JP7092121B2 - Positive photosensitive resin composition, thermal cross-linking agent for positive photosensitive resin, pattern cured film and its manufacturing method, semiconductor device, and electronic device. - Google Patents

Description

The present invention relates to a positive photosensitive resin composition, a thermal cross-linking agent for a positive photosensitive resin, a pattern cured film and a method for producing the same, a semiconductor device, and an electronic device.

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

Japanese Unexamined Patent Publication No. 2008-309885 Japanese Unexamined Patent Publication No. 2007-057595 International Publication No. 2010/073948

By the way, as the wafer becomes smaller and the insulating layer becomes multi-layered, the semiconductor element has a problem of warpage of the package due to the residual stress of the pattern curing film used for the insulating layer. Therefore, the material used is required to reduce the residual stress of the formed pattern cured film.

Generally, in order to reduce the residual stress of the cured film, it is considered effective to reduce the crosslink density of the cured film. However, when the crosslink density is lowered, the film strength tends to decrease at the same time, and the chemical resistance of the patterned cured film tends to decrease.

The present invention has been made in view of such circumstances, and is a positive photosensitive resin composition capable of forming a cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate. The main purpose is to provide things.

As a result of diligent studies to achieve the above object, the present inventors have found that a cured film having low residual stress and excellent chemical resistance can be formed by combining specific compounds in a positive photosensitive resin composition. I found it. Furthermore, they have found that the obtained cured film has excellent adhesion to the substrate, and have completed the present invention.

One aspect of the present invention is (A) an alkali-soluble resin, (B) a compound represented by the following general formula (1) or a compound represented by the following general formula (2), and (C) two or more. Provided is a positive photosensitive resin composition containing a compound having an epoxy group. According to such a positive photosensitive resin composition, it is possible to form a pattern cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate.

［一般式（１）中、Ｒ^１～Ｒ^６は、それぞれ独立に炭素数１～１０のアルキル基を示す。］

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

［一般式（２）中、Ｒ^７～Ｒ^１２は、それぞれ独立に炭素数１～１０のアルキル基を示す。］

[In the general formula (2), R ⁷ to R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. ]

The molar ratio of the component (C) to the component (B) may be 1.0 or less. When the molar ratio is in such a range, the chemical resistance and the breaking strength tend to be better.

The component (C) may be a compound having an aromatic ring or a heterocycle. Further, the component (C) may be a compound represented by the following general formula (3). When the component (C) is such a compound, the chemical resistance of the formed pattern cured film tends to be more excellent.

［一般式（３）中、Ｒ^１３～Ｒ^１５は、それぞれ独立に炭素数１～１０のアルキレン基を示す。］

[In the general formula (3), R ¹³ to R ¹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. ]

The positive photosensitive resin composition may further contain (D) an elastomer. Further, the positive photosensitive resin composition may further contain a compound that produces an acid by (E) light. By using these components, the heat resistance (coefficient of thermal expansion) and mechanical properties (breaking strength and breaking elongation) of the formed pattern cured film tend to be excellent.

In another aspect, a thermal cross-linking agent for a positive photosensitive resin comprising a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound having two or more epoxy groups. I will provide a. When such a thermal cross-linking agent for positive photosensitive resin is used, a positive photosensitive resin composition capable of forming a pattern cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate is possible. The thing can be easily prepared.

［一般式（１）中、Ｒ^１～Ｒ^６は、それぞれ独立に炭素数１～１０のアルキル基を示す。］

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

［一般式（２）中、Ｒ^７～Ｒ^１２は、それぞれ独立に炭素数１～１０のアルキル基を示す。］

[In the general formula (2), R ⁷ to R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms. ]

In another aspect, there is provided a pattern cured film comprising a cured product of a resin film having a pattern and the pattern comprising the above positive photosensitive resin composition.

In another aspect, a step of applying the above positive photosensitive resin composition to a part or all of the substrate and drying it to form a resin film, a step of exposing a part or all of the resin film, and a step after exposure. Provided is a method for producing a pattern cured film, comprising a step of developing the resin film of the above with an alkaline aqueous solution to form a pattern resin film and a step of heating the pattern resin film.

In another aspect, a semiconductor device provided with the above-mentioned pattern curing film as an interlayer insulating layer or a surface protective layer is provided.

In another aspect, an electronic device comprising the above semiconductor device is provided.

According to the present invention, it is possible to provide a positive photosensitive resin composition capable of forming a cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate. Further, it is possible to provide a thermal cross-linking agent for a positive photosensitive resin, which can easily prepare such a positive photosensitive resin composition. Further, it is possible to provide a pattern cured film using such a positive photosensitive resin composition, a method for producing the same, a semiconductor device, and an electronic device.

It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain one Embodiment of the manufacturing process of a semiconductor element. It is the schematic perspective view and the schematic end view which explain 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.

As used herein, "(meth) acrylic acid" means "acrylic acid" or "methacrylic acid", and is the same in other similar expressions such as (meth) acrylate.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of one embodiment includes (A) an alkali-soluble resin, (B) a compound represented by the general formula (1) or a compound represented by the general formula (2), and (C). Contains a compound having two or more epoxy groups.

<Ingredient (A)>
The component (A) is a resin that is soluble in an alkaline aqueous solution (developer). The alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. Generally, an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass is used for development.

It can be confirmed, for example, that the component (A) is soluble in an alkaline developer as follows.

The varnish obtained by dissolving the component (A) in an arbitrary solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having a film thickness of about 5 μm. This is immersed in any of 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 uniformly dissolved, the component (A) can be regarded as soluble in an alkaline developer.

Examples of the component (A) include polyester resin, polyether resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyurethane resin, polyurethaneimide resin, polyurethaneamideimide resin, siloxane polyimide resin, and polyesterimide resin. , Polybenzoxazole resin, phenoxy resin, polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin, polycarbonate resin, polyether ketone resin, (meth) acrylic copolymer, resin having a phenolic hydroxyl group and the like. These can be used alone or in combination of two or more. Further, the main chain or side chain of these resins may be provided with a glycol group such as ethylene glycol or propylene glycol, a carboxyl group or a hydroxyl group.

Among these, from the viewpoint of high temperature adhesiveness, heat resistance and film forming property, the component (A) is preferably a resin having a phenolic hydroxyl group.

Examples of the resin having a phenolic hydroxyl group include hydroxystyrene resins such as polyhydroxystyrene or a copolymer containing hydroxystyrene as a monomer unit, phenolic resins, and polybenzoxazole precursors such as poly (hydroxyamide). Examples thereof include 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 of them.

Among these, the (A1) hydroxystyrene resin is preferable because it has excellent electrical characteristics (insulation properties) and has a small volume shrinkage during curing. Further, the (A2) phenol resin is preferable, and the novolak type phenol resin is more preferable, because the price is low, the contrast is high, and the volume shrinkage at the time of curing is small.

(A1) The 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 indicates an integer of 0 to 3, and b indicates an integer of 1 to 3. The total of a and b is 5 or less.

(A1) The hydroxystyrene resin can be obtained by polymerizing a monoma or the like giving a structural unit represented by the general formula (21).

In the general 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. Groups, decyl groups and the like can be mentioned. These groups may be linear or branched. Examples of the aryl group having 6 to 10 carbon atoms represented by R ²² include a phenyl group and a naphthyl group. 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 decoxy group. Be done. These groups may be linear or branched.

Examples of the monoma giving the structural unit represented by the general formula (21) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenyl. Examples include phenol. Each of these monomas can be used alone or in combination of two or more.

The hydroxystyrene resin (A1) is not limited to the production method thereof, but for example, the hydroxyl group of the monomer giving the structural unit represented by the general formula (21) is protected by a t-butyl group, an acetyl group, or the like to protect the hydroxyl group. A polymer is obtained by polymerizing a monoma with a protected hydroxyl group to obtain a polymer, and the obtained polymer is deprotected under an acid catalyst and converted into a hydroxystyrene-based structural unit. Etc.) can be obtained by deprotecting.

(A1) The hydroxystyrene resin may be a polymer or a copolymer consisting only of a monoma giving a structural unit represented by the general formula (21), and the structural unit represented by the general formula (21) may be used. It may be a copolymer of the given monoma and other monomas. (A1) When the hydroxystyrene resin is a copolymer, the ratio of the structural units represented by the general formula (21) in the polymer is (A) from the viewpoint of solubility in the alkaline developing solution of the exposed portion. With respect to 100 mol% of the components, 10 to 100 mol% is preferable, 20 to 97 mol% is more preferable, 30 to 95 mol% is further preferable, and 50 to 95 mol% is particularly preferable.

The hydroxystyrene resin (A1) is preferably an alkali-soluble resin having a structural unit represented by the following general formula (22) from the viewpoint of further improving the dissolution inhibitory property of the unexposed portion in the alkaline 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.

Examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the alkoxy group having 1 to 10 carbon atoms represented by R ²⁴ are the same as those of R ²² .

The alkali-soluble resin having the structural unit represented by the general formula (22) can be obtained by using a monoma giving the structural unit represented by the general formula (22). Examples of the monoma 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. , P-Aromatic vinyl compounds such as methoxystyrene and the like. Each of these monomas can be used alone or in combination of two or more.

(A1) When the hydroxystyrene resin is an alkali-soluble resin having a structural unit represented by the general formula (22), it is generally used from the viewpoint of inhibition of dissolution of the unexposed portion in an alkaline developer and mechanical properties of the pattern cured film. The ratio of the structural unit represented by the formula (22) is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and 5 to 100 mol% of the component (A). -50 mol% is particularly preferred.

Further, the hydroxystyrene resin (A1) is preferably an alkali-soluble resin 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.

The alkali-soluble resin having the structural unit represented by the general formula (23) can be obtained by using a monoma giving the structural unit represented by the general formula (23). Examples of the monoma 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, (meth) hexyl acrylate, (meth) heptyl acrylate, (meth) octyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) Hydroxyethyl acrylate, (meth) hydroxypropyl acrylate, (meth) hydroxybutyl acrylate, (meth) hydroxypentyl acrylate, (meth) hydroxyhexyl acrylate, (meth) hydroxyheptyl acrylate, (meth) acrylate Examples thereof include hydroxyoctyl, hydroxynonyl (meth) acrylate, and hydroxydecyl (meth) acrylate. Each of these monomas can be used alone or in combination of two or more.

