KR102004129B1 - A photosensitive resin composition, a resin film, a cured film, a method of manufacturing a semiconductor device, and a semiconductor device - Google Patents

Abstract

To a photosensitive resin composition comprising a phenol resin (A) having a biphenol structure, a photo acid generator (B), and a solvent.

Description

A photosensitive resin composition, a resin film, a cured film, a method of manufacturing a semiconductor device, and a semiconductor device

The present invention relates to a photosensitive resin composition, a method of manufacturing a semiconductor device, a resin film, a cured film, and a semiconductor device. More particularly, the present invention relates to a photosensitive resin composition which can be used as a resist used for manufacturing a semiconductor device or as a precursor of a heat-resistant resin used for a protective film for a surface of a semiconductor element or an interlayer insulating film.

The present application claims priority based on Japanese Patent Application No. 2016-220584 filed on November 11, 2016, the contents of which are incorporated herein by reference.

2. Description of the Related Art Various resin compositions or photosensitive compositions have been proposed as materials for forming a surface protective film and an interlayer insulating film or the like used in semiconductor devices in electronic components (for example, Patent Document 1).

Patent Document 1 discloses a process for producing a phenolic resin composition which comprises reacting a phenolic resin (A) having a biphenyldiyl structure in its main chain with a photoacid generator (B) and an acid or heat generated from the above (B) (C) that can be used as a photopolymerizable compound. Patent Document 1 discloses a phenol resin containing an unsubstituted biphenyldiyl structure as the phenol resin (A).

Patent Document 1: JP-A-2012-123378

A cured resin film used for forming a surface protective film and an interlayer insulating film of a semiconductor device is obtained by applying a photosensitive resin composition to a substrate to obtain a resin film, patterning the resin film by exposure and development, and subsequently heating the patterned resin film And curing. In the conventional photosensitive resin composition, since the softening point of the obtained resin film is low, the heat resistance is low and the pattern shape is deformed by heating, so that the resin film can not be suitably used as a surface protective film or an interlayer insulating film of a semiconductor device.

According to the present invention for solving the above problems, there is provided a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film made of the photosensitive resin composition, a cured film of the resin film, And a method of manufacturing a semiconductor device using the photosensitive resin composition.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, they have completed the present invention including the following embodiments.

[1] A phenol resin (A) having a biphenol structure,

A photo acid generator (B)

A photosensitive resin composition comprising a solvent.

[2] The resin composition according to the above [1], wherein the phenol resin (A) is a structure derived from at least one compound selected from the group consisting of a biphenol compound and an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound 1 >. 3. The photosensitive resin composition according to the above-mentioned [1]

[3] The photosensitive resin composition according to the above [1] or [2], wherein the phenol resin (A) is a resin having a structural unit represented by the formula (1).

(In the formula (1)

R ₁₁ and R ₁₂ are each independently selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or unsaturated An alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded through an ester bond, an ether bond, an amide bond, or a carbonyl bond,

p and q are each independently an integer of 0 to 3,

X ₁ and Y ₁ each independently represent an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, which may have a single bond or an unsaturated bond Lt; 2 > is a divalent substituent selected from the group consisting of

Provided that Y < ₁ > is bonded to either one of the two benzene rings)

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the phenol resin (A) has a repeating structural unit represented by formula (2).

(In the formula (2)

m is an integer of 2 to 10000,

R ₁₁ and R ₁₂ are each independently selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or unsaturated An alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded through an ester bond, an ether bond, an amide bond, or a carbonyl bond,

p and q are each independently an integer of 0 to 3,

X ₁ and Y ₁ each independently represent an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, which may have a single bond or an unsaturated bond Lt; 2 > is a divalent substituent selected from the group consisting of

Provided that Y < ₁ > is bonded to either one of the two benzene rings)

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photoacid generator (B) is a compound which generates an acid upon irradiation with radiation having a wavelength of 200 to 500 nm.

[6] The photosensitive resin composition according to any one of [1] to [5], further comprising a crosslinking agent (C) having a group capable of reacting with the phenol resin (A).

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the phenol resin (A) has a weight average molecular weight in terms of polystyrene of 1000 to 100000.

