KR20200006522A - Positive photosensitive resin composition, thermal crosslinking agent for positive photosensitive resin, pattern cured film, its manufacturing method, semiconductor element, and electronic device - Google Patents

Abstract

[일반식 (1) 중, R¹∼R⁶은 각각 독립적으로 탄소수 1∼10의 알킬기를 나타낸다.]

[일반식 (2) 중, R⁷∼R¹²는 각각 독립적으로 탄소수 1∼10의 알킬기를 나타낸다.]Positive type photosensitive containing (A) alkali-soluble resin, (B) the compound represented by following General formula (1) or the compound represented by following General formula (2), and (C) the compound which has two or more epoxy groups A resin composition is disclosed.

[In General Formula (1), R <^1> -R <^6> respectively independently represents a C1-C10 alkyl group.]

[In General Formula (2), R <^7> -R <^12> respectively independently represents a C1-C10 alkyl group.]

Description

Positive photosensitive resin composition, thermal crosslinking agent for positive photosensitive resin, pattern cured film, its manufacturing method, semiconductor element, and electronic device

This invention relates to a positive photosensitive resin composition, the thermal crosslinking agent for positive photosensitive resins, a pattern cured film, its manufacturing method, a semiconductor element, and an electronic device.

In recent years, with high integration and miniaturization of semiconductor devices, it is required that insulating layers such as interlayer insulating layers and surface protection layers of semiconductor devices have more excellent heat resistance (coefficient of thermal expansion, etc.), mechanical properties (break strength, elongation at break, and the like). It is becoming. As a material for forming the insulating layer which has such a characteristic, the positive photosensitive resin composition containing alkali-soluble resin is developed (for example, refer patent document 1, 2 and 3). These positive photosensitive resin compositions are apply | coated and dried on a board | substrate, a resin film is formed, and a pattern resin film (pattern-formed resin film) is obtained by exposing and developing this resin film. And a pattern cured film (pattern formed cured film) can be formed by heat-hardening the said pattern resin film, This pattern cured film can be used as an insulating layer. Moreover, these photosensitive resin compositions have the advantage that the heat-hardening at low temperature is possible in the process of forming a pattern cured film.

Patent Document 1: Japanese Unexamined Patent Publication No. 2008-309885 Patent Document 2: Japanese Unexamined Patent Publication No. 2007-057595 Patent Document 3: International Publication No. 2010/073948

By the way, as a semiconductor element becomes smaller in size and an insulating layer becomes multilayer, the curvature of the package resulting from the residual stress of the pattern cured film used for an insulating layer becomes a problem. Therefore, the material to be used is requested | required to reduce the residual stress of the pattern cured film formed.

Generally, in order to reduce the residual stress of a cured film, it is thought that reducing the crosslinking density of a cured film is effective. However, when the crosslinking density is lowered, the film strength tends to decrease at the same time, and the chemical resistance of the pattern cured film tends to decrease.

This invention is made | formed in view of such a situation, Comprising: It aims at providing the positive photosensitive resin composition which can form the cured film which is low in residual stress, excellent in chemical-resistance resistance, and excellent in adhesiveness with a board | substrate.

As a result of earnestly examining in order to achieve the said objective, the present inventors discovered that by combining a specific compound in positive type photosensitive resin composition, the cured film which was low in residual stress and excellent in chemical-resistance was formed. Moreover, it discovered that the cured film obtained is excellent in adhesiveness with a board | substrate, and came to complete this invention.

One aspect of this invention has (A) alkali-soluble resin, (B) the compound represented by following General formula (1), or the compound represented by following General formula (2), and (C) two or more epoxy groups Provided is a positive photosensitive resin composition containing a compound. According to such a positive photosensitive resin composition, it becomes possible to form the pattern cured film which is low in residual stress, excellent in chemical-resistance tolerance, and excellent in adhesiveness with a board | substrate.

[In General Formula (1), R <^1> -R <^6> respectively independently represents a C1-C10 alkyl group.]

[In General Formula (2), R <^7> -R <^12> respectively independently represents a C1-C10 alkyl group.]

The molar ratio of the component (C) to the component (B) may be 1.0 or less. If the molar ratio is in this 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. In addition, the compound represented by following General formula (3) may be sufficient as (C) component. If (C) component is such a compound, it exists in the tendency for the chemical liquid tolerance of the pattern cured film formed to be more excellent.

[In General Formula (3), R <^13> -R <^15> respectively independently represents a C1-C10 alkylene group.]

The positive photosensitive resin composition may further contain (D) an elastomer. In addition, the positive photosensitive resin composition may further contain a compound that generates an acid by (E) light. By using these components, there exists a tendency which is excellent in the heat resistance (thermal expansion coefficient) and mechanical characteristics (breaking strength and elongation at break) of the patterned cured film formed.

In another aspect, there is provided a thermal crosslinking 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. By using such a positive photosensitive resin thermal crosslinking agent, the positive photosensitive resin composition which can form the pattern cured film which is low in residual stress, excellent in chemical-resistance resistance, and excellent in adhesiveness with a board | substrate can be easily prepared.

[In General Formula (1), R <^1> -R <^6> respectively independently represents a C1-C10 alkyl group.]

[In General Formula (2), R <^7> -R <^12> respectively independently represents a C1-C10 alkyl group.]

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

In another aspect, a process of forming a resin film by applying and drying the above-described positive photosensitive resin composition to a part or the whole of the substrate, exposing a part or the whole of the resin film, and developing the resin film after exposure using an aqueous alkali solution And the process of forming a pattern resin film, and the process of heating a pattern resin film are provided.

In another aspect, there is provided a semiconductor device comprising the above patterned cured film as an interlayer insulating layer or a surface protective layer.

In another aspect, an electronic device including the semiconductor element described above is provided.

ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which can form the cured film which is low in residual stress, excellent in chemical-resistance tolerance, and excellent in adhesiveness with a board | substrate can be provided. Moreover, the thermal crosslinking agent for positive photosensitive resins which can easily prepare such a positive photosensitive resin composition can be provided. Moreover, the pattern cured film using such a positive photosensitive resin composition, its manufacturing method, a semiconductor element, and an electronic device can be provided.

1 is a schematic perspective view and a schematic cross-sectional view illustrating an embodiment of a manufacturing process of a semiconductor device.
2 is a schematic perspective view and a schematic cross-sectional view illustrating an embodiment of a process for manufacturing a semiconductor device.
3 is a schematic perspective view and a schematic cross-sectional view illustrating an embodiment of a semiconductor device manufacturing process.
4 is a schematic perspective view and a schematic cross-sectional view illustrating an embodiment of a process for manufacturing a semiconductor device.
5 is a schematic perspective view and a schematic cross-sectional view illustrating an embodiment of a process for manufacturing a semiconductor device.
6 is a schematic cross-sectional view showing one embodiment of a semiconductor element.
7 is a schematic cross-sectional view showing one embodiment of a semiconductor element.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. However, this invention is not limited to the following embodiment.

"(Meth) acrylic acid" in this specification means "acrylic acid" or "methacrylic acid", and the same also in other similar expressions, such as (meth) acrylate.

[Positive photosensitive resin composition]

The positive photosensitive resin composition of one embodiment is (A) alkali-soluble resin, (B) the compound represented by General formula (1), or the compound represented by General formula (2), and (C) two or more epoxy groups It contains the compound which has.

<(A) component>

(A) component is resin soluble with respect to aqueous alkali solution (developer). Here, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide (TMAH) aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. Generally, the tetramethylammonium hydroxide aqueous solution of 2.38 mass% in concentration is used for image development.

It can be confirmed that (A) component is soluble in alkaline developing solution as follows, for example.

The varnish obtained by dissolving (A) component in arbitrary solvents is spin-coated and formed on the board | substrate, such as a silicon wafer, and it is set as the coating film with a film thickness of about 5 micrometers. This is immersed in either TMAH aqueous solution, metal hydroxide aqueous solution, or organic amine aqueous solution at 20-25 degreeC. As a result, when the coating film can be melt | dissolved uniformly, it can be said that (A) component is soluble in alkaline developing solution.

As the component (A), 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, polyether sulfone resin, polyphenylene sulfide resin, polycarbonate resin, polyether ketone resin, (meth) acrylic copolymer, The resin etc. which have phenolic hydroxyl group are mentioned. These can be used individually by 1 type or in combination of 2 or more type. Furthermore, glycol groups, carboxyl groups, or hydroxyl groups, such as ethylene glycol and propylene glycol, may be provided to the principal chain or side chain of these resin.

In these, it is preferable that (A) component is resin which has a phenolic hydroxyl group from a high temperature adhesiveness, heat resistance, and a film formability viewpoint.

As resin which has a phenolic hydroxyl group, For example, polybenzoxazole precursors, such as hydroxy styrene resin, such as a copolymer containing polyhydroxy styrene or hydroxy styrene as a monomeric unit, a phenol resin, poly (hydroxyamide), Poly (hydroxyphenylene) ether, polynaphthol and the like. (A) component may be comprised only 1 type in these resin, and may be comprised including 2 or more types.

Among them, (A1) hydroxystyrene-based resins are preferable in terms of excellent electrical properties (insulation) and small volume shrinkage during curing. In addition, from the viewpoint of low cost, high contrast, and small volume shrinkage during curing, the (A2) phenol resin is preferable, and a novolac phenol resin is more preferable.

The hydroxystyrene-based resin (A1) has a structural unit represented by the following general formula (21).

In general formula (21), R <^21> represents a hydrogen atom or a methyl group, R <^22> represents a C1-C10 alkyl group, a C6-C10 aryl group, or a C1-C10 alkoxy group, a is 0-3 An integer is shown and b represents the integer of 1-3. The sum of a and b is 5 or less.

(A1) hydroxy styrene resin can be obtained by polymerizing the monomer etc. which provide the structural unit represented by General formula (21).

In the general formula (21), examples of the alkyl group having 1 to 10 carbon atoms represented by R ²¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Can be mentioned. These groups may be linear or branched. Moreover, as a C6-C10 aryl group represented by R <^22> , a phenyl group, a naphthyl group, etc. are mentioned, for example. As a C1-C10 alkoxy group represented by R <^21> , a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group, a decock group etc. are mentioned, for example. . These groups may be linear or branched.

As a monomer which gives the structural unit represented by General formula (21), p-hydroxy styrene, m-hydroxy styrene, o-hydroxy styrene, p-isopropenyl phenol, m-isopropenyl phenol, o -Isopropenyl phenol etc. are mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types, respectively.

The hydroxystyrene-based resin (A1) is not particularly limited in its production method, but for example, the hydroxyl group of the monomer giving the structural unit represented by the general formula (21) is protected by t-butyl group, acetyl group or the like to protect the hydroxyl group. It is possible to obtain a polymer by polymerizing a monomer in which a hydroxyl group is protected, and to obtain a polymer, and to deprotect the obtained polymer by a known method (such as deprotection under an acid catalyst and conversion into a hydroxystyrene-based structural unit). .

The hydroxystyrene-based resin (A1) may be a polymer or a copolymer composed of only monomers giving the structural units represented by the general formula (21), monomers giving the structural units represented by the general formula (21), and others. The copolymer with the monomer of may be sufficient. When the hydroxystyrene resin (A1) is a copolymer, the proportion of the structural unit represented by the general formula (21) in the copolymer is based on 100 mol% of the component (A) in terms of solubility in the alkaline developer of the exposed part. , 10-100 mol% is preferable, 20-97 mol% is more preferable, 30-95 mol% is further more preferable, 50-95 mol% is especially preferable.

It is preferable that (A1) hydroxy styrene resin is alkali-soluble resin which has a structural unit further represented by following General formula (22) from a viewpoint of further improving the dissolution inhibition property to the alkali developing solution of an unexposed part.

In general formula (22), R <^23> represents a hydrogen atom or a methyl group, R <^24> represents a C1-C10 alkyl group, a C6-C10 aryl group, or a C1-C10 alkoxy group, c is a 0-3 Represents an integer.

An alkyl group having 1 to 10 carbon atoms represented by R ^24, alkoxy group of 1 to 10 carbon atoms or an aryl group of 6 to 10 carbon atoms, there can be mentioned the same as R ^22, respectively.

Alkali-soluble resin which has a structural unit represented by General formula (22) can be obtained by using the monomer which gives the structural unit represented by General formula (22). As a monomer which gives the structural unit represented by General formula (22), for example, styrene, (alpha) -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxy styrene, m-methoxy styrene and aromatic vinyl compounds such as p-methoxy styrene. These monomers can be used individually by 1 type or in combination of 2 or more types, respectively.

(A1) When the hydroxystyrene-based resin is an alkali-soluble resin having a structural unit represented by the general formula (22), in view of the dissolution inhibition property to the alkali developer of the unexposed part and the mechanical properties of the pattern cured film, the general formula ( As for the ratio of the structural unit represented by 22), 1-90 mol% is preferable with respect to 100 mol% of (A) component, 3-80 mol% is more preferable, 5-70 mol% is further more preferable, 5-50 mol% is especially preferable.

Moreover, it is preferable that (A1) hydroxy styrene resin is alkali-soluble resin which has a structural unit further represented by following General formula (23) from a viewpoint of reducing an elasticity modulus.

In general formula (23), R <^25> represents a hydrogen atom or a methyl group, R <^26> represents a C1-C10 alkyl group or a C1-C10 hydroxyalkyl group.

Alkali-soluble resin which has a structural unit represented by General formula (23) can be obtained by using the monomer which gives the structural unit represented by General formula (23). As a monomer which gives the structural unit represented by General formula (23), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) Hexyl acrylate, Heptyl (meth) acrylate, Octyl (meth) acrylate, Nonyl (meth) acrylate, Decyl (meth) acrylate, Hydroxymethyl (meth) acrylate, Hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate , (Meth) hydroxy butyl acrylate, (meth) hydroxy pentyl acrylate, (meth) hydroxyhexyl acrylate, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate nonyl, ( And meth) acrylic acid hydroxydecyl. These monomers can be used individually by 1 type or in combination of 2 or more types, respectively.

(A1) When the hydroxystyrene resin is an alkali-soluble resin having a structural unit represented by the general formula (23), from the viewpoint of the dissolution inhibiting property to the alkali developer of the unexposed part and the mechanical properties of the pattern cured film, the general formula ( As for the ratio of the structural unit represented by 23), 1-90 mol% is preferable with respect to 100 mol% of (A) component, 3-80 mol% is more preferable, 5-70 mol% is further more preferable, 5-50 mol% is especially preferable.

The phenol resin (A2) is a polycondensation product of phenol or its derivatives and aldehydes. Polycondensation is normally performed in presence of catalysts, such as an acid and a base. The phenol resin obtained when an acid catalyst is used is especially called a novolak-type phenol resin. As a novolak-type phenol resin, For example, a phenol / formaldehyde novolak resin, a cresol / formaldehyde novolak resin, xylenol / formaldehyde novolak resin, a resorcinol / formaldehyde novolak resin, a phenol naphthol / formaldehyde Novolak resin etc. are mentioned.

As a phenol derivative which comprises (A2) phenol resin, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-x Alkylphenols such as silenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol, 2-methoxy-4-methylphenol, vinylphenol, allylphenol and the like Aralkyl phenols such as alkenylphenol and benzylphenol, alkoxycarbonylphenols such as methoxycarbonylphenol, arylcarbonylphenols such as benzoyloxyphenol, halogenated phenols such as chlorophenol, catechol, resorcinol, pyrogallol Bisphenols such as polyhydroxybenzene, bisphenol A, bisphenol F, naphthol derivatives such as α- or β-naphthol, p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydride Hydroxyphenyl-4-butanol and the like Alcoholic hydroxyl group containing phenol derivatives, such as hydroxyalkyl cresols, such as a cyalkylphenol and hydroxyethyl cresol, the monoethylene oxide addition product of bisphenol, and the monopropylene oxide addition product of bisphenol, p-hydroxyphenyl acetic acid, p-hydroxyphenyl Carboxyl group-containing phenol derivatives such as propionic acid, p-hydroxyphenylbutanoic acid, p-hydroxy cinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxycyanic acid and diphenolic acid. These can be used individually by 1 type or in combination of 2 or more type.

Examples of the aldehydes constituting the phenol resin include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, and chloroacetaldehyde. , Chlorophenylacetaldehyde, Glycellaldehyde, Glyoxylic acid, Methyl Glyoxylate, Glyoxylic acid phenyl, Glyoxylic acid hydroxyphenyl, Formyl acetic acid, Methyl formyl acetate, 2-formylpropionic acid, 2-formyl Methyl propionate etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type. In addition, precursors of formaldehyde such as paraformaldehyde and trioxane, acetone, pyruvic acid, levulinic acid, 4-acetylbutyl acid, acetone dicarboxylic acid, 3,3'-4,4'-benzophenone tetracarboxylic You may use ketones, such as an acid, for reaction.

When (A) component contains (A1) hydroxy styrene resin or (A2) phenol resin, each weight average molecular weight of (A1) component and (A2) component is solubility with respect to aqueous alkali solution, photosensitive characteristic, and In view of the balance of the mechanical properties of the pattern cured film, the weight average molecular weight is preferably from 1000 to 500000, more preferably from 2000 to 200000, and even more preferably from 2000 to 100,000. A weight average molecular weight is a value measured by the gel permeation chromatography (GPC) method here, and is converted and obtained from a standard polystyrene calibration curve.

<(B) component>

The compound which is (B) component is a compound which has a structure which can react with (A) component, and can form a crosslinked structure, when heating and hardening the photosensitive resin film after pattern formation. (B) A component is a compound represented by following General formula (1), or a compound represented by following General formula (2).

In General Formula (1), R <^1> -R <^6> represents a C1-C10 alkyl group each independently.

The C1-C10 alkyl group represented by R <^1> -R <^6> can illustrate the same thing as R <^22> . It is preferable that carbon number of an alkyl group is 1-5, It is more preferable that it is 1-3, It is still more preferable that it is 1 or 2, It is especially preferable that it is 1.

In General Formula (2), R ⁷ to R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms.

The C1-C10 alkyl group represented by R <^7> -R <^12> can illustrate the same thing as R <^22> . It is preferable that carbon number of an alkyl group is 1-5, It is more preferable that it is 1-3, It is still more preferable that it is 1 or 2, It is especially preferable that it is 1.

<(C) component>

The compound as the component (C) has two or more epoxy groups, and when the photosensitive resin film after pattern formation is cured by heating with the compound as the component (B) described above, the compound can react with the component (A) to form a crosslinked structure. It is a compound having a structure.

The component (C) can be used without particular limitation as long as it has two or more epoxy groups. As (C) component, 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 etc. are mentioned, for example. Can be. These can be used individually by 1 type or in combination of 2 or more type.

Among these, from the viewpoint of better chemical resistance, the component (C) is preferably an epoxy compound having an aromatic ring or a heterocycle, more preferably an epoxy compound having a heterocycle, and an epoxy having a nitrogen-containing heterocycle. It is more preferable that it is a compound.

It is preferable that (C) component is a compound represented by following General formula (3) from a viewpoint that chemical | medical solution tolerance is more excellent.

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

In general formula (3), as a C1-C10 alkylene group represented by R <^13> -R <^15> , it is a methylene group, ethylene group, a propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, for example. And nonylene groups, decylene groups and the like. These groups may be linear or branched. It is preferable that it is 1-8, and, as for carbon number of an alkylene group, it is more preferable that it is 1-6.

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, preferably 0.9 or less, from the viewpoint of better chemical resistance and breaking strength. It is more preferable that it is 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.

It is preferable that it is 2-35 mass parts with respect to 100 mass parts of (A) component from a viewpoint that the total amount of (B) component and (C) component is more excellent in residual stress and chemical liquid tolerance, and it is 4-30 mass parts It is more preferable, and it is still more preferable that it is 5-25 mass parts.

In addition to (A)-(C) component, the positive photosensitive resin composition of this embodiment may further contain the compound which produces | generates an acid by (D) elastomer or (E) light. By using these components, the positive photosensitive resin composition excellent in breaking strength and thermal expansion property can be obtained.

<(D) component>

Examples of the elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers, and the like. These can be used individually by 1 type or in combination of 2 or more type. Among these, since the (D) component is excellent in breaking strength, breaking elongation, and thermal expansion property of the patterned cured film obtained, an acrylic elastomer may be sufficient.

It is preferable that an acryl-type elastomer has a structural unit represented by following General formula (31).

In 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 hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyheptyl group, hydroxyoctyl group, Hydroxynonyl group, hydroxydecyl group, hydroxy undecyl group, hydroxydodecyl group (sometimes called hydroxy lauryl group), hydroxy tridecyl group, hydroxy tetradecyl group, hydroxypentadecyl group , A hydroxyhexadecyl group, a hydroxyheptadecyl group, a hydroxyoctadecyl group, a hydroxy nonadecyl group, a hydroxyecosyl group, and the like.

The acrylic elastomer may further have 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).

In 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.

As a primary, secondary, or tertiary amino group represented by R ³⁴ , for example, aminoethyl group, N-methylaminoethyl group, N, N-dimethylaminoethyl group, N-ethylaminoethyl group, N, N-diethylaminoethyl group, amino Propyl group, N-methylaminopropyl group, N, N-dimethylaminopropyl group, N-ethylaminopropyl group, N, N-diethylaminopropyl group, piperidin-4-yl group, 1-methylpiperidine -4-yl group, 2,2,6,6-tetramethylpiperidin-4-yl group, 1,2,2,6,6-pentamethylpiperidin-4-yl group, (piperidin-4- (1) methyl group, 2- (piperidin-4-yl) ethyl group, and the like.

In 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.

As a C4-C20 alkyl group represented by R <^36> , 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 (lauryl group) may be mentioned, for example. ), Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. are mentioned. These groups may be linear or branched.

In General Formula (34), R ³⁷ represents a hydrogen atom or a methyl group.

An acrylic elastomer is a monomer which gives a structural unit represented by the said General formula (31), and the structural unit represented by General formula (32), general formula (33), or general formula (34) added as needed, for example. It can obtain by mix | blending the monomer to provide, stirring in solvent, such as ethyl lactate, toluene, and isopropanol, and heating as needed.

It is preferable that the weight average molecular weights of an acryl-type elastomer are 2000-100000, It is more preferable that it is 3000-60000, It is still more preferable that it is 5000-50000, It is especially preferable that it is 10000-40000. A weight average molecular weight is a value measured by the gel permeation chromatography (GPC) method here, and is converted and obtained from a standard polystyrene calibration curve.

It is preferable that it is 1-35 mass parts with respect to 100 mass parts of (A) component from a viewpoint that content of (D) component is more excellent in breaking strength and elongation at break, It is more preferable that it is 3-30 mass parts, 5 It is more preferable that it is -25 mass parts.

<(E) component>

The compound which produces | generates an acid by receiving light by (E) component functions as a photosensitive agent in the photosensitive resin composition. (E) component has the function which receives light irradiation, produces | generates an acid, and increases the solubility to the aqueous alkali solution of the part which received light irradiation further. As (E) component, the compound generally called a photo-acid generator can be used. Specific examples of the component (E) include an o-quinonediazide compound, an aryldiazonium salt, a diaryl iodonium salt, a triarylsulfonium salt, and the like. (E) A component may consist only of 1 type of these compounds, and may be comprised including 2 or more types. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

As an o-quinone diazide compound, what is obtained by condensation reaction of o-quinone diazide sulfonyl chloride, a hydroxy compound, an amino compound, etc. in presence of a dechlorination agent, etc. can be used, for example.

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

It is preferable that content of (E) component is 5-25 mass parts with respect to 100 mass parts of (A) component from a viewpoint that the difference of the dissolution rate between an exposure part and an unexposed part becomes larger, and a sensitivity becomes more favorable, It is more preferable that it is 6-20 mass parts, and it is still more preferable that it is 7-18 mass parts.

<Other ingredients>

Positive type photosensitive resin composition of this embodiment is a component, such as a solvent and the compound which produces | generates an acid by heating, a dissolution promoter, a dissolution inhibitor, a coupling agent, surfactant, a leveling agent other than said (A)-(E) component. It may contain.

(solvent)

By using a solvent, application | coating on a board | substrate can be made easy and the coating film of 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, and N-methyl-2- Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone And propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether and the like. These solvents can be used individually by 1 type or in combination of 2 or more type. Among them, ethyl lactate or propylene glycol monomethyl ether acetate is preferred from the viewpoint of solubility and uniformity of the coating film.

(Compound which generates acid by heating)

By using the compound which produces | generates an acid by heating, since acid can be generated when heating a patterned resin film, reaction of (A) component, (B) component, and (C) component, ie, thermal crosslinking reaction This is accelerated | stimulated and the heat resistance of a pattern cured film improves. Moreover, since the compound which produces | generates an acid by heating generates an acid also by light irradiation, solubility to the aqueous alkali solution of an exposure part increases. Therefore, the difference in solubility with respect to the aqueous alkali solution between an unexposed part and an exposure part becomes larger, and the resolution improves more.

The compound which produces | generates an acid by such a heating is what produces an acid, for example by heating to 50-250 degreeC. As a specific example of the compound which produces | generates an acid by heating, the salt formed from strong acids, such as an onium salt, and a base, an imide sulfonate, etc. are mentioned.

(Dissolution accelerator)

By using a dissolution accelerator, the dissolution rate of the exposed portion when developing with an aqueous alkali solution can be increased, and the sensitivity and resolution can be improved. As the dissolution accelerator, conventionally known ones can be used. As the specific example, the compound which has a carboxyl group, sulfonic acid, and sulfonamide group is mentioned.

The dissolution accelerator may be a phenolic low molecular compound represented by any of the following general formulas (41) to (43).

In General Formula (41), R ⁴¹ represents a hydrogen atom or a methyl group. a1-f1 represents the integer of 0-3, the sum of d1-f1 is one or more, the sum of a1 and d1 is five or less, the sum of b1 and e1 is five or less, and the sum of c1 and f1 is five or less to be.

In 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 5 or less.

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

(Dissolution release)

The dissolution inhibitor is a compound that inhibits dissolution of the (A) component into an aqueous alkali solution, and is used to control the residual film thickness, the development time, and the contrast. Examples of dissolution inhibitors include diphenyl iodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyl iodonium bromide, diphenyl iodonium chloride and diphenyl iodonium iodide. Deed and the like.

(Coupling agent)

By using a coupling agent, the adhesiveness of the pattern cured film formed and a board | substrate can be improved more. As a coupling agent, an organic silane compound, an aluminum chelate compound, etc. are mentioned, for example.

(Surfactant, leveling agent)

By using surfactant or a leveling agent, applicability | paintability can be improved more. Specifically, for example, by containing a surfactant or a leveling agent, it is possible to further prevent striation (staining of film thickness) or to improve developability. As surfactant or a leveling agent, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, etc. are mentioned, for example.

Content in the case of using another component may be 0.01-20 mass parts with respect to 100 mass parts of (A) component.

According to the positive photosensitive resin composition of this embodiment, it becomes possible to form the pattern cured film which is low in residual stress, excellent in chemical-resistance tolerance, and excellent in adhesiveness with a board | substrate.

[Heat crosslinking agent for positive photosensitive resin]

The thermal crosslinking agent for positive type photosensitive resin of one Embodiment is the above-mentioned (B) component (compound represented by General formula (1) or compound represented by General formula (2)), and (C) component (2 or more epoxy groups) Compound having; According to the thermal crosslinking agent for positive type photosensitive resin, the positive type photosensitive resin composition which can form the pattern cured film which is low in residual stress, excellent in chemical-resistance resistance, and excellent in adhesiveness with a board | substrate can be easily prepared.

[Pattern Cured Film and Manufacturing Method thereof]

The pattern cured film of one Embodiment has a pattern, and contains the hardened | cured material of the resin film in which a pattern consists of the positive photosensitive resin composition mentioned above. A pattern cured film is obtained by heating the positive photosensitive resin composition mentioned above. Hereinafter, the manufacturing method of a pattern cured film is demonstrated.

The manufacturing method of the pattern cured film of this embodiment is the process (coating, drying (film-forming) process) of apply | coating and drying the positive photosensitive resin composition mentioned above to one part or all part of a board | substrate, and forming a resin film, and a part or all of resin film. The step of exposing (exposing process), the process of developing the resin film after exposure by aqueous alkali solution, and forming a pattern resin film (development process), and the process of heating a pattern resin film (heating process process) are provided. Hereinafter, each process is demonstrated.

<Application and drying (film formation) process>

First, the positive photosensitive resin composition of this embodiment is apply | coated on a board | substrate, and is dried and a resin film is formed. In this step, the positive photosensitive resin composition of the present embodiment is spin-coated using a spinner or the like on a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ or the like), silicon nitride, or the like to form a coating film. To form. Although there is no restriction | limiting in particular in the thickness of a coating film, It is preferable that it is 0.1-40 micrometers. The board | substrate with which this coating film was formed is dried using a hotplate, oven, etc. Although there is no restriction | limiting in particular in drying temperature and drying time, It is preferable to carry out for 1 to 7 minutes at 80-140 degreeC. As a result, a resin film is formed on the support substrate. Although there is no restriction | limiting in particular in the thickness of a resin film, It is preferable that it is 0.1-40 micrometers.

Exposure process

Next, in an exposure process, actinic light, such as an ultraviolet-ray, a visible ray, a radiation, is irradiated to the resin film formed on the board | substrate through a mask. In the positive photosensitive resin composition of this embodiment, since (A) component has high transparency with respect to i line | wire, irradiation of i line | wire can be used suitably. In addition, post-exposure heating (PEB) can also be performed after the exposure from the viewpoint of improving the dissolution rate. As for the temperature in the case of heating after exposure, 1 minute-5 minutes of 70 degreeC-140 degreeC, and a post-exposure heating time are preferable.

Development Process

In a developing process, a resin film is patterned by removing the exposure part of the resin film after an exposure process with a developing solution, and a patterned resin film is obtained. As a developing solution, aqueous alkali solution, such as sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), is used suitably, for example. It is preferable to make the base concentration of these aqueous solutions into 0.1-10 mass%. Moreover, alcohol or surfactant can also be added and used to the said developing solution. These are each mix | blended in 100 mass parts of developing solutions, Preferably it is 0.01-10 mass parts, More preferably, it can mix | blend in the range of 0.1-5 mass parts. When developing using a developing solution, the developing solution is placed on the resin film by a method such as shower development, spray development, immersion development, paddle development, and the like, and left for 30 to 360 seconds under conditions of 18 to 40 ° C. . After standing, the pattern resin film is washed by washing with water and spin drying.

<Heating process>

Subsequently, in a heat processing process, a pattern cured film can be formed by heat-processing a pattern resin film. 250 degreeC or less is preferable and, as for the heating temperature in a heat processing process, fully preventing damage by the heat | fever with respect to a semiconductor device, 230 degreeC or less is more preferable.

The heat treatment can be performed using an oven such as a quartz tube, 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. In addition, although any of inert atmosphere, such as air | atmosphere or nitrogen, can be selected, since performing under nitrogen can prevent oxidation of a pattern, it is preferable. Since the range of the preferable heating temperature mentioned above is lower than the conventional heating temperature, the damage to a support substrate and a semiconductor device can be suppressed small. Therefore, the electronic device can be manufactured with high yield by using the manufacturing method of the resist pattern of this embodiment. It also leads to energy saving of the process. Furthermore, according to the positive photosensitive resin composition of this embodiment, since the volume shrinkage (hardening shrinkage) in the heat processing process shown to the photosensitive polyimide etc. is small, the fall of dimensional precision can be prevented.

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

Moreover, heat processing can also be performed using a microwave curing apparatus or a frequency variable microwave curing apparatus other than the oven mentioned above. By using these devices, only the photosensitive resin film can be effectively heated while maintaining the temperature of the substrate and the semiconductor device at, for example, 200 ° C. or lower (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)). ).

According to the manufacturing method of the pattern cured film of this embodiment mentioned above, the pattern cured film excellent also in adhesiveness and thermal shock can be obtained with sufficiently high sensitivity and resolution.

[Interlayer Insulation Layer, Surface Protection Layer]

The pattern cured film of this embodiment can be used as an interlayer insulation layer or surface protection layer of a semiconductor element.

[Semiconductor Device]

The semiconductor element of one embodiment includes the interlayer insulating layer or surface protective layer of this embodiment. Although the semiconductor element of this embodiment is not restrict | limited in particular, It means the memory, package, etc. which have a multilayer wiring structure, a redistribution structure, etc ..

Here, an example of the manufacturing process of a semiconductor element is demonstrated based on drawing. 1-5 is a schematic perspective view and schematic sectional drawing which shows one Embodiment of the manufacturing process of the semiconductor element which has a multilayer wiring structure. In FIGS. 1-5, (a) is a schematic perspective view, (b) is a schematic sectional drawing which shows Ib-Ib-Vb-Vb cross section 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 covering the semiconductor substrate 1, having a predetermined pattern to which the circuit element is exposed, The interlayer insulating layer 4 made of the first conductor layer 3 formed on the exposed circuit elements, and the protective film 2 and the polyimide resin formed on the first conductor layer 3 by spin coating or the like is formed. Equipped.

Next, the structure 200 shown in FIG. 2 is obtained by forming the photosensitive resin layer 5 which has the window part 6A on the interlayer insulation layer 4. The photosensitive resin layer 5 is formed by apply | coating photosensitive resin, such as a rubber chloride type, a phenol novolak type, a polyhydroxy styrene type, and a polyacrylic acid ester type, by a spin coat method, for example. The window portion 6A is formed such that the interlayer insulating layer 4 of a predetermined portion is exposed by a known photolithography technique.

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. 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 to obtain the interlayer insulating layer 4 provided with the window portion 6B so that the first conductor layer 3 is exposed. Lose. Next, the photosensitive resin layer 5 is removed using the etching solution which only corrodes the photosensitive resin layer 5, without corroding the 1st conductor layer 3 exposed from the window part 6B.

Moreover, the 2nd conductor layer 7 is formed in the part corresponding to the window part 6B, and the structure 400 shown in FIG. 4 is obtained. Known photolithography techniques can be used to form the second conductor layer 7. Thereby, the electrical connection of the 2nd conductor layer 7 and the 1st conductor layer 3 is made.

Finally, the surface protection layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain the semiconductor element 500 shown in FIG. 5. In this embodiment, the surface protection layer 8 is formed as follows. First, the photosensitive resin composition mentioned above is apply | coated on the interlayer insulation layer 4 and the 2nd conductor layer 7 by a spin coat method, and it dries to form a photosensitive resin film. Subsequently, after irradiating the pattern corresponding to the window part 6C to a predetermined part through the green mask, the resin film after exposure is developed by aqueous alkali solution, and a pattern resin film is formed. Thereafter, the patterned resin film used as the surface protective layer 8 is formed by curing the patterned resin film by heating. The surface protective layer 8 protects from the stress from the outside of the 1st conductor layer 3 and the 2nd conductor layer 7, alpha rays, etc., and uses the semiconductor using the surface protection layer 8 of this embodiment. The device 500 is excellent in reliability.

In addition, although the manufacturing method of the semiconductor element which has a 2-layer wiring structure was shown in embodiment mentioned above, when forming a multilayer wiring structure of three or more layers, the above-mentioned process can be repeated and each layer can be formed. . That is, a multi-layered pattern can be formed by repeating each process of forming the interlayer insulation layer 4 and each process of forming the surface protection layer 8. In addition, in the above-mentioned example, not only the surface protection layer 8 but also the interlayer insulation layer 4 can be formed using the photosensitive resin composition of this embodiment.

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

6 and 7 are schematic cross-sectional views showing one embodiment of a semiconductor device having a redistribution structure. Since the photosensitive resin composition of this embodiment is excellent also in stress relaxation property, adhesiveness, etc., it can be used in the semiconductor element which has a redistribution structure like FIG. 6 and 7 newly developed.

6 is a schematic cross-sectional view showing a wiring structure as an embodiment of a semiconductor element. The semiconductor element 600 illustrated in FIG. 6 includes a silicon substrate 23, an interlayer insulating layer 11 provided on one surface side of the silicon substrate 23, and a pad portion formed on the interlayer insulating layer 11. Al wiring layer 12 having a pattern including 15, and insulating layer 13 sequentially stacked on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15 (for example, P-SiN layer, etc.) and the surface protection layer 14, the island-shaped core 18 arranged in the vicinity of the opening on the surface protection layer 14, and the opening of the insulating layer 13 and the surface protection layer 14 The redistribution layer 16 extends on the surface protection layer 14 so as to contact the pad portion 15 and contact the surface opposite to the surface protection layer 14 of the core 18. In addition, the semiconductor device 600 is formed by covering the surface protection layer 14, the core 18, and the redistribution layer 16, and a cover coat having an opening formed in a portion of the redistribution layer 16 on the core 18. The conductive ball 17 connected to the redistribution layer 16 with the barrier metal 20 therebetween in the opening of the layer 19, the cover coat layer 19, the collar 21 holding the conductive ball, And an underfill 22 provided on the cover coat layer 19 around the conductive balls 17. 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 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 upper portion thereof. In addition, the surface protection layer 14 of the element is formed. The redistribution layer 16 is formed on the pad part 15, and this redistribution layer 16 extends to the upper part of the connection part 24 with the electroconductive ball 17. As shown in FIG. In addition, a cover coat layer 19 is formed on the surface protective layer 14. The redistribution layer 16 is connected to the conductive ball 17 through the barrier metal 20.

6 and 7, the photosensitive resin composition is not only an interlayer insulating layer 11 and a surface protective layer 14, but also a cover coat layer 19, a core 18, a collar 21, and an underfill. (22) and the like can be used as a material for forming. Since the pattern cured film using the photosensitive resin composition of this embodiment is excellent in adhesiveness with metal layers, sealing agents, etc., such as Al wiring layer 12 or the redistribution layer 16, and also has a high stress relaxation effect, this pattern cured film is The semiconductor element used 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 for flip chips, etc. is very It is excellent in reliability.

The photosensitive resin composition of this embodiment is used for the interlayer insulation layer 11, the surface protective layer 14, or the cover coat layer 19 of the semiconductor element which has the redistribution layer 16 in FIG. 6 and FIG. Suitable.

It is preferable that it is 3-20 micrometers, and, as for the film thickness of the interlayer insulation layer 11, the surface protective layer 14, and the said cover coat layer 19, it is more preferable that it is 5-15 micrometers.

[Electronic device]

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

Example

EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited to these.

The material used in the Example is shown below.

[(A) component]

A1: Polymer of 4-hydroxy styrene (weight average molecular weight = 10000, Maruzen Seki Yugaku Co., Ltd. make, brand name "Maruka linker M")

A2: copolymer of 4-hydroxystyrene / styrene = 85/15 (molar ratio) (weight average molecular weight = 10000, Maruzen Seki Yugaku Co., Ltd. make, brand name "Maruka linker CST")

A3: 4-hydroxy styrene / methyl methacrylate = 70/30 (molar ratio) copolymer (weight average molecular weight = 12000, Maruzen Seki Yugagaku Co., Ltd. make, brand names "Maruka linker CMM")

A4: cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, weight average molecular weight = 12000, Asahi Yuki Chemical Co., Ltd. make, brand name "EP4020G")

In addition, the weight average molecular weight was calculated | required by standard polystyrene conversion using the gel permeation chromatography (GPC) method, respectively.

Specifically, the weight average molecular weight was measured by the following apparatus and conditions.

Measuring device:

Detector: L4000UV manufactured by Hitachi Ltd. Hitachi Seisakusho

Pump: Corporation KK Hitachi Seisakusho L6000

Column: Gelpack GL-S300MDT-5 × 2

Measuring 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

About 0.5 mg of sample, it measured using the solution of 1 ml of solvent [THF / DMF = 1/1 (volume ratio)].

[(B) component]

B1: A compound in which all of R ¹ to R ^{6 in} the general formula (1) are methyl groups (hexakis (methoxymethyl) melamine, manufactured by Wawa Chemical Co., Ltd., trade name "Nikarak MW-30HM", molecular weight: 390.4)

B2: A compound in which all of R ⁷ to R ¹² in the general formula (2) are methyl groups (manufactured by Honshu Chemical Co., Ltd., trade name "HMOM-TPPA", molecular weight 688.9)

[(C) component]

C1: Trifunctional epoxy compound (The compound whose R <^13> -R <^15> of general formula (3) is all a methylene group, the Nissan Chemical Co., Ltd. make, brand name "TEPIC-L", molecular weight: 297.3)

C2: Trifunctional epoxy compound (Compound whose all R <^13> -R <^15> of General formula (3) is n-propylene group, the Nissan Kagaku Kogyo Co., Ltd. make, brand name "TEPIC-VL", molecular weight: 381.4)

C3: Trifunctional epoxy compound (The compound whose R <^13> -R <^15> of General formula (3) is all n-hexylene group, the Nissan Kagaku Kogyo Co., Ltd. make, brand name "TEPIC-FL", molecular weight: 507.7)

C4: trifunctional epoxy compound (compound represented by a following formula (X), the Corporation | KK make, brand name "TECHMORE VG3101L", molecular weight: 592.7)

C5: bifunctional epoxy compound (polyethylene glycol # 400 diglycidyl ether, Kyoeisha Chemical Co., Ltd. make, brand name "Eporite 400E", molecular weight: 526.6)

[(D) component]

D1: In a 100 ml three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 55 g of ethyl lactate was taken again and separately taken from the polymerizable monomer (34.7 g of n-butyl acrylate (BA), lauryl acrylate (LA)). 2.2 g, acrylic acid (AA) 3.9 g, hydroxybutyl acrylate (HBA) 2.6 g and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: FA-711MM, Hitachi) 1.7 g of Kasei Chemical Co., Ltd.) and 0.29 g of azobisisobutyronitrile (AIBN) were added, while nitrogen gas was mixed at a flow rate of 400 ml / min while stirring at a stirring speed of about 160 rpm at room temperature. After flowing for a minute, the dissolved oxygen was removed, 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 for about 25 minutes. D1 was obtained, and the polymerization rate at that time was 99% and the weight average molecular weight of D1 was about 22000. In addition, the molar ratio of the polymerizable monomer in elastomer D1 is as follows.

BA / LA / AA / HBA / FA-711MM = 70.5 / 2.5 / 20/5/2 (mol%)

In addition, the weight average molecular weight of (D) component was calculated | required by the method similar to the measurement of the weight average molecular weight of (A) component.

[(E) component]

E1: The compound (The Daito Chemicals Co., Ltd. make, brand name "PA-28") represented by following formula (Y).

(Examples 1-9 and Comparative Examples 1-3)

120 mass parts of ethyl lactates are mix | blended as a component (A)-(C) component of a compounding quantity (mass part) shown in Table 1, and this is pressure filtered using a 3 micrometer pore Teflon (trademark) filter, and Example 1 The positive photosensitive resin composition of -9 and Comparative Examples 1-3 was prepared.

<Evaluation of Positive Photosensitive Resin Composition>

(Production of hard film)

The positive photosensitive resin composition of Examples 1-9 and Comparative Examples 1-3 was spin-coated on a 6 inch silicon substrate, and it heated at 120 degreeC for 3 minutes, and formed the resin film with a film thickness of about 12-14 micrometers. Then, the resin film was heat-processed (cured) by the method of the following (i), and the cured film with a film thickness of about 10 micrometers was obtained.

(i) The resin film was heat-processed in nitrogen for 2 hours at 230 degreeC (heating time 1.5 hours) in nitrogen using the vertical diffusion furnace (The Koyo Thermo Systems company make, brand name "(micro) -TF").

(Liquid swelling ratio)

Flux (Senju Kinzo Kogyo Co., Ltd. brand name "WF-6300 LF") was apply | coated as a chemical liquid on the cured film obtained by the above-mentioned (production of a cured film), and it heat-processed at 260 degreeC for 3 minutes, The liquid was removed by washing with water. The film thickness of the cured film before and behind a chemical liquid process was measured, and the chemical liquid swelling ratio was computed from the following formula | equation. The chemical swelling ratio means that the smaller the value (25% or less), the better. The results are shown in Table 1.

Chemical liquid swelling ratio (%) = [(film thickness of cured film after chemical liquid process) / (film thickness of cured film before chemical liquid process) -1] x 100

(Residual stress)

The residual stress of the cured film obtained by the above-mentioned (preparation of a cured film) was measured using the stress measuring apparatus (KL Atten Co., FLX-2320 type). The residual stress means that the smaller the value (20 MPa or less), the better. The results are shown in Table 1.

(Al adhesion strength)

Spin coating the positive photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 onto a 6 inch aluminum substrate (substrate after sputtering Ti on a silicon substrate and further sputtering aluminum on the Ti) Then, it heated at 120 degreeC for 3 minutes, and formed the resin film of film thickness of 11-13 micrometers. Then, it heat-processed (cured) by the method of said (i), and obtained the cured film with a film thickness of about 10 micrometers. This cured film was cut into small pieces (1 cm x 1 cm) with the board | substrate, and the aluminum stud and the cured film were bonded through the epoxy resin layer. Subsequently, the stud was pulled out and the load at the time of peeling was measured. Adhesion strength means that the numerical value is large (39.2 MPa (400 kgf / cm 2) or more), the better. The results are shown in Table 1.

As shown in Table 1, the positive photosensitive resin composition containing (B) component and (C) component is hardening obtained compared with the positive photosensitive resin composition which does not contain (B) component and (C) component. In the film, the residual stress was reduced and was excellent also in chemical resistance and adhesion to the substrate.

(Examples 10 and 11 and Comparative Examples 4 to 6)

120 mass parts of ethyl lactates were mix | blended as a component and the solvent of the compounding quantity (mass part) shown in Table 2, and this was filtered under pressure using a 3 micrometer pore Teflon (trademark) filter, and Example 10 , 11 and the positive photosensitive resin composition of Comparative Examples 4-6 were prepared.

<Evaluation of Positive Photosensitive Resin Composition>

(Liquid swelling ratio, residual stress, adhesion strength)

Evaluation was performed by the same method as the method mentioned above. The results are shown in Table 2.

(Production of pattern cured film)

The positive photosensitive resin composition of Examples 10, 11 and Comparative Examples 4-6 was spin-coated on a 6 inch silicon substrate, and it heated at 120 degreeC for 3 minutes, and formed the resin film with a film thickness of about 12-14 micrometers. Then, this resin film was exposed at the exposure amount of 2 times the minimum exposure amount at all wavelengths through the mask using the proximity exposure machine (The Canon company make, brand name "PLA-600FA"). After exposure, image development was performed using the 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide), and the pattern resin film of 10 mm width was obtained. Then, the pattern resin film was heat-processed (cured) by the method of the following (i), and the pattern cured film with a film thickness of about 10 micrometers was obtained.

(i) The pattern resin film was heat-processed for 2 hours at 230 degreeC (heating time 1.5 hours) in nitrogen using the vertical diffusion furnace (The Koyo Thermo Systems company make, brand name "(mu) -TF").

(Break strength after curing, breaking elongation after curing)

The breaking strength and the 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 m, and the chuck was 20 mm. The pulling rate was 5 mm / min, and the measurement temperature was 20 ° C to 25 ° C. The average of the measured value of five or more test pieces obtained from the pattern cured film obtained on the same conditions was made into "break strength" and "break elongation." The breaking strength means that the numerical value is larger (100 MPa or more), the better. Elongation at break means that the higher the value (30% or more), the better. The results are shown in Table 2.

(CTE)

The average thermal expansion coefficient (CTE) of 50-150 degreeC of the cured film obtained by the same method as (preparation of a patterned cured film) mentioned above was measured using TMA / SS600 (made by Seiko Instruments Co., Ltd.). The sample used for the measurement adjusted the width to 2 mm, the film thickness to about 10 micrometers, and the chuck to 10 mm. In addition, the measurement conditions made load 10g and the temperature increase rate 5 degree-C / min. CTE means that the lower the value (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) contains the component (B) and the component (C). In the cured film obtained compared with the positive photosensitive resin composition which does not contain, residual stress was reduced and was excellent also in chemical-resistance tolerance and adhesiveness with a board | substrate. Moreover, it turned out that the pattern cured film obtained is excellent also in breaking strength, breaking elongation, and a thermal expansion coefficient.

As mentioned above, it was confirmed that the positive photosensitive resin composition of this invention can form the cured film which is low in residual stress, excellent in chemical-resistance resistance, and excellent in adhesiveness with a board | substrate.

1: semiconductor substrate, 2: protective film, 3: first conductor layer, 4: interlayer insulating film, 5: photosensitive resin layer, 6A, 6B, 6C: window portion, 7: second conductor layer, 8: surface protective layer, 11: Interlayer insulation layer, 12: Al wiring layer, 13: insulation layer, 14: surface protective layer, 15: pad portion, 16: redistribution 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, 500, 600, 700: semiconductor element

Claims (11)

(A) alkali-soluble resin,
(B) a compound represented by the following general formula (1) or a compound represented by the following general formula (2),
(C) a compound having two or more epoxy groups
Positive photosensitive resin composition containing these.

[In General Formula (1), R <^1> -R <^6> respectively independently represents a C1-C10 alkyl group.]

[In General Formula (2), R <^7> -R <^12> respectively independently represents a C1-C10 alkyl group.] The positive type photosensitive resin composition of Claim 1 whose molar ratio of the said (C) component with respect to the said (B) component is 1.0 or less. The positive photosensitive resin composition of Claim 1 or 2 whose said (C) component is a compound which has an aromatic ring or a heterocyclic ring. The positive photosensitive resin composition of any one of Claims 1-3 whose said (C) component is a compound represented by following General formula (3).

[In General Formula (3), R <^13> -R <^15> respectively independently represents a C1-C10 alkylene group.] The positive photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) an elastomer. The positive type photosensitive resin composition of any one of Claims 1-5 which further contains the compound which produces | generates an acid by light (E). The thermal crosslinking agent for positive photosensitive resins which consists of a compound represented by following General formula (1) or a compound represented by following General formula (2), and a compound which has 2 or more epoxy groups.

[In General Formula (1), R <^1> -R <^6> respectively independently represents a C1-C10 alkyl group.]

[In General Formula (2), R <^7> -R <^12> respectively independently represents a C1-C10 alkyl group.] The pattern cured film which has a pattern and the said pattern contains the hardened | cured material of the resin film which consists of a positive photosensitive resin composition in any one of Claims 1-5. The process of apply | coating and drying the positive photosensitive resin composition in any one of Claims 1-6 to one part or all part of a board | substrate, and forming a resin film,
Exposing a part or all of the resin film;
Developing the resin film after exposure with an aqueous alkali solution to form a patterned resin film,
Step of heating the pattern resin film
The manufacturing method of the pattern cured film provided with. The semiconductor element provided with the pattern cured film of Claim 8 as an interlayer insulation layer or a surface protection layer. An electronic device comprising the semiconductor element according to claim 10.

Images