydroxyalkyl group.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. (Meth) acrylic acid alkyl esters such as hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate; hydroxymethyl (meth) acrylate, (meth ) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, (meth) acrylic Hydroxyoctyl acid, (meth) acrylic Hydroxy nonyl, and (meth) (meth) acrylic acid hydroxyalkyl esters such as acrylic acid hydroxy decyl. These monomers can be used alone or in combination of two or more.

  When the hydroxystyrene-based resin is an alkali-soluble resin having a structural unit based on (meth) acrylic acid ester, the proportion of the structural unit based on (meth) acrylic acid ester is the component (A) from the viewpoint of mechanical properties of the cured film. 1 to 90 mol% is preferable with respect to 100 mol%, 3 to 80 mol% is more preferable, 5 to 70 mol% is still more preferable, and 5 to 50 mol% is particularly preferable.

  The weight average molecular weight (Mw) of the component (A) is preferably 1000 to 500000, more preferably 2000 to 200000, considering the balance between the solubility in an aqueous alkali solution and the mechanical properties of the cured film. More preferably, it is ˜100,000. Here, Mw is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

<(B) component>
The component (B) is a compound having two or more hydrazide groups, and improves the adhesion of the cured film formed from the resin composition to copper while having the storage stability of the resin composition at room temperature. Is a component that can.

When the component (B) is a compound having two hydrazide groups, it may be a dihydrazide compound represented by the following general formula (3).

  In formula (3), X represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 10 carbon atoms. When X is an alkylene group, from the viewpoint of further improving the adhesion to copper, the number of carbon atoms of the alkylene group is preferably 1-18, more preferably 1-14, and 1-10. More preferably. The alkylene group may be linear, branched or alicyclic. When X is an arylene group, it may be an m-phenylene group or a p-phenylene group from the viewpoint of further improving the adhesion to copper. These alkylene group and arylene group may be substituted with a group (for example, an alkoxy group, a nitro group, etc.) that does not inhibit the effect of the component (B). (B) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B) is 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of achieving both the storage stability of the resin composition at room temperature and the adhesion of the cured film to copper. 10 mass parts is preferable, 0.2-5 mass parts is more preferable, 0.3-3 mass parts is still more preferable.

<(C) component>
The thermal crosslinking agent as component (C) is a compound having a structure that can react with component (A) to form a bridge structure when a cured film is formed by heating the resin film. By using the component (C), the strength of the cured film can be improved. Examples of the component (C) include compounds having a phenolic hydroxyl group, compounds having an alkoxymethyl group, and compounds having an epoxy group.

  The “compound having a phenolic hydroxyl group” here does not include the component (A). The compound having a phenolic hydroxyl group as a thermal crosslinking agent can increase the dissolution rate of the exposed area when developing the resin film with an alkaline aqueous solution, and improve the sensitivity as well as the thermal crosslinking agent. Mw of such a compound having a phenolic hydroxyl group is preferably 2000 or less, more preferably 94 to 2000, more preferably 108 to 2000 in consideration of the balance between solubility in an alkaline aqueous solution and mechanical properties. More preferably, it is particularly preferably 108-1500.

  The component (C) is preferably a compound having an alkoxymethyl group from the viewpoint of excellent effect of preventing melting at the time of curing of the resin film. From the viewpoint of heat resistance and mechanical properties of the cured film, there are four components. A compound having the above alkoxymethyl group is more preferable.

  The compound having 4 or more alkoxymethyl groups is more preferably a compound represented by the following general formula (6) or a compound represented by the following general formula (7) from the viewpoint of heat resistance and chemical resistance. .

In formula (6), R ^{5 to} R ¹⁰ each independently represents an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{5 to} R ¹⁰ are the same as those of R ² . From the viewpoint of reactivity at low temperatures, the alkyl group preferably has 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1. preferable.

In formula (7), R ^{11 to} R ¹⁶ each independently represents an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{11 to} R ¹⁶ are the same as those of R ² . The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 or 2, and particularly preferably 1.

  The content of the component (C) improves the heat resistance of the cured film and reduces the warpage when the cured film is formed on the substrate, from the point of 0.5 to 100 parts by mass of the component (A). 50 mass parts is preferable, 1-40 mass parts is more preferable, and 2-30 mass parts is still more preferable.

<(D) component>
The resin composition of the present embodiment may further contain a compound that generates an acid by light (by receiving light) as the component (D). The component (D) functions as a photosensitizer in the resin composition and can impart photosensitivity to the resin composition. The component (D) has a function of generating acid upon irradiation with light and increasing the solubility of the resin film irradiated with light in the alkaline aqueous solution. As the component (D), a compound generally called a photoacid generator can be used. Specific examples of the component (D) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. (D) A component may consist only of 1 type in these compounds, and may be comprised including 2 or more types. Among these, since the sensitivity is high, the component (D) is preferably an o-quinonediazide compound.

  As the o-quinonediazide compound, for example, a compound obtained by a condensation reaction of o-quinonediazidesulfonyl chloride with a hydroxy compound and / or an amino compound in the presence of a dehydrochlorinating agent can be used.

  Examples of the o-quinonediazide sulfonyl chloride include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6-sulfonyl chloride. It is done.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl). ) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis ( 2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxypheny) ) Propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane and tris (4-hydroxyphenyl) ethane.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

  Among these, from the viewpoint of reactivity when synthesizing an o-quinonediazide compound and from the viewpoint of an appropriate absorption wavelength range when exposing the resin film, 1,1-bis (4-hydroxyphenyl) -1- A condensate of [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride, tris (4-hydroxyphenyl) methane or tris ( It is preferable to use a condensate of 4-hydroxyphenyl) ethane and 1-naphthoquinone-2-diazide-5-sulfonyl chloride.

  Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine and pyridine. Examples of the reaction solvent include dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and N-methylpyrrolidone.

  In the blending of o-quinonediazide sulfonyl chloride with a hydroxy compound and / or amino compound, the total number of moles of hydroxy group and amino group is 0.5 to 1 mole per mole of o-quinonediazide sulfonyl chloride. It is preferable to be blended as described above. A preferable blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 molar equivalent.

  In addition, the preferable reaction temperature of the above-mentioned reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

  The content of the component (D) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. 5-50 mass parts is more preferable, 5-30 mass parts is still more preferable, and it is especially preferable to set it as 5-20 mass parts.

<(E) component>
The resin composition of this embodiment may further contain an elastomer as the component (E). Examples of the component (E) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These can be used individually by 1 type or in combination of 2 or more types. Among these, the component (E) may be an acrylic elastomer because it is excellent in breaking strength and breaking elongation of the cured film.

  The acrylic elastomer may have a structural unit represented by the following general formula (8).

In formula (8), R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents a hydroxyalkyl group having 2 to 20 carbon atoms.

Since the acrylic elastomer has the structural unit represented by the general formula (8), the interaction between the component (A) and the component (E) is improved and the compatibility is improved. Adhesion to copper, mechanical properties and thermal shock resistance can be further improved. From the point that the compatibility with the component (A) and the thermal shock resistance of the cured film can be further improved, R ¹⁸ is preferably a C 2-15 hydroxyalkyl group, more preferably a C 2-10 hydroxyalkyl group. A hydroxyalkyl group having 2 to 8 carbon atoms is more preferable.

Examples of the hydroxyalkyl group having 2 to 20 carbon atoms represented by R ¹⁸ include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, and a hydroxynonyl group. , Hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group (sometimes referred to as hydroxylauryl group), hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxy Examples include octadecyl group, hydroxynonadecyl group and hydroxyeicosyl group. These groups may be linear or branched.

  Monomers that give the structural unit represented by the general formula (8) include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth) acrylate. , Hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, Hydroxydodecyl (meth) acrylate (sometimes referred to as hydroxylauryl (meth) acrylate), hydroxytridecyl (meth) acrylate, hydroxytetradecyl (meth) acrylate, hydroxypentadecyl (meth) acrylate, ( Meta) Acrylic acid hydroxy hexadecyl, (meth) acrylic acid hydroxy heptadecyl, (meth) acrylic acid hydroxy octadecyl, and (meth) hydroxy acrylate nonadecyl and (meth) acrylic acid hydroxy eicosyl. These monomers are used singly or in combination of two or more.

  Among these, from the viewpoint of further improving the compatibility with the component (A) and the elongation at break of the cured film, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ( Hydroxypentyl acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, (meth) It is preferable to use hydroxyundecyl acrylate or hydroxydodecyl (meth) acrylate.

  The component (E) may be an acrylic elastomer composed only of the structural unit represented by the general formula (8), or an acrylic elastomer having a structural unit other than the structural unit represented by the general formula (8). There may be. When the acrylic resin has a structural unit other than the structural unit represented by the general formula (8), the proportion of the structural unit represented by the general formula (8) in the acrylic resin is based on the total amount of the component (E). The content is preferably 0.1 to 30 mol%, more preferably 0.3 to 20 mol%, and still more preferably 0.5 to 10 mol%. When the composition ratio of the structural unit represented by the general formula (8) is 0.1 to 30 mol%, compatibility with the component (A) and thermal shock resistance of the cured film can be further improved. .

The acrylic elastomer may further have a structural unit represented by the following general formula (9).

In formula (9), R ¹⁹ represents a hydrogen atom or a methyl group, R ²⁰ represents a monovalent organic group having a primary, secondary or tertiary amino group, and the component (E) is represented by the general formula (9) In the resin film, the dissolution inhibition of the unexposed portion of the resin film with respect to the developer and the adhesion to the metal substrate can be further improved.

  Monomers that give an acrylic elastomer having a structural unit represented by the general formula (9) include, for example, aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meta ) Acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) ) Acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2 , 6,6-tetramethyl Peridin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate and 2- (piperidine- 4-yl) ethyl (meth) acrylate. These monomers are used alone or in combination of two or more.

式（１０）中、Ｙは炭素数１〜５のアルキレン基を示し、Ｒ^２１〜Ｒ^２５は各々独立に水素原子又は炭素数１〜２０のアルキル基を示し、ｅは０〜１０の整数を示す。 Among these, from the viewpoint of further improving the adhesion of the cured film to the substrate and the compatibility with the component (A), in the general formula (9), R ²⁰ is a monovalent represented by the following general formula (10). The organic group is preferably.

In formula (10), Y represents an alkylene group having 1 to 5 carbon atoms, R ^{21 to} R ²⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and e represents an integer of 0 to 10 Show.

In the general formula (9), examples of the monomer that gives a structural unit in which R ²⁰ is a monovalent organic group represented by the general formula (10) include piperidin-4-yl (meth) acrylate, 1- Methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) ) Acrylate, (piperidin-4-yl) methyl (meth) acrylate and 2- (piperidin-4-yl) ethyl (meth) acrylate. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Each is made by Hitachi Chemical Co., Ltd.) and is preferable because it is commercially available.

  When the component (E) has a structural unit represented by the general formula (9), the proportion of the structural unit represented by the general formula (9) is compatible with the component (A) and soluble in the developer. From the above point, it is preferably 0.3 to 10 mol%, more preferably 0.4 to 6 mol%, and more preferably 0.5 to 5 mol%, based on the total amount of component (E). More preferably it is.

The acrylic elastomer may further have a structural unit represented by the following general formula (11). When the acrylic elastomer has the structural unit represented by the general formula (11), the thermal shock resistance of the cured film can be further improved.

In formula (11), R ²⁶ represents a hydrogen atom or a methyl group, and R ²⁷ represents an alkyl group having 4 to 20 carbon atoms.

Examples of the alkyl group having 4 to 20 carbon atoms represented by R ²⁷ include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group (also called a lauryl group And tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group. These groups may be linear or branched.

In general formula (11), from the viewpoints of alkali solubility, thermal shock resistance, and compatibility with component (A), R ²⁷ is preferably an alkyl group having 4 to 16 carbon atoms, and having 4 to 12 carbon atoms. An alkyl group is more preferable, and an alkyl group having 4 carbon atoms (n-butyl group) is more preferable.

  Examples of the monomer represented by the general formula (11) include, for example, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, Nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (sometimes called lauryl (meth) acrylate), tridecyl (meth) acrylate, (meta And tetradecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate and eicosyl (meth) acrylate. These monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving the elongation at break of the cured film and lowering the elastic modulus, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate). preferable.

  When the component (E) has a structural unit represented by the general formula (11), the proportion of the structural unit represented by the general formula (11) is 50 to 93 mol% with respect to the total amount of the component (E). It is preferable that it is, It is more preferable that it is 55-85 mol%, It is still more preferable that it is 60-80 mol%. When the proportion of the structural unit represented by the general formula (11) is 50 to 93 mol%, the thermal shock resistance of the cured film can be further improved.

The acrylic elastomer may further have a structural unit represented by the following general formula (12). When the acrylic elastomer has the structural unit represented by the general formula (12), the alkali solubility of the exposed portion of the resin film can be further improved.

In formula (12), R ²⁸ represents a hydrogen atom or a methyl group.

  Examples of the monomer that gives the structural unit represented by the general formula (12) include acrylic acid and methacrylic acid.

  When the component (E) has a structural unit represented by the general formula (12), the proportion of the structural unit represented by the general formula (12) is 5 to 35 mol% with respect to the total amount of the component (E). It is preferably 10 to 30 mol%, more preferably 15 to 25 mol%. When the compositional ratio of the structural unit represented by the general formula (12) is 5 to 35 mol%, the compatibility with the component (A) and the alkali solubility of the exposed portion can be further improved.

  The acrylic elastomer includes, for example, a monomer that gives a structural unit represented by the general formula (8), and a structural unit represented by the general formula (9), (11), or (12) that is added as necessary. It is obtained by blending a monomer that gives water, stirring in a solvent such as ethyl lactate, toluene and isopropanol, and heating as necessary.

  The monomer used for the synthesis of the acrylic elastomer may further contain a monomer other than the monomer that gives the structural unit represented by the general formulas (8), (9), (11), and (12).

  Examples of such monomers include N- (meth) acryloyloxyethyl hexahydrophthalimide, 1,4-cyclohexanedimethanol mono (meth) acrylate, benzyl (meth) acrylate, and 4-methylbenzyl (meth) acrylate. , Esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid , Maleic anhydride, monomethyl maleate, maleic acid Aminoethyl, maleic acid monoesters such as maleic acid monoisopropyl, fumaric acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These monomers are used alone or in combination of two or more.

  (E) It is preferable that Mw of a component is 2000-100000, It is more preferable that it is 3000-60000, It is further more preferable that it is 5000-50000, It is especially preferable that it is 10000-40000. When the Mw of the component (E) is 2000 or more, the thermal shock resistance of the cured film can be further improved, and when it is 100000 or less, the compatibility with the component (A) and the developability of the resin film can be further improved.

  The content of the component (E) is determined from the viewpoint of the balance between the alkali solubility of the exposed portion and the alkali dissolution inhibitor of the unexposed portion in the resin film, the adhesion of the cured film to the metal substrate, and the thermal shock resistance. 1-50 mass parts is preferable with respect to 100 mass parts of components, 3-30 mass parts is more preferable, and 5-20 mass parts is still more preferable.

<Other ingredients>
In addition to the components (A) to (E), the resin composition of the present embodiment includes a solvent, a compound that generates an acid upon heating, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a surfactant or leveling. You may contain components, such as an agent.

(solvent)
By containing the solvent, the resin composition of this embodiment can be easily applied on the substrate and can form a coating film having a uniform thickness. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N , N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples include monobutyl ether and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. Among these, it is preferable to use ethyl lactate or propylene glycol monomethyl ether acetate as a solvent from the viewpoint of solubility and uniformity of the coating film.

(Compound that generates acid by heating)
By using a compound that generates an acid by heating, it becomes possible to generate an acid when the resin film is heated, and the reaction between the component (A) and the component (C), that is, the thermal crosslinking reaction is promoted and cured. The heat resistance of the film can be improved. Moreover, since the compound which produces | generates an acid by heating generate | occur | produces an acid also by light irradiation, the solubility to the alkaline aqueous solution of the exposure part in a resin film increases. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed portion and the exposed portion in the resin film is further increased, and the resolution is further improved.

  The compound that generates an acid by such heating may be, for example, a compound that generates an acid by heating to 50 to 250 ° C. Specific examples of the compound that generates an acid upon heating include a salt formed from a strong acid such as an onium salt and a base, and imide sulfonate.

  When using the compound which produces | generates an acid by heating, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, 0.2-20 mass parts is more preferable, 0.5 More preferably, it is 10 mass parts.

(Dissolution promoter)
By blending a dissolution accelerator in the resin composition, the dissolution rate of the exposed area when the resin film is developed with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. A conventionally well-known thing can be used as a dissolution promoter. Specific examples of the dissolution accelerator include compounds having a carboxyl group, a sulfonic acid or a sulfonamide group.

  Content in the case of using a dissolution promoter can be determined by the melt | dissolution rate with respect to aqueous alkali solution, for example, can be 0.01-30 mass parts with respect to 100 mass parts of (A) component.

(Dissolution inhibitor)
The dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Examples of the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. In the case of using a dissolution inhibitor, the content is preferably 0.01 to 20 parts by mass, and 0.01 to 15 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of sensitivity and the allowable range of development time. More preferably, 0.05-10 mass parts is still more preferable.

(Coupling agent)
By mix | blending a coupling agent with a resin composition, the adhesiveness with the board | substrate of the cured film formed can be improved more. Examples of the coupling agent include organic silane compounds and aluminum chelate compounds. Examples of the organic silane compound include KBM-403, KBM-803, and KBM-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using a coupling agent, 0.5-10 mass parts is more preferable.

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent into the resin composition, the coatability can be further improved. Specifically, for example, by containing a surfactant or a leveling agent, striation (film thickness unevenness) can be further prevented, and developability can be further improved. Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Examples of commercially available products include Megafac F-171, F-565, and RS-78 (manufactured by DIC Corporation, trade names).

  0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using surfactant or a leveling agent, 0.01-3 mass parts is more preferable.

  The resin composition of this embodiment can be developed using an aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH). By using the resin composition of the present embodiment as a photosensitive resin, it is possible to form a cured pattern film having sufficiently high developability and good adhesion to copper and thermal shock.

[Curing film]
The cured film of the present embodiment includes a cured product of the resin film made of the above-described resin composition. The cured film is obtained by heating the above-described resin composition. The cured film may have a pattern. When the resin composition contains the component (D) in addition to the components (A), (B) and (C), the patterned resin film can be formed by exposing and developing the resin film. A patterned cured film is obtained by heating the pattern resin film.

[Method for producing patterned cured film]
The pattern cured film manufacturing method of the present embodiment includes a step of applying and drying the resin composition described above on a part or the entire surface of a substrate to form a resin film (application / drying (film formation) step), A step of exposing part or the entire surface (exposure step), a step of developing the exposed resin film with an alkaline aqueous solution to form a pattern resin film (development step), and a step of heating the pattern resin film (heat treatment step) ). Hereinafter, each step will be described.

<Application / drying (film formation) process>
First, the resin composition of this embodiment is applied on a substrate and dried to form a resin film. In this step, first, the resin composition of the present embodiment is spin-coated using a spinner or the like on a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride. Then, a coating film is formed. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.1-40 micrometers. The substrate on which this coating film has been formed is dried using a hot plate, oven, or the like. Although there is no restriction | limiting in particular in drying temperature and drying time, It is preferable to carry out for 1 to 7 minutes at 80-140 degreeC. Thereby, a resin film is formed on the support substrate. Although there is no restriction | limiting in particular in the thickness of a resin film, It is preferable that it is 0.1-40 micrometers.

<Exposure process>
Next, in the exposure step, the resin film formed on the substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the resin composition of this embodiment, since the component (A) is highly transparent to g-line, h-line, and i-line, any or all of g-line, h-line, and i-line may be used for irradiation.

<Development process>
In the development step, the exposed portion of the resin film after the exposure step is removed with a developer, whereby the resin film is patterned and a patterned resin film is obtained. As the developer, for example, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, TMAH or the like is preferably used. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, an alcohol or a surfactant can be added to the developer. Each of these can be blended in the range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer. When developing using a developing solution, for example, the developing solution is arranged on a resin film by a method such as shower development, spray development, immersion development, paddle development, and the like, and the temperature is 18 to 40 ° C., and 30 to 360. Leave for seconds. After leaving, the pattern resin film is washed by washing with water and spin drying.

<Heat treatment process>
In the heat treatment step, the pattern cured film can be formed by heat treating the pattern resin film. The heating temperature in the heat treatment step is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 230 ° C. or lower, from the viewpoint of sufficiently preventing damage to the semiconductor device due to heat.

  The heat treatment can be performed using an oven such as a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the pattern can be prevented. Since the above-mentioned preferable heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the semiconductor device can be reduced. Therefore, an electronic device can be manufactured with a high yield by using the method for manufacturing a patterned cured film of the present embodiment. It also leads to energy savings in the process. Furthermore, according to the positive photosensitive resin composition of the present embodiment, the volumetric shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide or the like is small, so that a reduction in dimensional accuracy can be prevented.

  The heat treatment time in the heat treatment step may be a time sufficient for the resin composition to cure, but is preferably about 5 hours or less in view of work efficiency.

  The heat treatment can be performed using a microwave curing device or a variable frequency microwave curing device in addition to the above-described oven. By using these devices, it is possible to effectively heat only the photosensitive resin film while keeping the temperature of the substrate and the semiconductor device at, for example, 200 ° C. or less (J. Photopolym. Sci. Technol., 18, 327-332 (2005)).

  According to the manufacturing method of the pattern cured film of this embodiment mentioned above, the pattern cured film which is excellent in adhesiveness and thermal shock property with sufficiently high developability and resolution can be obtained. The patterned cured film of the present embodiment has particularly high adhesion to copper.

[Interlayer insulation layer, surface protective layer]
The cured film of this embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor element.

[Semiconductor element]
The semiconductor element of this embodiment has the interlayer insulation layer or surface protective layer of this embodiment. The semiconductor element of the present embodiment is not particularly limited, but means a memory, a package, or the like having a multilayer wiring structure, a rewiring structure, or the like.

  An example of a semiconductor element manufacturing process will be described with reference to the drawings. 1 to 5 are a schematic perspective view and a schematic end view showing an embodiment of a manufacturing process of a semiconductor device having a multilayer wiring structure. 1 to 5, (a) is a schematic perspective view, and (b) is a schematic end view showing Ib-Ib to Vb-Vb end surfaces in (a), respectively.

  First, the structure 100 shown in FIG. 1 is prepared. The structure 100 includes a semiconductor substrate 1 such as a Si substrate having circuit elements, a protective film 2 such as a silicon oxide film covering the semiconductor substrate 1 and having a predetermined pattern from which the circuit elements are exposed, and exposed circuit elements. A first conductor layer 3 formed thereon, and an interlayer insulating layer 4 made of polyimide resin or the like formed on the protective film 2 and the first conductor layer 3 by a spin coat method or the like are provided.

  Next, a photosensitive resin layer 5 having a window portion 6A is formed on the interlayer insulating layer 4 to obtain a structure 200 shown in FIG. The photosensitive resin layer 5 is formed, for example, by applying a photosensitive resin such as chlorinated rubber, phenol novolac, polyhydroxystyrene, or polyacrylate ester by a spin coating method. The window 6A is formed so that a predetermined portion of the interlayer insulating layer 4 is exposed by a known photolithography technique.

  After the interlayer insulating layer 4 is etched to form the window 6B, the photosensitive resin layer 5 is removed to obtain the structure 300 shown in FIG. For etching the interlayer insulating layer 4, dry etching means using a gas such as oxygen or carbon tetrafluoride can be used. By this etching, the portion of the interlayer insulating layer 4 corresponding to the window portion 6A is selectively removed, and the interlayer insulating layer 4 provided with the window portion 6B so that the first conductor layer 3 is exposed is obtained. Next, the photosensitive resin layer 5 is removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

  Furthermore, the 2nd conductor layer 7 is formed in the part corresponding to the window part 6B, and the structure 400 shown in FIG. 4 is obtained. A known photolithography technique can be used to form the second conductor layer 7. As a result, the second conductor layer 7 and the first conductor layer 3 are electrically connected.

  Finally, the surface protective layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain the semiconductor element 500 shown in FIG. In the present embodiment, the surface protective layer 8 is formed as follows. First, the resin composition described above is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, after irradiating light through a mask on which a pattern corresponding to the window portion 6C is drawn at a predetermined portion, the exposed resin film is developed with an alkaline aqueous solution to form a patterned resin film. Thereafter, the pattern resin film used as the surface protective layer 8 is formed by curing the pattern resin film by heating. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, etc., and the semiconductor element 500 using the surface protective layer 8 of the present embodiment is reliable. Excellent.

  In the above-described embodiment, a method for manufacturing a semiconductor device having a two-layer wiring structure has been described. However, when a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer. Can do. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. In the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed using the resin composition of the present embodiment. The electronic device of the present embodiment is not limited to one having a surface protective layer, a cover coat layer, or an interlayer insulating layer formed using the above-described resin composition, and can have various structures.

  6 and 7 are schematic cross-sectional views showing an embodiment of a semiconductor device having a rewiring structure. Since the resin composition of this embodiment is excellent in stress relaxation property, adhesiveness, and the like, it can be used in a semiconductor element having a rewiring structure as shown in FIGS.

  FIG. 6 is a schematic cross-sectional view showing a wiring structure as one embodiment of a semiconductor element. A semiconductor element 600 shown in FIG. 6 includes a silicon substrate 23, an interlayer insulating layer 11 provided on one side of the silicon substrate 23, and an Al having a pattern including a pad portion 15 formed on the interlayer insulating layer 11. A wiring layer 12, an insulating layer 13 (for example, a P-SiN layer) and a surface protective layer 14, which are sequentially stacked on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and a surface protective layer 14 in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14 and the surface of the core 18 opposite to the surface protective layer 14. And a rewiring layer 16 extending on the surface protective layer 14. Furthermore, the semiconductor element 600 is formed so as to cover the surface protective layer 14, the core 18, and the rewiring layer 16, and a cover coat layer 19 in which an opening is formed in a portion of the rewiring layer 16 on the core 18. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the layer 19, the collar 21 that holds the conductive ball, and the cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is formed of solder, gold or the like. The underfill 22 is provided to relieve stress when the semiconductor element 600 is mounted.

  In the semiconductor element 700 of FIG. 7, an Al wiring layer (not shown) and an Al wiring layer pad portion 15 are formed on a silicon substrate 23, and an insulating layer 13 is formed on the Al wiring layer. A surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.

  6 and 7, the resin composition is used as a material for forming not only the interlayer insulating layer 11 and the surface protective layer 14, but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. can do. The pattern cured film using the resin composition of the present embodiment is excellent in adhesion with a metal layer such as the Al wiring layer 12 or the rewiring layer 16 or a sealing agent, and has a high stress relaxation effect. A semiconductor element in which the film is used for an interlayer insulating layer 11, a surface protective layer 14, a cover coat layer 19, a core 18, a collar 21 such as solder, an underfill 22 used in a flip chip, etc., is extremely excellent in reliability. Become.

  The resin composition of this embodiment is preferably used for the interlayer insulating layer 11, the surface protective layer 14, and / or the cover coat layer 19 of the semiconductor element having the rewiring layer 16 in FIGS.

  The thicknesses of the interlayer insulating layer 11, the surface protective layer 14, and the cover coat layer 19 are preferably 3 to 20 μm, and more preferably 5 to 15 μm.

[Electronic device]
The electronic device of this embodiment has the semiconductor element of this embodiment. The electronic device includes the above-described semiconductor element, and examples thereof include a mobile phone, a smartphone, a tablet terminal, a personal computer, and a hard disk suspension.

  As described above, since the resin composition of the present embodiment has excellent storage stability at room temperature, it can be used for a long time without wasting the resin composition. And since the cured film formed with the resin composition of this embodiment is excellent in adhesiveness with copper, it can provide the semiconductor element and electronic device excellent in reliability.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

  The materials used in this example are shown below.

[(A) component]
100 parts by mass of A1: 4-tert-butoxystyrene and styrene in a molar ratio of 80:20 were prepared in total, dissolved in 150 parts by mass of propylene glycol monomethyl ether, and the reaction temperature was 70 ° C. in a nitrogen atmosphere. The mixture was stirred for 10 hours with 4 parts by mass of azobisisobutyronitrile at a stirring speed of about 160 rpm for polymerization. Thereafter, sulfuric acid was added to the reaction solution, the reaction temperature was kept at 90 ° C., and the reaction was carried out for 10 hours. The p-tert-butoxystyrene was deprotected and converted to p-hydroxystyrene. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and a p-hydroxystyrene / styrene copolymer A1 was obtained. The Mw in terms of polystyrene of this copolymer A1 was 10,000. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and styrene was 80:20.
A2: A p-hydroxystyrene homopolymer A2 was obtained in the same manner as the synthesis of A1, except that only 100 parts by mass of p-tert-butoxystyrene was dissolved in 150 parts by mass of propylene glycol monomethyl ether. The Mw of the homopolymer A2 was 10,000.
A3: Copolymer of p-hydroxystyrene / methyl methacrylate = 50/50 (molar ratio) (Mw10000, manufactured by Maruzen Petrochemical Co., Ltd., trade name “Marcalinker CMM”)

Mw was calculated | required by standard polystyrene conversion using the gel permeation chromatography (GPC) method, respectively. Specifically, Mw was measured with the following apparatus and conditions.
(measuring device)
Detector: “L4000UV” manufactured by Hitachi, Ltd.
Pump: “L6000” manufactured by Hitachi, Ltd.
Column: Gelpack GL-S300MDT-5 × 2 Data processor: “Chromatopack C-R4A” manufactured by Shimadzu Corporation
(Measurement condition)
Eluent: Tetrahydrofuran (THF) containing LiBr (0.03 mol / L) and H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min Measurement wavelength: UV 270 nm
Measurement sample: A sample solution in which 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] was added to 0.5 mg of the sample was used.

[Component (B)]
B1: Adipic acid dihydrazide B2: Isophthalic acid dihydrazide

[Component (C)]
C1: Compound in which R ^{5 to} R ^{10 in} the general formula (6) are all methyl groups (hexakis (methoxymethyl) melamine, manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30HM”)
C2: Compound in which R ^{11 to} R ^{16 in} the general formula (7) are all methyl groups (Honshu Chemical Co., Ltd., trade name “HMOM-TPPA”)

[(D) component]
D1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Esters (Esterification rate of about 90%, manufactured by Daitokemix Co., Ltd., trade name “PA28”)

[(E) component]
E1: In a 100 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 55 g of ethyl lactate was weighed, and separately weighed monomers (n-butyl acrylate (BA) 34.7 g, lauryl acrylate ( LA) 2.2 g, acrylic acid (AA) 3.9 g, hydroxybutyl acrylate (HBA) 2.6 g and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) (Trade name “FA-711MM”) 1.7 g) and 0.29 g of azobisisobutyronitrile (AIBN) were added. While stirring at room temperature with a stirring speed of about 160 rpm, nitrogen gas was passed at a flow rate of 400 mL / min for 30 minutes to remove dissolved oxygen. Thereafter, the inflow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65 ° C. in about 25 minutes in a constant temperature water bath. A polymerization reaction was carried out while maintaining the same temperature for 10 hours to obtain an elastomer E1. The polymerization rate at this time was 99%. Moreover, Mw of E1 was about 22000. The molar ratio of monomers in the elastomer E1 is as follows.
BA / LA / AA / HBA / FA711MM = 75.5 / 2.5 / 15/5/2 (mol%)
E2: Elastomer E2 was obtained by carrying out the same polymerization reaction as E1 except that the amount of monomer was changed. The polymerization rate at this time was 99%. Moreover, Mw of E2 was about 15000. The molar ratio of monomers in the elastomer E2 is as follows.
BA / LA / AA / HBA / FA711MM = 65.0 / 5.0 / 20/5/5 (mol%)

[Component (F): Adhesion aid having an amino group]
F1: 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-903M”)

(Examples 1-7 and Comparative Examples 1-2)
(A)-(C) component of the compounding quantity (mass part) shown in Table 1, 120 mass parts of ethyl lactate as a solvent, and 2 mass parts of 50% methanol solutions of urea propyltriethoxysilane as a coupling agent, This was pressure filtered using a 1 μm pore Teflon (registered trademark) filter to prepare resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2.

<Evaluation of resin composition>
(Viscosity change rate)
1.1 mL of the resin composition was weighed, and the initial viscosity of the resin composition was measured using an E-type viscometer. Subsequently, after storing the resin composition at room temperature for 2 weeks, the viscosity was measured, and the change rate of the viscosity after storage with respect to the initial viscosity was calculated.

(Thickness change rate)
The resin composition was spin-coated on a 6-inch silicon wafer and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of 11 to 13 μm. Subsequently, after storing the resin composition at room temperature for 2 weeks, a resin film was formed under the same conditions. The rate of change in the thickness of the resin film after storage relative to the thickness of the resin film before storage was calculated.

(Cu adhesion strength)
Using a roughening agent (trade name “CZ8101” manufactured by MEC Co., Ltd.), a 35 μm thick copper foil whose surface was roughened was prepared. Subsequently, the resin composition was spin-coated on the roughened surface of the copper foil and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of 11 to 13 μm. Then, using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name “μ-TF”), heat treatment was performed in nitrogen at a temperature of 230 ° C. (temperature increase time: 1.5 hours) for 2 hours to obtain a cured film. Got. The test piece which wet-etched this so that the width | variety of copper foil might be 5 mm was produced. A part of the copper foil is peeled off from the test piece and fixed to a jig of Autograph (manufactured by Shimadzu Corporation, trade name “Autograph AGS-H100N”), and 50 mm / min at room temperature (20 to 25 ° C.). The load (kN / m) when the copper foil was peeled off from the cured film in the vertical direction was measured as the peel strength. It means that the adhesiveness with respect to copper is so favorable that a numerical value is large.

  As shown in Table 1, the resin composition containing the components (A), (B), and (C) forms a cured film having higher adhesion strength to copper than the resin composition containing no component (B). The change in viscosity and film thickness after storage at room temperature was small.

(Examples 8 to 15 and Comparative Examples 3 to 4)
Components (A) to (F) in the compounding amounts (parts by mass) shown in Table 2, 120 parts by mass of ethyl lactate as the solvent, and 2 parts by mass of 50% methanol solution of urea propyltriethoxysilane as the coupling agent This was subjected to pressure filtration using a 1 μm pore Teflon (registered trademark) filter to prepare photosensitive resin compositions of Examples 8 to 15 and Comparative Examples 3 to 4.

<Evaluation of photosensitive resin composition>
About the photosensitive resin composition of Examples 8-15 and Comparative Examples 3-4, the viscosity change rate, the film thickness change rate, and Cu adhesion strength were evaluated similarly to evaluation of the resin composition mentioned above.

(Sensitivity, resolution)
The photosensitive resin composition was spin-coated on a 35 μm-thick copper foil whose surface was subjected to a roughening treatment (a roughening treatment agent (CZ8101) manufactured by MEC Co., Ltd.), heated at 120 ° C. for 3 minutes, A resin film having a thickness of 11 to 13 μm was formed. Next, the i-line stepper (product name “FPA-3000iW” manufactured by Canon Inc., trade name “FPA-3000iW”) is applied to the resin film through a mask having a square hole pattern of 1 μm × 1 μm to 100 μm × 100 μm ( (365 nm). Reduced projection exposure was performed. Exposure amount was carried out while changing to 100~1520mJ / cm ² by 20mJ / cm ^2. After the exposure, development was performed using a 2.38% aqueous solution of TMAH, and then rinsed with water to obtain a patterned resin film. The minimum exposure amount that can form a square hole pattern of 100 μm × 100 μm was defined as sensitivity. Further, the minimum size (length of one side) of the open square hole patterns within the above exposure amount range was used as an index of resolution. The smaller the sensitivity and resolution, the better.

(Sensitivity change rate)
A patterned resin film was formed under the above conditions using the resin composition, and the initial sensitivity was measured. Next, after storing the resin composition at room temperature for 2 weeks, a patterned resin film was formed under the same conditions, and the sensitivity was measured. The rate of change in sensitivity after storage relative to the initial sensitivity was calculated.

  As shown in Table 2, the photosensitive resin composition in which the components (A), (B) and (C) were further blended with the components (D) and (E), the component (B) Compared with the photosensitive resin composition which does not contain, the cured film with the high adhesive strength with respect to copper was able to be formed, and the change of the viscosity after a storage at room temperature, a film thickness, and the sensitivity was small.

  From the above, it was confirmed that the resin composition of the present invention has excellent storage stability at room temperature and can form a cured film having excellent adhesion to copper.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... 1st conductor layer, 4 ... Interlayer insulation layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window part, 7 ... 2nd conductor layer, 8 ... Surface protection 11 ... Interlayer insulating layer, 12 ... Al wiring layer, 13 ... Insulating layer, 14 ... Surface protective layer, 15 ... Pad part, 16 ... Re-wiring layer, 17 ... Conductive ball, 18 ... Core, 19 ... Cover coat Layer, 20 ... barrier metal, 21 ... color, 22 ... underfill, 23 ... silicon substrate, 24 ... connecting portion, 100, 200, 300,400 ... structure, 500,600,700 ... semiconductor element.

Claims (11)

  A resin composition containing (A) an alkali-soluble resin, (B) a compound having two or more hydrazide groups, and (C) a thermal crosslinking agent.   The resin composition according to claim 1, wherein the (A) alkali-soluble resin is a resin having a phenolic hydroxyl group.   The resin composition according to claim 1 or 2, wherein the (C) thermal crosslinking agent is a compound having four or more alkoxymethyl groups.   (D) The resin composition as described in any one of Claims 1-3 which further contains the compound which produces | generates an acid by light.   The resin composition according to claim 4, wherein the compound (D) that generates an acid by light is an o-quinonediazide compound.   (E) The resin composition as described in any one of Claims 1-5 which further contains an elastomer.   The resin composition according to claim 6, wherein the (E) elastomer is an acrylic elastomer.   The cured film containing the hardened | cured material of the resin film which consists of a resin composition as described in any one of Claims 1-7.   A semiconductor element comprising the cured film according to claim 8 as an interlayer insulating layer or a surface protective layer.   An electronic device comprising the semiconductor element according to claim 9. Applying and drying the resin composition according to any one of claims 4 to 7 on a part or the entire surface of a substrate to form a resin film;
A step of exposing a part or the entire surface of the resin film, a step of developing the resin film after exposure with an alkaline aqueous solution to form a patterned resin film,
Heating the pattern resin film;
A method for producing a patterned cured film.

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