(A1) When the hydroxystyrene resin is an alkali-soluble resin having a structural unit represented by the general formula (23), it is generally used from the viewpoint of inhibition of dissolution of the unexposed portion in an alkaline developer and mechanical properties of the pattern cured film. The ratio of the structural unit represented by the formula (23) is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and 5 to 100 mol% of the component (A). -50 mol% is particularly preferred.

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

Examples of the phenol derivative constituting the (A2) phenol resin include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-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, 3 , Alkylphenol such as 4,5-trimethylphenol, methoxyphenol, alkoxyphenol such as 2-methoxy-4-methylphenol, alkenylphenol such as vinylphenol and allylphenol, aralkylphenol such as benzylphenol, alkoxy such as methoxycarbonylphenol. Arylcarbonylphenol such as carbonylphenol and benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol and pyrogallol, bisphenol such as bisphenol A and bisphenol F, and naphthol derivatives such as α- or β-naphthol. , P-Hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, hydroxyalkylphenol such as p-hydroxyphenyl-4-butanol, hydroxyalkylcresol such as hydroxyethylcrezole, monoethylene oxide adduct of bisphenol, bisphenol Alcoholic hydroxyl group-containing phenol derivatives such as monopropylene oxide adducts, p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxykatsura acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, Examples thereof include carboxyl group-containing phenol derivatives such as hydroxyphenoxybenzoic acid and diphenolic acid. These can be used alone or in combination of two or more.

Examples of the aldehydes constituting the (A2) phenol resin include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, and glyceraldehyde. Examples thereof include glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formaldehyde acetic acid, methyl formyl acetate, 2-formylpropionic acid, methyl 2-formylpropionic acid and the like. These can be used alone or in combination of two or more. In addition, formaldehyde precursors such as paraformaldehyde and trioxane, and ketones such as acetone, pyruvate, levulinic acid, 4-acetylbutyl acid, acetone dicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid. It may be used for the reaction.

When the component (A) contains (A1) hydroxystyrene resin or (A2) phenol resin, the weight average molecular weights of the components (A1) and (A2) are the solubility in an alkaline aqueous solution, the photosensitive characteristics and the pattern. Considering the balance of the mechanical properties of the cured film, the weight average molecular weight is preferably 1000 to 500,000, more preferably 2000 to 200,000, and even more preferably 2000 to 100,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

<Ingredient (B)>
The compound (B) is a compound having a structure capable of reacting with the component (A) to form a bridging structure when the photosensitive resin film after pattern formation is heated and cured. The component (B) is a compound represented by the following general formula (1) or a compound represented by the following general formula (2).

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

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ to R ⁶ are the same as those of R ²² . The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1.

In the general formula (2), 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 , the same as R ²² can be exemplified. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1.

<Ingredient (C)>
The compound (C) has two or more epoxy groups, and when the photosensitive resin film after pattern formation is heated and cured together with the above-mentioned compound (B), the component (A) is formed. It is a compound having a structure capable of forming a bridging structure by reacting with.

The component (C) can be used without particular limitation as long as it has two or more epoxy groups. Examples of the component (C) include 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, and a halogenated epoxy. Examples include compounds. These can be used alone or in combination of two or more.

Of these, the component (C) is preferably an epoxy compound having an aromatic ring or a heterocycle, more preferably an epoxy compound having a heterocycle, and a nitrogen-containing heterocycle, from the viewpoint of being more excellent in chemical resistance. It is more preferably an epoxy compound having.

The component (C) is preferably a compound represented by the following general formula (3) from the viewpoint of being more excellent in chemical resistance.

In the general formula (3), R ¹³ to R ¹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms.

In the general formula (3), 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. Examples include a group, a nonylene group, a decylene group and the like. These groups may be linear or branched. The alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

The molar ratio of the component (C) to the component (B) (the number of moles of the component (C) / the number of moles of the component (B)) is 1.0 or less from the viewpoint of being superior in chemical resistance and breaking strength, and is 0. It is preferably 9 or less, and more preferably 0.8 or less. The lower limit of the molar ratio of the component (C) to the component (B) is not particularly limited, but may be 0.1 or more, 0.2 or more, or 0.3 or more.

The total amount of the component (B) and the component (C) is preferably 2 to 35 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of being superior in residual stress and chemical resistance. It is more preferably parts, and even more preferably 5 to 25 parts by mass.

The positive photosensitive resin composition of the present embodiment may further contain (D) an elastomer or (E) a compound that produces an acid by light, in addition to the components (A) to (C). By using these components, a positive photosensitive resin composition having excellent breaking strength and thermal expansion property can be obtained.

<(D) component>
Examples of the elastomer 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 alone or in combination of two or more. Of these, the component (D) may be an acrylic elastomer because the obtained pattern cured film is excellent in breaking strength, breaking elongation and thermal expansion.

The acrylic elastomer preferably has 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.

Examples of the hydroxyalkyl group having 2 to 20 carbon atoms represented by R ³² 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 thereof include an octadecyl group, a hydroxynonadecil group and a hydroxyeicocil 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). May be good.

In the general 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 primary, secondary or tertiary amino group represented by R ³⁴ include 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-methyl Piperidine-4-yl group, 2,2,6,6-tetramethylpiperidin-4-yl group, 1,2,2,6,6-pentamethylpiperidin-4-yl group, (piperidin-4-yl) Examples thereof include a methyl group and a 2- (piperidine-4-yl) ethyl group.

In the general formula ( ³³ ), ^R35 represents a hydrogen atom or a methyl group, and R36 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 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 referred to as a lauryl group). ), Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, eikosyl group 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 is, for example, a monoma giving a structural unit represented by the above general formula (31), and a structural unit represented by the general formula (32), (33) or (34) added as needed. It can be obtained by blending a monoma to give the above product, stirring it in a solvent such as ethyl lactate, toluene, or isopropanol, and heating it if necessary.

The weight average molecular weight of the acrylic elastomer is preferably 2000 to 100,000, more preferably 3000 to 60,000, further preferably 5000 to 50,000, and particularly preferably 10,000 to 40,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

The content of the component (D) is preferably 1 to 35 parts by mass and 3 to 30 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of being superior in breaking strength and breaking elongation. More preferably, it is 5 to 25 parts by mass.

<(E) component>
The compound (E) that produces an acid by light (by receiving light), which is a component, functions as a photosensitive agent in the photosensitive resin composition. The component (E) has a function of generating an acid by being irradiated with light and further increasing the solubility of the portion irradiated with light in an alkaline aqueous solution. As the component (E), a compound generally called a photoacid generator can be used. Specific examples of the component (E) include an o-quinone diazode compound, an aryldiazonium salt, a diallyliodonium salt, a triarylsulfonium salt and the like. The component (E) may be composed of only one of these compounds, or may be composed of two or more of them. Among these, the o-quinone diazide compound is preferable because of its high sensitivity.

As the o-quinone diazide compound, for example, a compound obtained by condensing an o-quinone diazidosulfonyl chloride with a hydroxy compound or an amino compound in the presence of a dehydrochloric acid agent can be used.

The o-quinone diazide compounds are 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1-naphthoquinone-2-diazide-. It is preferable to use a condensate with 5-sulfonyl chloride, a condensate of tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane with 1-naphthoquinone-2-diazide-5-sulfonyl chloride.

The content of the component (E) is 5 to 25 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 becomes larger and the sensitivity becomes better. It is preferably 6 to 20 parts by mass, more preferably 7 to 18 parts by mass.

<Other ingredients>
In addition to the above components (A) to (E), the positive photosensitive resin composition of the present embodiment includes a solvent, a compound that produces an acid by heating, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a surfactant. , A leveling agent or the like may be contained.

(solvent)
By using a solvent, it is possible to facilitate coating on a substrate and 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, and N. , N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylenesulfone, diethylketone, diisobutylketone, methylamylketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol Examples thereof include monobutyl ether and dipropylene glycol monomethyl ether. These solvents may be used alone or in combination of two or more. Among these, ethyl lactate or propylene glycol monomethyl ether acetate is preferable from the viewpoint of solubility and uniformity of the coating film.

(Compound that produces acid by heating)
By using a compound that produces an acid by heating, it is possible to generate an acid when the patterned resin film is heated, so that the reaction between the component (A) and the components (B) and (C), that is, The thermal cross-linking reaction is promoted, and the heat resistance of the pattern cured film is improved. Further, since the compound that produces an acid by heating also generates an acid by light irradiation, the solubility of the exposed portion in the alkaline aqueous solution is increased. Therefore, the difference in solubility between the unexposed portion and the exposed portion in the alkaline aqueous solution becomes larger, and the resolution is further improved.

Examples of the compound that produces an acid by such heating include a compound that produces an acid by heating to 50 to 250 ° C. Specific examples of the compound that produces an acid by heating include a salt formed from a strong acid such as an onium salt and a base, an imide sulfonate, and the like.

(Dissolution accelerator)
By using the dissolution accelerator, the dissolution rate of the exposed portion when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. As the dissolution accelerator, conventionally known ones can be used. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.

Further, the dissolution accelerator may be a phenolic small molecule compound represented by any of 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 integers of 0 to 3, the total of d1 to f1 is 1 or more, the total of a1 and d1 is 5 or less, the total of b1 and e1 is 5 or less, and the total 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 indicate an integer of 0 to 3, d2 to f2 indicate an integer of 1 to 3, the total of a2 and d2 is 5 or less, the total of b2 and e2 is 5 or less, and c2 and f2. The total is 5 or less.

In the general formula (43), a3, c3, h and i indicate an integer of 0 to 3, d3 and f3 indicate an integer of 1 to 3, the total of a3 and d3 is 5 or less, and c3 and f3. The total is 5 or less, and the total 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 an alkaline aqueous solution, and is used to control the residual film thickness, development time, and contrast. Examples of the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodinenium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodine and the like.

(Coupling agent)
By using the coupling agent, the adhesiveness between the formed pattern curing film and the substrate can be further enhanced. Examples of the coupling agent include an organic silane compound and an aluminum chelate compound.

(Surfactant, Leveling agent)
By using a surfactant or a leveling agent, the coatability can be further improved. Specifically, for example, by containing a surfactant or a leveling agent, striation (unevenness of film thickness) 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, polyoxyethylene octylphenol ether and the like.

When other components are used, the content may be 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A).

According to the positive photosensitive resin composition of the present embodiment, it is possible to form a pattern cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate.

[Thermal cross-linking agent for positive photosensitive resin]
The thermal cross-linking agent for a positive photosensitive resin of one embodiment includes the above-mentioned component (B) (compound represented by the general formula (1) or compound represented by the general formula (2)) and the component (C) ( It consists of a compound having two or more epoxy groups). According to such a thermal cross-linking agent for positive photosensitive resin, a positive photosensitive resin composition capable of forming a pattern cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate. The thing can be easily prepared.

[Pattern cured film and its manufacturing method]
The pattern cured film of one embodiment includes a cured product of a resin film having a pattern and having the pattern made of the above-mentioned positive photosensitive resin composition. The pattern cured film is obtained by heating the above-mentioned positive photosensitive resin composition. Hereinafter, a method for manufacturing a pattern cured film will be described.

The method for producing the pattern cured film of the present embodiment includes a step of applying and drying the above-mentioned positive photosensitive resin composition to a part or all of the substrate to form a resin film (coating / drying (deposition) step). , A step of exposing a part or all of the resin film (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) is provided. Hereinafter, each step will be described.

<Applying / drying (deposition) process>
First, the positive photosensitive resin composition of the present embodiment is applied onto a substrate and dried to form a resin film. In this step, the positive photosensitive resin composition of the present embodiment is applied to a substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ , etc.), silicon nitride, etc. using a spinner or the like. And apply by rotation to form a coating film. The thickness of the coating film is not particularly limited, but is preferably 0.1 to 40 μm. The substrate on which this 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 it is preferably carried out at 80 to 140 ° C. for 1 to 7 minutes. As a result, a resin film is formed on the support substrate. The thickness of the resin film is not particularly limited, but is preferably 0.1 to 40 μm.

<Exposure process>
Next, in the exposure step, the resin film formed on the substrate is irradiated with active rays such as ultraviolet rays, visible rays, and radiation through a mask. In the positive photosensitive resin composition of the present embodiment, since the component (A) has high transparency to i-rays, i-ray irradiation can be suitably used. After exposure, post-exposure heating (PEB) can also be performed, if necessary, from the viewpoint of improving the dissolution rate. The temperature for post-exposure heating is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

<Development process>
In the developing step, the exposed portion of the resin film after the exposure step is removed with a developing solution, so that the resin film is patterned and a patterned resin film is obtained. As the developing solution, for example, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is preferably used. Be done. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Further, alcohols or surfactants may be added to the developer for use. 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 developing solution. When developing with a developer, the developer is placed on a resin film by, for example, shower development, spray development, immersion development, paddle development, etc., and 30 to 360 ° C. under the conditions of 18 to 40 ° C. Leave for a second. After leaving it to stand, the pattern resin film is washed by washing with water and performing spin drying.

<Heat treatment process>
Next, 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 250 ° C. or lower, more preferably 230 ° C. or lower, from the viewpoint of sufficiently preventing heat damage to the semiconductor device.

The heat treatment can be performed using, for example, an oven such as a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, or a microwave curing furnace. Further, either the atmosphere or the inert atmosphere such as nitrogen can be selected, but it is preferable to carry out under nitrogen because the pattern oxidation 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 suppressed to a small extent. Therefore, by using the method for manufacturing the resist pattern of the present embodiment, the electronic device can be manufactured with a high yield. It also leads to energy saving of the process. Further, according to the positive photosensitive resin composition of the present embodiment, since the volume shrinkage (curing shrinkage) in the heat treatment step seen in the photosensitive polyimide or the like is small, it is possible to prevent a decrease in dimensional accuracy.

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

Further, the heat treatment can be performed by using a microwave curing device or a frequency variable microwave curing device in addition to the above-mentioned 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, for example, 200 ° C. or lower (J. Photopolym. Sci. Technol.,. 18,327-332 (2005)).

According to the method for producing a pattern-cured film of the present embodiment described above, a pattern-cured film having sufficiently high sensitivity and resolution and excellent adhesion and thermal shock resistance can be obtained.

[Interlayer insulation layer, surface protection layer]
The pattern cured film of the present embodiment can be used as an interlayer insulating layer or a surface protective layer of a semiconductor device.

[Semiconductor device]
The semiconductor device of one embodiment includes an interlayer insulating layer or a surface protective layer of the present embodiment. The semiconductor element of the present embodiment is not particularly limited, but means a memory, a package, or the like having a multi-layer wiring structure, a rewiring structure, or the like.

Here, an example of the manufacturing process of the semiconductor element 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 element having a multilayer wiring structure. In FIGS. 1 to 5, (a) is a schematic perspective view, and (b) is a schematic end view showing the 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 a circuit element, a protective film 2 such as a silicon oxide film having a predetermined pattern on which the circuit element is exposed, and a silicon oxide film covering the semiconductor substrate 1, and an exposed circuit element. The first conductor layer 3 formed above and the interlayer insulating layer 4 made of a polyimide resin or the like formed on the protective film 2 and the first conductor layer 3 by a spin coating method or the like are provided.

Next, the structure 200 shown in FIG. 2 is obtained by forming the photosensitive resin layer 5 having the window portion 6A on the interlayer insulating layer 4. The photosensitive resin layer 5 is formed by applying a photosensitive resin such as a rubber chloride type, a phenol novolac type, a polyhydroxystyrene type, or a polyacrylic acid ester type by a spin coating method. The window portion 6A is formed by a known photographic etching technique so that the interlayer insulating layer 4 of a predetermined portion is exposed.

After the interlayer insulating layer 4 is etched to form the window portion 6B, the photosensitive resin layer 5 is removed to obtain the structure 300 shown in FIG. A dry etching means using a gas such as oxygen or carbon tetrafluoride can be used for etching the interlayer insulating layer 4. By this etching, the interlayer insulating layer 4 of the portion 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 portion 6B.

Further, the second conductor layer 7 is formed in the portion corresponding to the window portion 6B to obtain the structure 400 shown in FIG. A known photographic etching 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, and the semiconductor element 500 shown in FIG. 5 is obtained. In the present embodiment, the surface protective layer 8 is formed as follows. First, the above-mentioned photosensitive resin composition is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by a spin coating method, and dried to form a photosensitive resin film. Next, after irradiating a predetermined portion with light through a mask on which a pattern corresponding to the window portion 6C is drawn, the exposed resin film is developed with an alkaline aqueous solution to form a pattern resin film. After that, the pattern resin film is cured by heating to form a pattern cured film used as the surface protective layer 8. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, and the like, and the semiconductor element 500 using the surface protective layer 8 of the present embodiment is reliable. Excellent in sex.

Although the above-described embodiment shows a method for manufacturing a semiconductor element having a two-layer wiring structure, when forming a three-layer or more multi-layer wiring structure, the above steps are repeated to form each layer. Can be done. That is, it is possible to form a multi-layered pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. Further, in the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed by using the photosensitive resin composition of the present embodiment.
The electronic device of the present embodiment is not limited to the one having a surface protective layer, a cover coat layer or an interlayer insulating layer formed by using the above-mentioned positive photosensitive 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 photosensitive resin composition of the present embodiment is also excellent in stress relaxation property, adhesiveness, etc., it can be used in a semiconductor device having a rewiring structure as shown in FIGS. 6 and 7 which has been developed in recent years.

FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of a semiconductor element. The semiconductor element 600 shown in FIG. 6 has an Al having a pattern including a silicon substrate 23, an interlayer insulating layer 11 provided on one side of the silicon substrate 23, and a pad portion 15 formed on the interlayer insulating layer 11. The surface of the wiring layer 12, the insulating layer 13 (for example, P-SiN layer, etc.) and the surface protective 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. The island-shaped core 18 arranged in the vicinity of the opening on the protective layer 14 is in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14, and is on the surface of the core 18 opposite to the surface protective layer 14. It is provided with a rewiring layer 16 extending on the surface protective layer 14 so as to be in contact with the surface protective layer 14. Further, the semiconductor element 600 is formed by covering the surface protection layer 14, the core 18, and the rewiring layer 16, and the cover coat layer 19 having an opening formed in the portion of the rewiring layer 16 on the core 18 and the cover coat. A conductive ball 17 connected to the rewiring layer 16 with a barrier metal 20 sandwiched between the openings of the layer 19, a collar 21 for holding the conductive ball, and a 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 mounting the semiconductor element 600.

In the semiconductor element 700 of FIG. 7, an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon substrate 23, and an insulating layer 13 is formed on the pad portion 15 of the Al wiring layer. The surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to the upper part of the connecting 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 via the barrier metal 20.

In the semiconductor devices of FIGS. 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 adhesion to a metal layer such as the Al wiring layer 12 or the rewiring layer 16 or a sealing agent, and has a high stress relaxing effect. Semiconductor devices in which the pattern curing film is used for the interlayer insulating layer 11, the surface protective layer 14, the cover coat layer 19, the core 18, the color 21 such as solder, the underfill 22 used in flip chips, etc. are extremely excellent in reliability. It becomes a thing.

The photosensitive resin composition of the present 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. 6 and 7.

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

[Electronic device]
The electronic device of one embodiment has the semiconductor device of this embodiment. The electronic device includes the above-mentioned semiconductor element, and examples thereof include mobile phones, smartphones, tablet terminals, personal computers, hard disk suspensions, and the like.

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

The materials used in the examples are shown below.

[(A) component]
Polymer of A1: 4-hydroxystyrene (weight average molecular weight = 10,000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker M")
A2: 4-Hydroxystyrene / styrene = 85/15 (molar ratio) copolymer (weight average molecular weight = 10,000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker CST")
A3: 4-hydroxystyrene / methyl methacrylate = 70/30 (molar ratio) copolymer (weight average molecular weight = 12000, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Marcalinker CMM")
A4: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, weight average molecular weight = 12000, manufactured by Asahi Organic Materials Co., Ltd., trade name "EP4020G")

The weight average molecular weight was determined by gel permeation chromatography (GPC) method in terms of standard polystyrene.

Specifically, the weight average molecular weight was measured with the following devices and conditions.
measuring device:
Detector: L4000UV manufactured by Hitachi, Ltd.
Pump: L6000 manufactured by Hitachi, Ltd.
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: UV270 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]
B1: Compounds in which R ¹ to R ⁶ of the general formula (1) are all methyl groups (hexakis (methoxymethyl) melamine, manufactured by Sanwa Chemical Co., Ltd., trade name "Nicarac MW-30HM", molecular weight: 390.4).
B2: A compound in which R ⁷ to R ¹² of the general formula (2) are all methyl groups (manufactured by Honshu Chemical Industry Co., Ltd., trade name "HMOM-TPPA", molecular weight 688.9).

Ｃ５：２官能エポキシ化合物（ポリエチレングリコール＃４００ジグリシジルエーテル、共栄社化学株式会社製、商品名「エポライト４００Ｅ」、分子量：５２６．６）[(C) component]
C1: 3 functional epoxy compound (compound in which R ¹³ to R ¹⁵ of the general formula (3) are all methylene groups, manufactured by Nissan Chemical Industries, Ltd., trade name "TEPIC-L", molecular weight: 297.3)
C2: Trifunctional epoxy compound (compound ⁱⁿ which R13 to R15 of the general formula ⁽ 3) are all n-propylene groups, manufactured by Nissan Chemical Industries, Ltd., trade name "TEPIC-VL", molecular weight: 381.4)
C3: Trifunctional epoxy compound (compound ⁱⁿ which R13 to R15 of the general formula ⁽ 3) are all n-hexylene groups, manufactured by Nissan Chemical Industries, Ltd., trade name "TEPIC-FL", molecular weight: 507.7)
C4: Trifunctional epoxy compound (compound represented by the following formula (X), manufactured by Printec Co., Ltd., trade name "TECHMORE VG3101L", molecular weight: 592.7)

C5: Bifunctional epoxy compound (polyethylene glycol # 400 diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd., trade name "Epolite 400E", molecular weight: 526.6)

[(D) component]
D1: 55 g of ethyl lactate was weighed in a 100 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, and a separately weighed polymerizable monomer (n-butyl (BA) 34.7 g). , 2.2 g of lauryl acrylate (LA), 3.9 g of acrylic acid (AA), 2.6 g of hydroxybutyl acrylate (HBA) and 1,2,2,6,6-pentamethylpiperidin-4-ylmethacrylate ( Product name: FA-711MM, manufactured by Hitachi Kasei Co., Ltd.) 1.7 g and 0.29 g of azobisisobutyronitrile (AIBN) were added. Nitrogen gas was added while stirring at room temperature at a stirring speed of about 160 rpm. Was flown at a flow rate of 400 ml / min for 30 minutes to remove dissolved oxygen. After that, the inflow 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. The polymerization reaction was carried out for a long time to obtain Elastoma D1. The polymerization rate at this time was 99%, and the weight average molecular weight of this D1 was about 22000. The polymerizable property in Elastoma D1. The molar ratio of the monomers is as follows.
BA / LA / AA / HBA / FA-711MM = 70.5 / 2.5 / 20/5/2 (mol%)

The weight average molecular weight of the component (D) was determined by the same method as the measurement of the weight average molecular weight of the component (A).

[(E) component]
E1: Compound represented by the following formula (Y) (manufactured by Daito Chemix Co., Ltd., trade name "PA-28")

(Examples 1 to 9 and Comparative Examples 1 to 3)
The components (A) to (C) of the blending amount (parts by mass) shown in Table 1 and 120 parts by mass of ethyl lactate as a solvent are blended, and this is pressure-filtered using a Teflon (registered trademark) filter having 3 μm pores. , Examples 1 to 9 and Comparative Examples 1 to 3 were prepared as positive photosensitive resin compositions.

<Evaluation of positive photosensitive resin composition>
(Preparation of cured film)
The positive photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a film thickness of about 12 to 14 μm. did. Then, the resin film was heat-treated (cured) by the following method (i) to obtain a cured film having a film thickness of about 10 μm.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name "μ-TF"), the resin membrane was heat-treated in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. ..

(Chemical swelling rate)
Flux (manufactured by Senju Metal Industry Co., Ltd., trade name "WF-6300LF") was applied as a chemical solution on the cured film obtained by the above-mentioned (preparation of cured film), and heat-treated at 260 ° C. for 3 minutes. Later, it was washed with water to remove the chemical solution. The film thickness of the cured film before and after the chemical treatment was measured, and the chemical swelling rate was calculated from the following formula. The smaller the value (25% or less), the better the chemical swelling rate. The results are shown in Table 1.
Chemical solution swelling rate (%) = [(Thickness of cured film after chemical solution treatment) / (Thickness of cured film before chemical solution treatment) -1] x 100

(Residual stress)
The residual stress of the cured film obtained by the above-mentioned (preparation of the cured film) was measured using a stress measuring device (FLX-2320 type manufactured by KLA Tencor Co., Ltd.). The smaller the value (20 MPa or less), the better the residual stress. The results are shown in Table 1.

(Al adhesion strength)
The positive photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 are spun on a 6-inch aluminum substrate (a substrate in which Ti is sputtered on a silicon substrate and then aluminum is spattered on the Ti). It was coated and heated at 120 ° C. for 3 minutes to form a resin film having a film thickness of 11 to 13 μm. Then, it was heat-treated (cured) by the method of (i) above to obtain a cured film having a film thickness of about 10 μm. This cured film was cut into small pieces (1 cm × 1 cm) together with the substrate, and the aluminum stud and the cured film were bonded via an epoxy resin layer. Next, the stud was pulled and the load at the time of peeling was measured. The larger the value (39.2 MPa (400 kgf / cm ² ) or more), the better the adhesion strength. The results are shown in Table 1.

As shown in Table 1, the positive photosensitive resin composition containing the component (B) and the component (C) is compared with the positive photosensitive resin composition containing the component (B) and the component (C). In the obtained cured film, the residual stress was reduced, and the chemical solution resistance and the adhesion to the substrate were also excellent.

(Examples 10 and 11 and Comparative Examples 4 to 6)
The components (A) to (E) in the blending amount (parts by mass) shown in Table 2 and 120 parts by mass of ethyl lactate as a solvent are blended, and this is pressure-filtered using a Teflon (registered trademark) filter having 3 μm pores. , And the positive photosensitive resin compositions of Examples 10 and 11 and Comparative Examples 4 to 6 were prepared.

<Evaluation of positive photosensitive resin composition>
(Chemical swelling rate, residual stress, adhesion strength)
The evaluation was performed by the same method as the above-mentioned method. The results are shown in Table 2.

(Preparation of pattern cured film)
The positive photosensitive resin compositions of Examples 10 and 11 and Comparative Examples 4 to 6 were spin-coated on a 6-inch silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a film thickness of about 12 to 14 μm. did. Then, this resin film was exposed using a proximity exposure machine (manufactured by Canon Inc., trade name "PLA-600FA") through a mask at all wavelengths with an exposure amount twice the minimum exposure amount. After the exposure, development was carried out using a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) to obtain a pattern resin film having a width of 10 mm. Then, the pattern resin film was heat-treated (cured) by the following method (i) to obtain a pattern-cured film having a film thickness of about 10 μm.
(I) Using a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name "μ-TF"), heat-treat the pattern resin film in nitrogen at a temperature of 230 ° C. (heating time 1.5 hours) for 2 hours. did.

(Breaking strength after curing, breaking elongation after curing)
The breaking strength and breaking elongation of the obtained pattern cured film were measured using Autograph AGS-H100N (manufactured by Shimadzu Corporation). The width of the sample was 10 mm, the film thickness was 9 to 11 μm, and the distance between the chucks was 20 mm. The pulling speed was 5 mm / min and the measurement temperature was 20 ° C to 25 ° C. The average of the measured values of five or more test pieces obtained from the pattern cured film obtained under the same conditions was defined as "break strength" and "break elongation". The larger the value (100 MPa or more), the better the breaking strength. The larger the value (30% or more), the better the elongation at break. The results are shown in Table 2.

(CTE)
The average coefficient of thermal expansion (CTE) at 50 to 150 ° C. of the cured film obtained by the same method as described above (preparation of the patterned cured film) was measured using TMA / SS600 (manufactured by Seiko Instruments Inc.). The width of the sample used for the measurement was adjusted to 2 mm, the film thickness was adjusted to about 10 μm, and the chuck spacing was adjusted to 10 mm. The measurement conditions were a load of 10 g and a heating rate of 5 ° C./min. The lower the value of CTE (70 ppm / K or less), the better. The results are shown in Table 2.

As shown in Table 2, the positive photosensitive resin composition containing the component (B) and the component (C) and further containing the component (D) and the component (E) is the component (B) and the component (C). Compared with the positive photosensitive resin composition containing no, the residual stress was reduced in the obtained cured film, and the chemical solution resistance and the adhesion to the substrate were also excellent. It was also found that the obtained pattern cured film was excellent in breaking strength, breaking elongation and thermal expansion coefficient.

From the above, it was confirmed that the positive photosensitive resin composition of the present invention can form a cured film having low residual stress, excellent chemical resistance, and excellent adhesion to a substrate.

1 ... semiconductor substrate, 2 ... protective film, 3 ... first conductor layer, 4 ... interlayer insulating layer, 5 ... photosensitive resin layer, 6A, 6B, 6C ... window, 7 ... second conductor layer, 8 ... surface protection Layer, 11 ... Interlayer insulation layer, 12 ... Al wiring layer, 13 ... Insulation layer, 14 ... Surface protection layer, 15 ... Pad part, 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 element.

Claims (7)

(A) A hydroxystyrene resin having a structural unit represented by the following general formula (21), and
(B) The compound represented by the following general formula (1) and
(C) The compound represented by the following general formula (3) and
Contains,
The total amount of the component (B) and the component (C) is 5 to 25 parts by mass with respect to 100 parts by mass of the component (A).
A positive photosensitive resin composition in which the molar ratio of the component (C) to the component (B) is 0.2 to 1.0.

[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 indicate an integer of 0 to 3, and b indicates an integer of 1 to 3. The total of a and b is 5 or less. ]

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

[In the general formula (3), R ¹³ to R ¹⁵ each independently represent an alkylene group having 1 to 10 carbon atoms. ] (D) The positive photosensitive resin composition according to claim 1, further containing an elastomer. (E) The positive photosensitive resin composition according to claim 1 or 2, further containing a compound that produces an acid by light. A pattern cured film having a pattern, wherein the pattern contains a cured product of a resin film comprising the positive photosensitive resin composition according to any one of claims 1 to 3. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 3 to a part or all of a substrate and drying it to form a resin film.
The step of exposing a part or all of the resin film and
A step of developing the resin film after exposure with an alkaline aqueous solution to form a pattern resin film, and
The step of heating the pattern resin film and
A method for producing a patterned cured film. A semiconductor device comprising the pattern curing film according to claim 4 as an interlayer insulating layer or a surface protective layer. An electronic device comprising the semiconductor device according to claim 6 .

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