[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a silane coupling agent (D).

[9] The photosensitive resin composition according to any one of [1] to [8], further comprising a nonionic surfactant (E).

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising a reaction promoter (F).

[11] the following steps:

A step of applying the photosensitive resin composition described in any one of [1] to [10] above onto a semiconductor substrate,

A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin layer,

A step of exposing the photosensitive resin layer with an actinic ray,

A step of developing the exposed photosensitive resin layer to obtain a patterned resin layer, and

And heating the patterned resin layer to obtain a cured resin layer.

[12] A resin film comprising the photosensitive resin composition according to any one of [1] to [10].

[13] A cured film of the resin film according to the above [12].

[14] A semiconductor device comprising the cured film described in [13] above.

According to the present invention, there is provided a semiconductor device comprising a photosensitive resin composition capable of forming a resin film or a cured film having excellent heat resistance, a resin film made of the photosensitive resin composition, a cured film of the resin film, and the cured film, A method of manufacturing a semiconductor device using a composition is provided.

Hereinafter, an embodiment of the present invention will be described.

(Photosensitive resin composition)

The photosensitive resin composition according to the present embodiment includes a phenol resin (A) having a biphenol structure, a photo acid generator (B), and a solvent.

The resin composition of the present embodiment is a resin composition comprising a resin having a biphenol structure, that is, a phenol resin having a biphenyldiyl structure having at least one hydroxyl group in each of the phenyl groups, as the phenol resin (A) The heat resistance of the film is improved. Thus, when a resin film made of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

(Phenol resin (A))

In one embodiment, the phenol resin (A) is derived from at least one compound selected from the group consisting of a biphenol compound and an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound Lt; / RTI > In other words, the phenol resin (A) is obtained by reacting a biphenol compound with at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound .

As used herein, the term " structure derived from (substance) "refers to a structure produced using the above substance, and the structure can be identified using conventional methods in the art, If not, include both.

Such a phenol resin (A) can be produced by using commercially available raw monomers without requiring a troublesome process, so that the resulting photosensitive resin composition can be produced at low cost.

The phenol resin (A) can be produced by any known method. Examples of the production method include a condensation reaction of a biphenol compound with an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound or a dihaloalkyl compound.

Examples of biphenol compounds which can be used for producing the phenol resin (A) include 2,2'-biphenol, 4,4'-biphenol and isomers thereof. These biphenol compounds may have a substituent. Examples of the substituent include a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, An unsaturated alicyclic group, or an organic group having an aromatic structure of 6 to 20 carbon atoms.

Such biphenol compounds are exemplified by, for example, the following compounds, but are not limited thereto.

Examples of the aldehyde compound which generates the phenolic resin (A) by reaction with the biphenol compound include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexyl But are not limited to, aldehyde, diphenylacetaldehyde, ethylbutylaldehyde, benzaldehyde, cinnamaldehyde, diphenylacetaldehyde, methyl fumaraldehyde, 3-methyl-2-butenal, glyoxylic acid, Malondialdehyde, succinic dialdehyde, glutaraldehyde, naphthaldehyde, terephthalaldehyde and the like.

Examples of the dimethylol compound which generates the phenolic resin (A) by reaction with the biphenol compound include 2,2-bis (hydroxymethyl) butyric acid, 1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, Naphthalene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol (Hydroxymethyl) durene, 2-nitro-p-xylylene glycol, 1,10-dihydroxydecane, 1,6- (Hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane , 1,4-benzenedimethanol, 1,3-benzenedimethanol, 2,6-bis (hydroxymethyl) -1,4- (Hydroxymethyl) naphthalene, 2,8-bis (hydroxymethyl) -p-cresol, 2,3-bis (hydroxymethyl) naphthalene, 2,6- Bis (hydroxymethyl) diphenylacetate, 4,4'-bis (hydroxymethyl) diphenyl ether, 4,4'- (Hydroxymethyl) benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid-4'-hydroxymethylanilide, 4, Bis (hydroxymethyl) phenylurea, 4,4'-bis (hydroxymethyl) phenylurea, 4,4'-bis ) Biphenyl, 2,2'-dimethyl-4,4'-bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane and the like.

Examples of the dimethoxymethyl compound which generates the phenol resin (A) by reaction with the biphenol compound include 2,2-bis (methoxymethyl) butyric acid, 1,3-dimethoxymethylpropane , 2-benzyloxy-1,3-dimethoxymethyl propane, 2,2-dimethyl-1,3-dimethoxymethyl propane, 2,2-diethyl-1,3-dimethoxymethyl Propane, 2-methyl-2-nitro-1,3-dimethoxymethylpropane, 5-norbornene-2,2-dimethoxymethyl, (Methoxymethyl) methane, 2-phenyl-1,3-dimethoxymethyl propane, trimethoxyethane, trimethoxypropane, (Methoxymethyl) benzene, 1,10-dimethoxydecane, 1,12-dimethoxydodecane, 1, 3-bis , 4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis Bis (methoxymethyl) -1,4-dimethoxybenzene, 2, 4-bis (methoxymethyl) benzene, 1,3-dimethoxymethylbenzene, Bis (methoxymethyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, (Methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl thioether, 4 , 4'-bis (methoxymethyl) benzophenone, 4-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'- methoxymethylanilide, Bis (methoxymethyl) biphenyl, 2, 4'-bis (methoxymethyl) phenylurea, 4,4'- , 2'-dimethyl-4,4'-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxymethylphenyl) propane and the like.

Examples of the dihaloalkyl compound which generates the phenolic resin (A) by reaction with the biphenol compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethylduren, bischloromethylbiphenyl , Bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether , Diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether and tetraethylene glycol bis (chloroethyl) ether.

These compounds may be used alone or in combination of two or more.

The phenol resin (A) can be obtained by condensing the above-described biphenol compound and the above-mentioned polymerization component with dehydration or dehydrogenation hydrogen, but a catalyst may be used at the time of polymerization. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, 1'-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex and the like. Examples of the alkaline catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N- dimethylaminopyridine, piperidine, Diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Ammonia, hexamethylenetetramine, and the like.

When the synthesis reaction of the phenol resin (A) is carried out, an organic solvent may be used if necessary. Specific examples of the organic solvent that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether, glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene,? -Butyrolactone, N-methyl- However, the present invention is not limited thereto.

The phenol resin (A) may be obtained by further polymerizing a phenol compound other than the biphenol compound described above within a range not hindering the effect of the present invention.

In one embodiment, the phenol resin (A) obtained from the above compound may have a structural unit represented by the formula (1).

In the formula (1)

R ₁₁ and R ₁₂ are each independently selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or unsaturated An alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded through an ester bond, an ether bond, an amide bond, or a carbonyl bond,

p and q are each independently an integer of 0 to 3,

X ₁ and Y ₁ each independently represent an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms, which may have a single bond or an unsaturated bond Lt; 2 > is a divalent substituent selected from the group consisting of

Provided that Y < ₁ > is bonded to one of two benzene rings.

In the structural unit of the formula (1) capable of having the phenol resin (A), the biphenol structure, that is, the biphenyldiyl structure having at least one hydroxyl group in each phenyl group is contained, The heat resistance of the resin film made of the composition including the resin is improved. Thus, when a resin film made of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

R ₁₁ and R ₁₂ are each independently preferably a hydroxyl group.

p, and q are each independently an integer of 0 to 2.

X ₁ and Y ₁ each independently represent a divalent substituent selected from the group consisting of a single bond or an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond and an organic group having an aromatic structure having 6 to 20 carbon atoms .

The "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" in X ₁ and Y ₁ may be straight chain or branched chain. The number of carbon atoms may be from 1 to 7, from 1 to 5, and from 1 to 3. As the aliphatic group, an aliphatic hydrocarbon group includes an alkylene group, an alkenylene group, and an alkynylene group. Of these, an alkylene group is preferable. For example, a methylene group, an ethylene group, .

The organic group having an aromatic structure having 6 to 20 carbon atoms in X ₁ and Y ₁ may have 6 to 14 carbon atoms, 6 to 12 carbon atoms, 6 to 9 carbon atoms, or 6 to 8 carbon atoms do. