WO2020066137A1 - Resin composition, cured film, photosensitive resin composition, pattern cured film and manufacturing method therefor, semiconductor element, and electronic device - Google Patents

Abstract

Disclosed is a resin composition including an alkali-soluble resin, a thermal crosslinking agent, and an elastomer, wherein the alkali-soluble resin includes a resin that has an alicyclic ring. Also disclosed is a photosensitive resin composition including an alkali-soluble resin, a thermal crosslinking agent, an elastomer, and a compound that generates an acid using light, wherein the alkali-soluble resin includes a resin that has an alicyclic ring.

Description

Resin composition, cured film, photosensitive resin composition, cured pattern film and method for producing the same, semiconductor element, and electronic device

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

In recent years, with high integration and miniaturization of semiconductor devices, insulating layers such as interlayer insulating layers and surface protective layers of semiconductor devices have improved heat resistance (thermal expansion coefficient, etc.) and mechanical properties (breaking strength, breaking elongation). Etc.) are required. As a material for forming an insulating layer having such characteristics, a photosensitive resin composition containing an alkali-soluble resin has been developed (for example, see Patent Documents 1, 2, and 3). A resin film is formed by applying and drying these photosensitive resin compositions on a substrate, and a pattern resin film (pattern-formed resin film) can be obtained by exposing and developing the resin film. Then, by heating and curing the pattern resin film, a pattern cured film (patterned cured film) can be formed, and the pattern cured film can be used as an insulating layer. Moreover, these photosensitive resin compositions have the advantage that they can be cured by heating at a low temperature in the step of forming a pattern cured film.

JP 2008-309885 A JP 2007-055755 A International Publication No. 2010/073948

By the way, a cured film (patterned cured film) used as an insulating layer of a semiconductor element has a problem of transmission loss when used in a high-frequency region. Therefore, from the viewpoint of reducing transmission loss, a material having a low dielectric loss tangent is desired.

Accordingly, an object of the present invention is to provide a resin composition capable of sufficiently reducing the dielectric loss tangent.

の 一 One aspect of the present invention provides a resin composition containing an alkali-soluble resin, a thermal crosslinking agent, and an elastomer, wherein the alkali-soluble resin includes a resin having an alicyclic ring. By using such a resin composition, the dielectric loss tangent of a cured product of the resin composition can be sufficiently reduced.

The resin having an alicyclic ring may be a resin having a phenolic hydroxyl group.

The elastomer may include an acrylic elastomer.

に お い て In another aspect, the present invention provides a cured film containing a cured product of the above resin composition.

In another aspect, the present invention provides a photosensitive composition comprising an alkali-soluble resin, a thermal crosslinking agent, an elastomer, and a compound that generates an acid by light, wherein the alkali-soluble resin includes a resin having an alicyclic ring. Provided is a resin composition. By using such a photosensitive resin composition, the dielectric loss tangent of a cured product of the photosensitive resin composition can be sufficiently reduced.

に お い て In another aspect, the present invention provides a cured pattern film having a pattern, the pattern including a cured product of the above-described photosensitive resin composition.

In another aspect, the present invention provides a step of forming a resin film by applying the photosensitive resin composition to a part or the whole of a substrate and drying the same, a step of exposing a part of the resin film, Provided is a method for manufacturing a cured pattern film, comprising: a step of forming a patterned resin film by developing a later resin film with a developer; and a step of heating the patterned resin film to obtain a cured pattern film.

に お い て In another aspect, the present invention provides a semiconductor device including the above-described cured pattern film as an interlayer insulating layer or a surface protection layer.

に お い て In another aspect, the present invention provides an electronic device including the above semiconductor element.

According to the present invention, a resin composition and a photosensitive resin composition capable of sufficiently reducing the dielectric loss tangent are provided. The photosensitive resin compositions according to some embodiments are also excellent in resolution. Further, according to the present invention, there is provided a cured film using such a resin composition. Further, according to the present invention, there is provided a pattern cured film and a method for producing the same, a semiconductor element, and an electronic device using such a photosensitive resin composition.

It is the schematic explaining one Embodiment of the manufacturing process of a semiconductor element, (a) is a schematic perspective view, (b) is a schematic end view which shows the Ib-Ib end surface in (a). It is a schematic diagram explaining one embodiment of a manufacturing process of a semiconductor element, (a) is a schematic perspective view, (b) is a schematic end view showing IIb-IIb end face in (a). It is a schematic diagram explaining one embodiment of a manufacturing process of a semiconductor element, (a) is a schematic perspective view, (b) is a schematic end view showing IIIb-IIIb end face in (a). It is the schematic explaining one Embodiment of the manufacturing process of a semiconductor element, (a) is a schematic perspective view, (b) is a schematic end view which shows the IVb-IVb end surface in (a). It is the schematic explaining one Embodiment of the manufacturing process of a semiconductor element, (a) is a schematic perspective view, (b) is a schematic end view which shows the Vb-Vb end surface in (a). FIG. 2 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device. FIG. 2 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

「“ (Meth) acrylic acid ”in the present specification means“ acrylic acid ”or“ methacrylic acid ”, and the same applies to other similar expressions such as (meth) acrylate.

[Resin composition]
The resin composition according to one embodiment includes an alkali-soluble resin (hereinafter, sometimes referred to as “component (A)”) and a thermal crosslinking agent (hereinafter, sometimes referred to as “component (B)”). Elastomer (hereinafter sometimes referred to as “component (C) component”).

<(A) component: alkali-soluble resin>
The component (A) is an alkali-soluble resin. The component (A) includes a resin having an alicyclic ring (hereinafter, may be referred to as “component (A1)”). When the component (A) includes the component (A1), the dielectric loss tangent can be sufficiently reduced.

に お い て In the present specification, the alkali-soluble resin means a resin that is soluble in an aqueous alkali solution. The aqueous alkaline solution is an alkaline solution such as an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of a metal hydroxide, or an aqueous solution of an organic amine. Generally, a tetramethylammonium hydroxide aqueous solution having a concentration of 2.38% by mass is used for development.

(4) The solubility in an alkali developer can be confirmed, for example, by the following method.

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

The component (A1) is not particularly limited as long as the resin has an alicyclic ring in the molecule. By using the component (A1), the dielectric loss tangent of the resin composition can be sufficiently reduced.

成分 The component (A1) may be a resin in which a glycol group such as ethylene glycol or propylene glycol, a carboxyl group, or a hydroxyl group is added to the main chain or side chain of these resins. Among them, the component (A1) may be a resin having a phenolic hydroxyl group from the viewpoints of high-temperature adhesion, heat resistance, and film formability.

The component (A1) may be, for example, a resin having a phenolic hydroxyl group represented by the following general formula (1).

In the general formula (1), E represents an alicyclic ring, G represents a single bond or an alkylene group, and R ^1A each independently represents a hydrogen atom or a monovalent hydrocarbon group. n1 represents an integer of 1 to 10, and m represents an integer of 1 to 3.

E may have from 4 to 14, 5 to 12, or 6 to 10 carbon atoms. E may be monocyclic or polycyclic, but E may be polycyclic or dicyclopentadiene. Examples of the alkylene group for G include an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. G may be a single bond. Examples of the monovalent hydrocarbon group for R ^1A include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, an aryl group such as a phenyl group and a naphthyl group, and a heteroaryl group such as a pyridyl group. And the like. R ^1A may be a hydrogen atom.

樹脂 The resin having a phenolic hydroxyl group represented by the general formula (1) may be a resin having a phenolic hydroxyl group represented by the following general formula (1a).

中 In the general formula (1a), n1 is as defined above.

Commercially available resins having a phenolic hydroxyl group represented by the general formula (1a) include, for example, “J-DPP-115” and “J-DPP-140” (both manufactured by JFE Chemical Corporation). Can be

The weight average molecular weight of the component (A1) may be 100 to 5000, 300 to 3000, or 500 to 1500. Here, the weight average molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) and conversion by a standard polystyrene calibration curve.

成分 The component (A) may contain, in addition to the component (A1), an alkali-soluble resin having no alicyclic ring (hereinafter sometimes referred to as “component (A2)”). As the component (A2), for example, polyester resin, polyether resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyurethane resin, polyurethaneimide resin, polyurethaneamideimide resin, siloxane polyimide resin, polyesterimide resin Polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polycarbonate resin, polyetherketone resin, (meth) acrylic copolymer, resin having phenolic hydroxyl group, etc. Those having no formula ring are mentioned. These may be used alone or in combination of two or more. Further, the component (A2) may be a resin in which a glycol group such as ethylene glycol or propylene glycol, a carboxyl group, or a hydroxyl group is added to a main chain or a side chain of these resins.

の Among these, the component (A2) may be a resin having a phenolic hydroxyl group from the viewpoints of high-temperature adhesion, heat resistance, and film formability.

Examples of the resin having a phenolic hydroxyl group include hydroxystyrene-based resins such as polyhydroxystyrene or a copolymer containing hydroxystyrene as a monomer unit, phenol resins, polybenzoxazole precursors such as poly (hydroxyamide), Poly (hydroxyphenylene) ether, polynaphthol and the like can be mentioned. The component (A2) may be composed of only one of these resins, or may be composed of two or more of these resins.

中 で Among these, the component (A2) may be (A2-1) a hydroxystyrene resin because of its excellent electrical properties (insulating properties) and small volume shrinkage upon curing. In addition, because of low cost, high contrast, and small volume shrinkage upon curing, the component (A2) may be a phenolic resin (A2-2) or a novolak phenolic resin. Is also good.

(A2-1) Hydroxystyrene resin has a structural unit represented by the following general formula (21).

In the general formula (21), R ²¹ represents a hydrogen atom or a methyl group, and R ²² 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.

(A2-1) Hydroxystyrene resin can be obtained by polymerizing a monomer or the like giving a structural unit represented by the general formula (21).

In Formula (21), examples of the alkyl group having 1 to 10 carbon atoms represented by R ²¹ 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, and a nonyl group. And a decyl group. These groups may be linear or branched. The aryl group having 6 to 10 carbon atoms represented by R ^22, for example, a phenyl group, a naphthyl group, and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ²¹ 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 decoroxy group. Can be These groups may be linear or branched.

Examples of the monomer giving the structural unit represented by the general formula (21) include, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenyl Phenol and the like. These monomers can be used alone or in combination of two or more.

(A2-1) The hydroxystyrene-based resin is not limited to its production method. For example, the hydroxyl group of a monomer giving a structural unit represented by the general formula (21) is protected with a t-butyl group, an acetyl group, or the like. Is a protected monomer, and the monomer having a protected hydroxyl group is polymerized to obtain a polymer. The obtained polymer is converted to a hydroxystyrene-based structural unit by a known method (deprotection under an acid catalyst). Deprotection).

(A2-1) The hydroxystyrene-based resin may be a polymer or a copolymer consisting of only a monomer that provides a structural unit represented by the general formula (21), and may have a structure represented by the general formula (21) It may be a copolymer of a monomer giving a unit and another monomer. When the (A2-1) hydroxystyrene-based resin is a copolymer, the proportion of the structural unit represented by the general formula (21) in the copolymer is determined by considering the component (A2) from the viewpoint of solubility in a developing solution. It may be from 10 to 100 mol%, from 20 to 97 mol%, from 30 to 95 mol%, or from 50 to 95 mol%, based on the total molar amount of all constituents.

(A2-1) The hydroxystyrene-based resin may be a resin further having a structural unit represented by the following general formula (22) from the viewpoint of dissolution inhibiting properties in a developer.

In the general formula (22), R ²³ represents a hydrogen atom or a methyl group, and R ²⁴ 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.

As the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, or the alkoxy group having 1 to 10 carbon atoms represented by R ²⁴ , those similar to R ²² can be exemplified.

ア ル カ リ The alkali-soluble resin having the structural unit represented by the general formula (22) can be obtained by using a monomer that gives the structural unit represented by the general formula (22). Examples of the monomer giving the structural unit represented by the general formula (22) 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.

(A2-1) When the hydroxystyrene-based resin is a resin having a structural unit represented by the general formula (22), the resin is represented by the general formula (22) from the viewpoint of dissolution inhibition properties in a developer and mechanical properties of the cured film. The proportion of the structural unit is 1 to 90 mol%, 3 to 80 mol%, 5 to 70 mol%, or 5 to 50 mol% based on the total molar amount of all the components constituting the component (A2). May be.

In addition, the (A2-1) hydroxystyrene-based resin may be a resin further having a structural unit represented by the following general formula (23) from the viewpoint of lowering the elastic modulus.

In the general formula (23), R ²⁵ represents a hydrogen atom or a methyl group, and R ²⁶ represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms.

樹脂 The resin having the structural unit represented by the general formula (23) can be obtained by using a monomer giving the structural unit represented by the general formula (23). Examples of the monomer giving the structural unit represented by the general formula (23) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) acrylate Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, (meth) acrylic acid Hydroxyoctyl, hydroxynonyl (meth) acrylate (Meth) hydroxy decyl acrylate and the like. These monomers can be used alone or in combination of two or more.

(A2-1) When the hydroxystyrene-based resin is a resin having a structural unit represented by the general formula (23), the resin is represented by the general formula (23) from the viewpoint of dissolution inhibition properties in a developer and mechanical properties of the cured film. The proportion of the structural unit is 1 to 90 mol%, 3 to 80 mol%, 5 to 70 mol%, or 5 to 50 mol% based on the total molar amount of all the components constituting the component (A2). May be.

(A2-2) Phenol resin is a polycondensation product of phenol or a derivative thereof and aldehydes. The polycondensation is usually performed in the presence of a catalyst such as an acid and a base. A phenol resin obtained when an acid catalyst is used is particularly called a novolak type phenol resin. Examples of the novolak phenol resin include phenol / formaldehyde novolak resin, cresol / formaldehyde novolak resin, xylenol / formaldehyde novolak resin, resorcinol / formaldehyde novolak resin, and phenol-naphthol / formaldehyde novolak resin.

(A2-2) Examples of the phenol derivative constituting the phenol resin include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-cresol. Butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol Phenols such as 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, aralkylphenols such as benzylphenol, methoxy Alkoxycarbonylphenols such as rubonylphenol; arylcarbonylphenols such as benzoyloxyphenol; halogenated phenols such as chlorophenol; polyhydroxybenzenes such as catechol, resorcinol and pyrogallol; bisphenols such as bisphenol A and bisphenol F; Naphthol derivatives such as naphthol; hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; monoethylene bisphenols Alcoholic hydroxyl-containing phenol derivatives such as oxide adducts and bisphenol monopropylene oxide adducts Containing carboxyl groups such as p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid and diphenolic acid Phenol derivatives and the like. These may be used alone or in combination of two or more.

(A2-2) Examples of the aldehyde constituting the phenol resin include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, and glycerol. Examples thereof include aldehyde, glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formyl acetate, 2-formylpropionic acid, and methyl 2-formylpropionate. These may be used alone or in combination of two or more. Also, formaldehyde precursors such as paraformaldehyde and trioxane, and ketones such as acetone, pyruvic acid, levulinic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3′-4,4′-benzophenonetetracarboxylic acid are used. You may use for reaction.

When the component (A2) contains the (A2-1) hydroxystyrene-based resin or the (A2-2) phenol resin, the weight average molecular weight of each of the component (A2-1) and the component (A2-2) is determined by using a developer Taking into account the balance among solubility, photosensitivity and mechanical properties of the cured film, the weight average molecular weight may be from 1,000 to 500,000, from 2,000 to 200,000, or from 2,000 to 100,000. Here, the weight average molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) and conversion by a standard polystyrene calibration curve.

The mass ratio of the component (A1) to the component (A) (the total amount of the components (A1) and (A2)) (the mass of the component (A1) / the mass of the component (A)) is 0.05 to 0.95. It may be. The mass ratio may be 0.10 or more, 0.15 or more, or 0.20 or more, and may be 0.90 or less, 0.85 or less, or 0.80 or less.

The content of the component (A) (the total amount of the components (A1) and (A2)) is 5 to 95% by mass based on the total amount of the components (A), (B), and (C). May be. The content of the component (A) may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 90% by mass or less, 85% by mass or less, or 80% by mass or less. .

<(B) component: thermal crosslinking agent>
The component (B) includes, for example, a compound having two or more alkoxymethyl groups (hereinafter sometimes referred to as “component (B1)”) and a compound having two or more epoxy groups (hereinafter, “(B2) Component).))).

成分 The component (B1) is a compound having an alkoxymethyl group that can react with the component (A) to form a bridged structure (crosslinked structure) when the resin film is cured by heating. The component (B1) is not particularly limited as long as it is a compound having two or more alkoxymethyl groups, and is, for example, a compound represented by the following general formula (2) or a compound represented by the following general formula (3). May be.

In the general formula (2), R ¹ to R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms.

As the alkyl group having 1 to 10 carbon atoms represented by R ¹ to R ⁶ , those similar to R ²² can be exemplified. The alkyl group may have 1 to 5, 1 to 3, 1 or 2, or 1 carbon atoms.

In the general formula (3), R ⁷ to R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms.

As the alkyl group having 1 to 10 carbon atoms represented by R ⁷ to R ¹² , those similar to R ²² can be exemplified. The alkyl group may have 1 to 5, 1 to 3, 1 or 2, or 1 carbon atoms.

The component (B2) has two or more epoxy groups, and together with the component (B1), when the resin film is cured by heating, it reacts with the component (A) to form a bridged structure (crosslinked structure). It is a compound having an epoxy group that can be formed.

The component (B2) is not particularly limited as long as it is a compound having two or more epoxy groups. As the component (B2), for example, an aliphatic epoxy compound, an aromatic epoxy compound, an alicyclic epoxy compound, a heterocyclic epoxy compound, a bisphenol type epoxy compound, a novolak type epoxy compound, a glycidylamine type epoxy compound, a halogenated epoxy compound And the like. These may be used alone or in combination of two or more.

The component (B2) may be an epoxy compound having an aromatic ring or an epoxy compound having a heterocyclic ring from the viewpoint of more excellent chemical resistance. The component (B2) may be an epoxy compound having a heterocyclic ring or an epoxy compound having a nitrogen-containing heterocyclic ring.

The component (B2) may be a compound represented by the following general formula (4) from the viewpoint of more excellent chemical resistance.

In the general formula (4), R ¹³ to R ¹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms.

In the general formula (4), examples of the alkylene group having 1 to 10 carbon atoms represented by R ¹³ to R ¹⁵ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene. Group, nonylene group, decylene group and the like. These groups may be linear or branched. The carbon number of the alkylene group may be 1 to 8 or 1 to 6.

The component (B2) may be, for example, an aliphatic epoxy compound or an alicyclic epoxy compound from the viewpoint of developability and dielectric properties. The aliphatic epoxy compound or the alicyclic epoxy compound may be an epoxy compound having a weight average molecular weight of 1,000 or less.

Examples of the aliphatic epoxy compound or alicyclic epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6- Hexanediol diglycidyl ether, glycerin diglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, epoxy compounds having a branched alkyl chain structure (for example, Nissan Chemical Corporation "FOLDI" series, etc.), dicyclopentadiene dimethano Rudiglycidyl ether, dicyclopentadiene dioxide, 1,2,5,6-diepoxycyclooctane, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl-1,2-cyclohexanedicarboxylate, 3,4-epoxy Cyclohexylmethyl 3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, cyclohexene oxide type epoxy resin, and the like.

The aliphatic epoxy compound or alicyclic epoxy compound may be trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, an epoxy compound having a branched alkyl chain structure, or dicyclopentadiene dimethanol diglycidyl ether.

The molar ratio of the component (B2) to the component (B1) (the number of moles of the component (B2) / the number of moles of the component (B1)) is 1.0 or less and 0.9 or less from the viewpoint of more excellent chemical resistance and breaking strength. Or 0.8 or less. The lower limit of the molar ratio is not particularly limited, but may be 0.1 or more, 0.2 or more, or 0.3 or more.

The content of the component (B) (the total amount of the component (B1) and the component (B2)) is from 5 to 80 parts by mass relative to 100 parts by mass of the component (A) from the viewpoint of better residual stress and chemical resistance. It may be 10 to 70 parts by mass, or 20 to 60 parts by mass.

<(C) component: Elastomer>
Examples of the elastomer include styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic-based elastomer, and silicone-based elastomer. These may be used alone or in combination of two or more. Among them, the component (C) may include an acrylic elastomer because the obtained cured film is excellent in breaking strength, breaking elongation and thermal expansion property.

The acrylic elastomer may have a structural unit represented by the following general formula (31).

In the general formula (31), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydroxyalkyl group having 2 to 20 carbon atoms.

The hydroxyalkyl group having 2 to 20 carbon atoms represented by R ^32, for example, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group, hydroxy nonyl group , Hydroxydecyl, hydroxyundecyl, hydroxydodecyl (sometimes referred to as hydroxylauryl), hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxy Examples include an octadecyl group, a hydroxynonadecyl group, and a hydroxyeicosyl group.

The acrylic elastomer further has a structural unit represented by the following general formula (32), a structural unit represented by the following general formula (33), or a structural unit represented by the following general formula (34). Is also good.

In Formula (32), R ³³ represents a hydrogen atom or a methyl group, and R ³⁴ represents a monovalent organic group having a primary, secondary, or tertiary amino group.

Examples of the monovalent organic group having a primary, secondary or tertiary amino group represented by R ³⁴ include, for example, aminoethyl group, N-methylaminoethyl group, N, N-dimethylaminoethyl group, N- Ethylaminoethyl group, N, N-diethylaminoethyl group, aminopropyl group, N-methylaminopropyl group, N, N-dimethylaminopropyl group, N-ethylaminopropyl group, N, N-diethylaminopropyl group, piperidine- 4-yl group, 1-methylpiperidin-4-yl group, 2,2,6,6-tetramethylpiperidin-4-yl group, 1,2,2,6,6-pentamethylpiperidin-4-yl group , (Piperidin-4-yl) methyl group, 2- (piperidin-4-yl) ethyl group and the like.

In the general formula (33), R ³⁵ represents a hydrogen atom or a methyl group, and R ³⁶ represents an alkyl group having 4 to 20 carbon atoms.

Examples of the alkyl group having 4 to 20 carbon atoms represented by R ³⁶ include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (also referred to as lauryl). ), Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like. These groups may be linear or branched.

In the general formula (34), R ³⁷ represents a hydrogen atom or a methyl group.

The acrylic elastomer may further have a structural unit derived from a crosslinkable monomer or a structural unit derived from another monomer.

The crosslinkable monomer is not particularly limited as long as it is a compound having two or more polymerizable unsaturated groups. For example, divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Examples include methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Among these, the crosslinkable monomer may be divinylbenzene.

Examples of other monomers include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, and 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, and α-methoxyacrylonitrile. Unsaturated nitrile compounds such as ethoxyacrylonitrile, nitrile crotonic acid, nitrile cinnamate, dinitrile itaconate, dinitrile maleate, dinitrile fumarate, (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N ' -Ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, , N-bis (2-hydroxyethyl) (meth) acrylamide, unsaturated amide compounds such as crotonamide, cinnamamide, styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-iso Examples thereof include aromatic vinyl compounds such as propenylphenol, and epoxy group-containing unsaturated compounds such as glycidyl (meth) acrylate. Among these, the other monomer may be butadiene, isoprene, (meth) acrylonitrile, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, or butadiene.

The acrylic elastomer is, for example, a monomer giving the structural unit represented by the general formula (31), and, if necessary, a structural unit represented by the general formula (32) and a structural unit represented by the general formula (33). A monomer that gives at least one selected from the group consisting of a structural unit and a structural unit represented by the following general formula (34), and a crosslinkable monomer and other monomers are blended, and ethyl lactate, toluene, isopropanol, etc. And then, if necessary, by heating.

The weight average molecular weight of the acrylic elastomer may be 2,000 to 100,000, 3,000 to 60,000, 5,000 to 50,000, or 10,000 to 40,000. Here, the weight average molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) and conversion by a standard polystyrene calibration curve.

The content of the component (C) is 5 to 60 parts by mass, 10 to 55 parts by mass, or 20 to 50 parts by mass based on 100 parts by mass of the component (A) from the viewpoint of more excellent breaking strength and elongation at break. May be.

In the resin composition of the present embodiment, in addition to the above components (A) to (C), as other components, an adhesion aid (hereinafter, sometimes referred to as “component (D)”), a solvent, and an acid by heating. , A surfactant, a leveling agent, and other components.

<(D) component: adhesion aid>
By using the component (D) in the resin composition, it is possible to further improve the adhesion to the substrate. The component (D) may contain a nitrogen-containing aromatic compound represented by the following general formula (5) or a silane compound represented by the following general formula (6).

In the general formula (5), R ⁵¹ represents a hydrogen atom or a hydrocarbon group, and R ⁵² represents a hydrogen atom, an amino group, or a phenyl group. A and B each independently represent a nitrogen atom or a carbon atom and a hydrogen atom bonded thereto (ie, CH).

窒 素 The nitrogen-containing aromatic compound represented by the general formula (5) may be a nitrogen-containing aromatic compound represented by the general formula (5a).

In the general formula (5a), R ⁵² has the same meaning as described above.

窒 素 Examples of the nitrogen-containing aromatic compound represented by the general formula (5a) include 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, 5-methyltetrazole and the like. Among them, the nitrogen-containing aromatic compound represented by the general formula (5a) may be 1H-tetrazole or 5-aminotetrazole from the viewpoint of obtaining better adhesion to a substrate.

In the general formula (6), R ⁶¹ represents an alkylene group, and R ⁶² represents an alkoxy group or an alkoxyalkyl group. A plurality of R ⁶² may be the same or different.

R ⁶² is excellent in adhesion to easily and that the substrate to obtain an inexpensive, R ⁶² is a methoxy group, or an alkoxy group such as ethoxy groups.

シ ラ ン The silane compound represented by the general formula (6) may be 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane.

<Solvent>
By using a solvent for the resin composition, coating on a substrate is facilitated, and a coating film having a uniform thickness can be formed. Examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, 1-methoxy-2-propanol, N -Methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, Examples include propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more. Among these, the solvent may be ethyl lactate or 1-methoxy-2-propanol 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 in the resin composition, it is possible to generate an acid when the resin film is heated, so that the reaction between the components (A) and (C), that is, thermal crosslinking The reaction is accelerated, and the heat resistance of the cured film is improved. In addition, since a compound that generates an acid by heating generates an acid even when irradiated with light, the solubility of the exposed portion (exposed portion) in a developer increases. Therefore, the difference in solubility of the photosensitive resin composition between the unexposed portion (unexposed portion) and the exposed portion in the developing solution is further increased by the compound that generates an acid by heating, and the resolution is further improved.

化合物 Examples of the compound that generates an acid by heating include those that generate an acid by heating to 50 to 250 ° C. Specific examples of the compound that generates an acid by heating include a salt formed from a strong acid such as an onium salt and a base, and imidosulfonate.

<Surfactant or leveling agent>
By using a surfactant or a leveling agent in the resin composition, coatability can be further improved. Specifically, for example, when the photosensitive resin composition contains a surfactant or a leveling agent, striation (unevenness in film thickness) can be more sufficiently prevented, and developability can be further improved. it can. Examples of the surfactant or the leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether.

The content of the solvent may be from 10 to 200 parts by mass, where the total amount of the components (A), (B) and (C) is 100 parts by mass.

含有 The content of other components other than the solvent may be 0.01 to 20 parts by mass based on 100 parts by mass of component (A).

[Curing film]
The cured film of one embodiment includes a cured product of the above resin composition. The cured film can be obtained by forming a resin film using the above resin composition and heating the formed resin film. The cured film of the present embodiment can be suitably used as an interlayer insulating layer or a surface protective layer (buffer coat film).

The method for producing a cured film according to the present embodiment includes a step of forming a resin film by applying and drying the above resin composition on a part or the whole of a substrate (coating / drying (film formation) step); To obtain a cured film by heating (heat treatment step).

<Coating and drying (film formation) process>
First, a resin film is formed by applying and drying the resin composition of the present embodiment on a substrate. In this step, the resin composition of the present embodiment is spin-coated on a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride using a spinner or the like. , To form a coating film. The thickness of the coating film is not particularly limited, but may be 0.1 to 40 μm. The substrate on which the coating film is formed is dried using a hot plate, an oven, or the like. The drying temperature and drying time are not particularly limited, but may be 80 to 140 ° C. for 1 to 7 minutes. Thus, a resin film is formed on the support substrate. The thickness of the resin film is not particularly limited, but may be 0.1 to 40 μm.

<Heat treatment step>
Next, in a heat treatment step, a cured film can be formed by heat-treating the resin film. The heating temperature in the heat treatment step may be 250 ° C. or lower or 230 ° C. or lower from the viewpoint of sufficiently preventing heat damage to the semiconductor device.

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, and a microwave curing furnace. In addition, either air or an inert atmosphere such as nitrogen can be selected, but it is preferable to perform the treatment under nitrogen because oxidation of the pattern can be prevented. Since the above heating temperature range is lower than the conventional heating temperature, damage to the supporting substrate and the semiconductor device can be suppressed to a small value. Therefore, by using the method for manufacturing a cured film of the present embodiment, an electronic device can be manufactured with high yield. It also leads to energy savings in the process. Further, according to the resin composition of the present embodiment, since the volume shrinkage (curing shrinkage) in the heat treatment step, which is observed in the photosensitive polyimide or the like, is small, it is possible to prevent a decrease in dimensional accuracy.

加熱 The heat treatment time in the heat treatment step may be a time sufficient for the resin composition to cure, but may be 5 hours or less from the viewpoint of work efficiency.

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

According to the method for producing a cured film of the present embodiment, a cured film having excellent adhesion and thermal shock properties can be obtained. The obtained cured film can be suitably used as an interlayer insulating layer or a surface protective layer (buffer coat film).

[Photosensitive resin composition]
The photosensitive resin composition of one embodiment contains an alkali-soluble resin, a thermal crosslinking agent, an elastomer, and a compound that generates an acid by light (hereinafter, may be referred to as “component (E)”). And the alkali-soluble resin includes a resin having an alicyclic ring. The properties (for example, solubility and photocurability) of the photosensitive resin composition of the present embodiment are changed by light irradiation, so that the photosensitive resin composition can be used in accordance with a desired purpose, and an exposed portion is removed after development. It can be suitably used both for forming a positive pattern and for forming a negative pattern in which unexposed portions are removed after development. The alkali-soluble resin (resin having an alicyclic ring), the thermal crosslinking agent, and the elastomer in the photosensitive resin composition are the same as the alkali-soluble resin (the resin having an alicyclic ring) in the resin composition described above. Same as agents and elastomers. Therefore, duplicate description is omitted here.

<(E) component: a compound that generates an acid by light>
The compound which generates an acid by light (by receiving light), which is the component (E), functions as a photosensitive agent in the photosensitive resin composition, and generates an acid upon irradiation with light. As the component (E), a compound generally called a photoacid generator can be used. Specific examples of the component (E) include an o-quinonediazide compound, a triarylsulfonium salt, an aryldiazonium salt, and a diaryliodonium salt. As the component (E), one type may be used alone, or two or more types may be used in combination.

Examples of the o-quinonediazide compound include compounds obtained by subjecting o-quinonediazide sulfonyl chloride to a hydroxy compound or an amino compound by a condensation reaction in the presence of a dehydrochlorinating agent.

The o-quinonediazide compounds include 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1-naphthoquinone-2-diazide- It may be a condensate with 5-sulfonyl chloride, tris (4-hydroxyphenyl) methane, or a condensate of 1-naphthoquinone-2-diazide-5-sulfonyl chloride with tris (4-hydroxyphenyl) ethane.

Examples of the triarylsulfonium salt include, for example, triarylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, and triphenylsulfonium hexafluoroantimonate.

The content of the component (E) is from 5 to 40 parts by mass based on 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 becomes larger and the sensitivity becomes better. , 6 to 30 parts by mass, or 7 to 25 parts by mass.

感光 The photosensitive resin composition of the present embodiment can be suitably used for forming a positive pattern or for forming a negative pattern. These can be used properly by adjusting the type or content of the component (B) (the component (B1) and the component (B2)), for example. When the photosensitive resin composition is used for forming a positive pattern, the photosensitive resin composition may be an epoxy compound having an aromatic ring or an epoxy compound having a heterocycle as the component (B) (particularly, the component (B2)). It is preferred to contain. When the photosensitive resin composition is used for forming a positive pattern, the content of the component (B) is preferably reduced in the photosensitive resin composition. On the other hand, it may be less than 35 parts by mass or 30 parts by mass or less. On the other hand, when the photosensitive resin composition is used for forming a negative pattern, the photosensitive resin composition contains an aliphatic epoxy compound or an alicyclic epoxy compound as the component (B) (particularly, the component (B2)). Is preferred. When the photosensitive resin composition is used for forming a negative pattern, it is preferable to increase the content of the component (B) in the photosensitive resin composition. On the other hand, it may be 35 parts by mass or more or 40 parts by mass or more.

The content of the component (E) is from 5 to 40 parts by mass based on 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 becomes larger and the sensitivity becomes better. , 6 to 30 parts by mass, or 7 to 25 parts by mass.

The photosensitive resin composition of the present embodiment generates an acid by an adhesion aid (component (D)), a solvent, and heating as other components in addition to the components (A) to (C) and (E). It may contain components such as a compound, a surfactant, a leveling agent, a dissolution promoter (hereinafter, sometimes referred to as “component (F)”), a dissolution inhibitor, and the like. The component (D) in the photosensitive resin composition, the solvent, the compound that generates an acid by heating, the surfactant, and the leveling agent generate the acid by the component (D) in the resin composition, the solvent, and the heating. The same applies to compounds, surfactants and leveling agents. Therefore, duplicate description is omitted here.

<(F) component: dissolution accelerator>
By using a dissolution accelerator in the photosensitive resin composition, the dissolution rate of the exposed portion when developing with a developer can be increased, and the sensitivity and resolution can be improved. A conventionally known dissolution accelerator can be used. Specific examples thereof include compounds having a phenolic hydroxyl group, a carboxyl group, a sulfonic acid, a sulfonamide group, and the like.

The dissolution promoter may be any of the phenolic low molecular weight compounds represented by the following general formulas (41) to (43).

In the general formula (41), R ⁴¹ represents a hydrogen atom or a methyl group. a1 to f1 represent an integer of 0 to 3, the sum of d1 to f1 is 1 or more, the sum of a1 and d1 is 5 or less, the sum of b1 and e1 is 5 or less, and the sum of c1 and f1 Is 5 or less.

In the general formula (42), R ⁴² represents a hydrogen atom or a methyl group. a2 to c2 represent an integer of 0 to 3, d2 to f2 represent an integer of 1 to 3, the sum of a2 and d2 is 5 or less, the sum of b2 and e2 is 5 or less, and the sum of c2 and f2 is The sum is 5 or less.

In the general formula (43), a3, c3, h, and i each represent an integer of 0 to 3, d3 and f3 each represent an integer of 1 to 3, the sum of a3 and d3 is 5 or less, and c3 and f3 Is 5 or less, and the sum of h and i is 4 or less.

<Dissolution inhibitor>
The dissolution inhibitor is a compound that inhibits the dissolution of the component (A) in a developer, and is used for controlling the remaining film thickness, the development time, and the contrast. Examples of the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like.

The content of the solvent may be from 10 to 200 parts by mass, where the total amount of the components (A), (B), (C) and (E) is 100 parts by mass.

含有 The content of other components other than the solvent may be 0.01 to 20 parts by mass based on 100 parts by mass of component (A).

According to the photosensitive resin composition of the present embodiment, the dielectric loss tangent can be sufficiently reduced. The photosensitive resin composition of the present embodiment can be suitably used both for forming a positive pattern and for forming a negative pattern.

[Patterned cured film and manufacturing method thereof]
The pattern cured film of one embodiment has a pattern, and the pattern includes a cured product of the above-described photosensitive resin composition. The pattern cured film can be obtained by forming a pattern using the above-mentioned photosensitive resin composition and heating the formed pattern. Hereinafter, a method for manufacturing a pattern cured film will be described.

The method for producing a cured pattern film according to this embodiment includes a step of forming a resin film by applying the photosensitive resin composition to a part or the whole of a substrate and drying the applied resin (coating / drying (film formation) step). Exposing a part of the resin film (exposure step), developing the exposed resin film with a developer to form a pattern resin film (development step), and heating the pattern resin film to cure the pattern. A step of obtaining a film (a heat treatment step). Hereinafter, each step will be described.

<Coating and drying (film formation) process>
The coating / drying (film formation) step is the same as the <coating / drying (film formation) step> of the method for producing a cured film. Therefore, duplicate description is omitted here.

<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 radiation through a mask. In the photosensitive resin composition of the present embodiment, the component (A) has high transparency to i-line, so that irradiation with i-line can be suitably used. After the exposure, post-exposure baking (PEB) can be performed, if necessary, from the viewpoint of improving the dissolution rate. The temperature for performing post-exposure heating may be 70 ° C. to 140 ° C., and the post-exposure heating time may be 1 to 5 minutes.

<Development process>
In the developing step, the exposed or unexposed part of the resin film after the exposure step is removed with a developing solution, whereby the resin film is patterned into a positive type or a negative type, whereby a patterned resin film can be obtained. The developer can be appropriately selected according to the pattern resin film (positive pattern resin film or negative pattern resin film) to be formed. Examples of the developer include an alkali aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), and a ketone-based solvent. And organic solvents such as ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents. The base concentration of the aqueous alkali solution may be 0.1 to 10% by mass. Further, an alcohol or a surfactant may be added to an aqueous alkali solution for use. Each of these may be added in the range of 0.01 to 10 parts by mass or 0.1 to 5 parts by mass with respect to 100 parts by mass of the alkaline aqueous solution. In the case of performing development using a developer, for example, the developer is disposed on the resin film by a method such as shower development, spray development, immersion development, or paddle development, and is subjected to 30 to 360 ° C. at 18 to 40 ° C. The pattern resin film can be obtained by leaving it for 2 seconds. After the standing, the pattern resin film is washed by water and spin-dried.

<Heat treatment step>
The heat treatment step is the same as the <heat treatment step> of the method for producing a cured film. Therefore, duplicate description is omitted here.

According to the method of manufacturing a cured pattern film of the present embodiment, a cured pattern film having sufficiently high sensitivity and resolution, and excellent adhesion and thermal shock properties can be obtained. The cured pattern film of the present embodiment can be used as an interlayer insulating layer or a surface protection layer of a semiconductor device.

[Semiconductor device]
A semiconductor device according to an embodiment includes the interlayer insulating layer or the surface protection layer according to the 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.

Here, an example of a manufacturing process of a semiconductor element will be described with reference to the drawings. 1 to 5 are schematic views (a schematic perspective view and a schematic end view) illustrating 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 faces in (a), respectively.

First, the structure 100 shown in FIG. 1 is prepared. The structure 100 has a semiconductor substrate 1 such as a Si substrate having circuit elements, a predetermined pattern for exposing the circuit elements, a protective film 2 such as a silicon oxide film covering the semiconductor substrate 1, and an exposed circuit element. The semiconductor device includes a first conductive layer 3 formed thereon, and an interlayer insulating layer 4 made of a polyimide resin or the like formed on the protective film 2 and the first conductive layer 3 by a spin coating method or the like.

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

(4) 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. Dry etching using a gas such as oxygen or carbon tetrafluoride can be used for etching the interlayer insulating layer 4. By this etching, the portion of the interlayer insulating layer 4 corresponding to the window 6A is selectively removed, and the interlayer insulating layer 4 provided with the window 6B such that the first conductor layer 3 is exposed can be 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.

(4) Further, the second conductor layer 7 is formed in a portion corresponding to the window 6B to obtain the structure 400 shown in FIG. For forming the second conductor layer 7, a known photolithography technique can be used. Thus, electrical connection between the second conductor layer 7 and the first conductor layer 3 is performed.

(4) Finally, the surface protection layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain the semiconductor device 500 shown in FIG. In the present embodiment, the surface protective layer 8 is formed as follows. First, the photosensitive resin composition is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by spin coating and dried to form a resin film. Next, after a predetermined portion is irradiated with light through a mask in which a pattern corresponding to the window 6C is drawn, the exposed resin film is developed with an alkaline aqueous solution to form a patterned resin film. After that, by curing the pattern resin film by heating, a pattern cured film used as the surface protection layer 8 is formed. The surface protection 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 protection layer 8 of the present embodiment is reliable. Excellent in nature.

In the above embodiment, a method of 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 may be repeated to form each layer. it can. That is, a multilayer pattern can be formed by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protection 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 photosensitive resin composition of the present embodiment.

電子 The electronic device of the present embodiment is not limited to a device having a surface protective layer, a cover coat layer, or an interlayer insulating layer formed using the above-described photosensitive resin composition, and may have various structures.

FIGS. 6 and 7 are schematic sectional views showing one embodiment of the semiconductor device. More specifically, it is a schematic sectional view showing one embodiment of a semiconductor device having a rewiring structure. Since the photosensitive resin composition of this embodiment is excellent in stress relaxation property, adhesiveness, and the like, it can be used in a recently developed semiconductor element having a rewiring structure shown in FIGS.

A semiconductor element 600 shown in FIG. 6 includes a silicon substrate 23, an interlayer insulating layer 11 provided on one surface 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 or the like) and a surface protection layer 14 sequentially laminated on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and An island-shaped core 18 disposed in the vicinity of the opening on the protective layer 14 and in contact with the pad portion 15 in the opening of the insulating layer 13 and the surface protective layer 14 and on a surface of the core 18 opposite to the surface protective layer 14. And a redistribution layer 16 extending on the surface protection layer 14 so as to be in contact with it. Further, the semiconductor element 600 is formed so as to cover the surface protective layer 14, the core 18, and the redistribution layer 16, and has a cover coat layer 19 having an opening at a portion of the redistribution layer 16 on the core 18, and a cover. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the coat layer 19, the collar 21 holding the conductive ball, and the cover coat layer 19 around the conductive ball 17 And an underfill 22 provided. The conductive balls 17 are used as external connection terminals, and are formed of solder, gold, or the like. The underfill 22 is provided to reduce stress when the semiconductor element 600 is mounted.

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

6 and 7, the photosensitive resin composition is 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 be used as The pattern cured film using the photosensitive resin composition of the present embodiment has excellent adhesiveness to a metal layer such as the Al wiring layer 12 and the rewiring layer 16 and a sealing agent, and has a high stress relaxation effect. A semiconductor element using the pattern cured film for the interlayer insulating layer 11, the surface protective layer 14, the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used in flip chips, and the like is extremely excellent in reliability. It will be.

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

膜厚 The film thickness of the interlayer insulating layer 11, the surface protective layer 14, and the cover coat layer 19 may be 3 to 20 μm or 5 to 15 μm.

[Electronic device]
An electronic device according to one embodiment has the semiconductor element according to the present embodiment. The electronic device includes the above-described semiconductor element, and includes, for example, a mobile phone, a smartphone, a tablet terminal, a personal computer, a hard disk suspension, and the like.

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

(Examples 1-1 to 1-4 and Comparative Example 1-1)
[Preparation of photosensitive resin composition for forming a positive pattern]
The materials used in the examples are shown below.

<(A) component: alkali-soluble resin>
Component (A1): Resin having an alicyclic ring A1-1: Phenolic resin having a dicyclopentadiene ring (weight average molecular weight: 1100 to 1400, trade name “J-DPP-140” manufactured by JFE Chemical Corporation)
A1-2: Phenolic resin having a dicyclopentadiene ring (weight average molecular weight: 700 to 900, trade name “J-DPP-115” manufactured by JFE Chemical Corporation)
Component (A2): Resin having no alicyclic ring A2-1: Copolymer of 4-hydroxystyrene / styrene (70/30 (molar ratio)) (weight average molecular weight: 10,000, manufactured by Maruzen Petrochemical Co., Ltd.) Product name "Marca Linker CST")

重量 In the present specification, the weight average molecular weight means a value determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

Specifically, the weight average molecular weight was measured using the following apparatus and conditions.
measuring device:
Detector: Hitachi Ltd. L4000UV
Pump: Hitachi Ltd. L6000
Column: Gelpack GL-S300MDT-5 x 2 Measurement conditions:
Eluent: THF
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 mL / min, detector: UV 270 nm
The measurement was performed using a solution of 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the sample.

<(B) component: thermal crosslinking agent>
Component (B1): Compound having two or more alkoxymethyl groups B1-1: Hexakis (methoxymethyl) melamine (a compound in which R ¹ to R ^{6 in} general formula (2) are all methyl groups, manufactured by Nippon Cytec Industries, Ltd.) , Product name "Cymel-300")
Component (B2): a compound having two or more epoxy groups B2-1: 1,3,5-tris (4,5-epoxypentyl) -1,3,5-triazine-2,4,6-trione (general Compound in which R ¹³ to R ^{15 in} the formula (4) are all n-propylene groups, manufactured by Nissan Chemical Industries, Ltd., trade name “TEPIC-VL”)

<(C) component: Elastomer>
C-1: 55 g of ethyl lactate was weighed and placed in a 100 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, and separately weighed out of a polymerizable monomer (n-butyl acrylate (BA)). 34.7 g, dodecyl acrylate (DDA) 2.2 g, acrylic acid (AA) 3.9 g, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: LA82, Hitachi Chemical Co., Ltd.) 1.7 g), 2.6 g of hydroxybutyl acrylate (HBA), and 0.29 g of azobisisobutyronitrile (AIBN) at room temperature with stirring at about 160 rpm. Nitrogen gas was flowed at a flow rate of 400 mL / min for 30 minutes to remove dissolved oxygen, then the flow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65 ° C. in a constant temperature water bath in about 25 minutes. A polymerization reaction was carried out at the same temperature for 10 hours to obtain an acrylic elastomer, at which the polymerization rate was 99%, and the weight average molecular weight of the acrylic elastomer was about 22,000. The molar ratio of the polymerizable monomer in the acrylic elastomer is as follows.
BA / DDA / AA / LA82 / HBA = 75.5 / 2.5 / 15/2/5 (mol%)

<(D) component: adhesion aid>
D-1: 5-aminotetrazole (manufactured by Toyobo Co., Ltd., trade name "HAT")
D-2: 3-glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)

<(E) component: a compound that generates an acid by light>
E-1: o-quinonediazide compound (trade name "PA-28", manufactured by Daito Chemmix Co., Ltd.)
E-2: o-quinonediazide compound (trade name “4C-PA-280” manufactured by Daito Mix)

E-1 and E-2 are 4,4 '-(1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol and 1,2-naphtho. It is a condensate with quinonediazide-5-sulfonyl chloride, but has a different main absorption wavelength (having a different elimination skeleton).

<(F) component: dissolution accelerator>
F-1: 4,4 ′-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) -phenyl) -ethylidene) -bisphenol (trade name “TrisP” manufactured by Honshu Chemical Industry Co., Ltd.) -PA-MF ")

１６０ 160 parts by mass of ethyl lactate and 5 parts by mass of 1-methoxy-2-propanol were blended with the components (A) to (F) in the amounts (parts by mass) shown in Table 1. The resulting mixture was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to prepare positive-type photosensitive resin compositions of Examples 1-1 to 1-4 and Comparative Example 1-1. .

[Evaluation of photosensitive resin composition for forming positive pattern]
<Measurement of dielectric loss tangent>
The photosensitive resin compositions for forming a positive pattern of Examples 1-1 to 1-4 and Comparative Example 1-1 were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes to form a film having a thickness of about 1: 1. A resin film of 12 to 14 μm was produced. Thereafter, the resin film was heated and cured by the following method (i) to obtain a cured film having a thickness of about 10 μm.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., product name “μ-TF”), heat-treat the resin film in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. did.

<Evaluation of film formability and developability>
The photosensitive resin compositions for forming a positive pattern of Examples 1-1 to 1-4 and Comparative Example 1-1 were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes. Regardless of which of the photosensitive resin compositions for forming a positive pattern of Examples 1-1 to 1-4 and Comparative Example 1-1 is used, a resin film having a film thickness of about 12 to 14 μm can be formed. Was confirmed. Thereafter, the produced resin film was subjected to reduced projection exposure with i-line (365 nm) through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After exposure, development is performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), and development is performed so that the remaining film thickness of the unexposed portion is about 80 to 95% of the initial film thickness. The exposed part was removed. Thereafter, the developed pattern resin film was rinsed with water. It was confirmed that a square hole pattern could be formed using any of the positive-type photosensitive resin compositions for pattern formation of Examples 1-1 to 1-4 and Comparative Example 1-1.

<Evaluation of resolution>
In the evaluation of the film formability and the developability, one side of a square hole pattern formed using the photosensitive resin composition for forming a positive pattern of Examples 1-1, 1-4 and Comparative example 1-1 was used. The length was measured, and this was taken as the size (X1) of the hole pattern of the developed pattern resin film. Thereafter, the pattern resin film after development is heat-treated and cured by the following method (i), the length of one side of a square hole pattern is measured, and the size of the hole pattern of the cured pattern cured film is measured. (X2). The ratio ((X2) / (X1)) of the size (X2) of the hole pattern of the cured pattern cured film to the size (X1) of the hole pattern of the developed pattern resin film is determined, and this is used to cure the pattern. Change rate before and after. Table 1 shows the results. As the numerical value of the change rate is closer to 1, it means that the change in the size of the hole pattern before and after curing is smaller and the resolution is better.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name “μ-TF”), heat the pattern resin film in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. Processed.

に つ い て Using the SPDR dielectric resonator (manufactured by Keysight Technology GK), the dielectric loss tangent of the obtained cured film was measured at a frequency of 3 GHz. Table 1 shows the results.

As shown in Table 1, the cured products of the positive-type photosensitive resin compositions for pattern formation of Examples 1-1 to 1-4 containing the resin having an alicyclic ring were obtained by curing the resin having an alicyclic ring. It was found that the cured product of the positive-type photosensitive resin composition for pattern formation of Comparative Example 1-1 which did not contain the same had a lower dielectric loss tangent. Further, it has been found that the photosensitive resin compositions for forming a positive pattern according to some embodiments are also excellent in resolution.

(Examples 2-1 to 2-4)
[Preparation of photosensitive resin composition for negative pattern formation]
The materials used in the examples are shown below.

<(A) component: alkali-soluble resin>
Component (A1): Resin having alicyclic ring A1-3: Phenol resin same as A1-2 above A1-4: Phenolic resin having dicyclopentadiene ring (weight average molecular weight: 400 to 600, manufactured by JFE Chemical Corporation) , Product name "J-DPP-95")
Component (A2): Resin having no alicyclic ring A2-2: Same copolymer as above A2-1

<(B) component: thermal crosslinking agent>
Component (B1): a compound having two or more alkoxymethyl groups B1-2: 4,4 ′-[1- [4- [1- [4-hydroxy-3,5-bis (methoxymethyl) phenyl] -1 ” -Methylethyl] phenyl] ethylidene] bis [2,6-bis (methoxymethyl) phenol] (a compound in which R ⁷ to R ^{12 in} the general formula (3) are all methyl groups, manufactured by Honshu Chemical Industry Co., Ltd., trade name "HMOM-TPPA")
Component (B2): Compound having two or more epoxy groups B2-2: Trimethylolpropane triglycidyl ether (trade name “EX-321L” manufactured by Nagase ChemteX Corporation)
B2-3: Dicyclopentadiene dimethanol diglycidyl ether (trade name "EP-4088L" manufactured by ADEKA Corporation)
B2-4: Epoxy compound having a branched alkyl chain structure (trade name “E201” manufactured by Nissan Chemical Industries, Ltd.)
B2-5: The same compound as B2-1

<(C) component: Elastomer>
C-2: 55 g of ethyl lactate was weighed and placed in a 100 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer, and separately weighed out of a polymerizable monomer (n-butyl acrylate (BA)). 36.57 g, dodecyl acrylate (DDA) 0.09 g, acrylic acid (AA) 5.50 g, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: LA82, Hitachi Chemical Co., Ltd.) 0.09 g), 2.75 g of hydroxybutyl acrylate (HBA), and 0.31 g of azobisisobutyronitrile (AIBN) at room temperature with stirring at about 160 rpm. Dissolved oxygen was removed by flowing nitrogen gas at a flow rate of 400 mL / min for 30 minutes, then the flow of nitrogen gas was stopped, the flask was sealed, and the temperature was kept at 65 ° C. in a constant temperature water bath for about 25 minutes. A polymerization reaction was carried out at the same temperature for 10 hours to obtain an acrylic elastomer, at which the polymerization rate was 99%, and the weight average molecular weight of the acrylic elastomer was about 22,000. The molar ratio of the polymerizable monomer in the acrylic elastomer is as follows.
BA / DDA / AA / LA82 / HBA = 74.8 / 0.1 / 20 / 0.1 / 5 (mol%)

<(D) component: adhesion aid>
D-3: the same compound as the above D-2

<(E) component: a compound that generates an acid by light>
E-3: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name "CPI-310B")

１６０ 160 parts by mass of ethyl lactate and 5 parts by mass of 1-methoxy-2-propanol were blended with the components (A) to (E) in the amounts (parts by mass) shown in Table 2. The resulting mixture was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to prepare negative-type photosensitive resin compositions for pattern formation in Examples 2-1 to 2-4.

[Evaluation of photosensitive resin composition for negative pattern formation]
<Measurement of dielectric loss tangent>
The photosensitive resin composition for forming a negative pattern of Examples 2-1 to 2-4 was spin-coated on a 6-inch silicon substrate, and heated at 120 ° C. for 3 minutes to obtain a resin film having a thickness of about 12 to 14 μm. Was prepared. Thereafter, the resin film was heated and cured by the following method (i) to obtain a cured film having a thickness of about 10 μm.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., product name “μ-TF”), heat-treat the resin film in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. did.

に つ い て Using the SPDR dielectric resonator (manufactured by Keysight Technology GK), the dielectric loss tangent of the obtained cured film was measured at a frequency of 3 GHz. Table 2 shows the results.

(Evaluation of photosensitive characteristics)
The negative pattern forming resin compositions of Examples 2-1 to 2-4 in which the dielectric loss tangent of the cured film was sufficiently reduced were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes. Then, a resin film having a thickness of about 12 to 14 μm was formed. Thereafter, the produced resin film was subjected to reduced projection exposure with i-line (365 nm) through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After exposure, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) to remove unexposed portions. After the development, post-baking was performed on a hot plate at 95 ° C. for 6 minutes. The pattern resin film after the post-baking was observed, and the case where the resin film did not remain in the unexposed portion was evaluated as “A”, and the case where the resin film remained remained was evaluated as “B”. Further, the residual film ratio of the resin film in the exposed portion after the development was calculated by the following equation. Table 2 shows the results.
Residual film ratio (%) = (film thickness of resin film after development / film thickness of resin film before development) × 100

As shown in Table 2, the cured products of the negative-type photosensitive resin compositions for pattern formation of Examples 2-1 to 2-4 containing an alkali-soluble resin containing a resin having an alicyclic ring had low dielectric constants. It was found to show a tangent.

From the above results, it was confirmed that the photosensitive resin composition of the present invention can sufficiently reduce the dielectric loss tangent.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer, 4 ... Interlayer insulation layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window part, 7 ... Second conductor layer, 8 ... Surface protection Layer, 11: interlayer insulating layer, 12: Al wiring layer, 13: insulating layer, 14: surface protection layer, 15: pad portion, 16: rewiring layer, 17: conductive ball, 18: core, 19: cover coat Layer, 20 barrier metal, 21 color, 22 underfill, 23 silicon substrate, 24 connection, 100, 200, 300, 400 structure, 500, 600, 700 semiconductor device.

Claims (11)

1. An alkali-soluble resin,
   A thermal crosslinking agent,
   Elastomer and
   Containing
   A resin composition, wherein the alkali-soluble resin includes a resin having an alicyclic ring.
2. 樹脂 The resin composition according to claim 1, wherein the resin having an alicyclic ring is a resin having a phenolic hydroxyl group.
3. 樹脂 The resin composition according to claim 1, wherein the elastomer includes an acrylic elastomer.
4. (4) A cured film containing a cured product of the resin composition according to any one of (1) to (3).
5. An alkali-soluble resin,
   A thermal crosslinking agent,
   Elastomer and
   A compound that generates an acid by light,
   Containing
   A photosensitive resin composition, wherein the alkali-soluble resin includes a resin having an alicyclic ring.
6. The photosensitive resin composition according to claim 5, wherein the resin having an alicyclic ring is a resin having a phenolic hydroxyl group.
7. 7. The photosensitive resin composition according to claim 5, wherein the elastomer includes an acrylic elastomer. 8.
8. A cured pattern film having a pattern, wherein the pattern contains a cured product of the photosensitive resin composition according to any one of claims 5 to 7.
9. A step of forming a resin film by applying the photosensitive resin composition according to any one of claims 5 to 7 to a part or all of a substrate and drying the substrate.
   Exposing a part of the resin film,
   A step of developing the resin film after exposure with a developer to form a patterned resin film,
   Heating the pattern resin film to obtain a cured pattern film,
   A method for producing a cured pattern film, comprising:
10. A semiconductor device comprising the pattern cured film according to claim 8 as an interlayer insulating layer or a surface protection layer.
11. An electronic device comprising the semiconductor element according to claim 10.

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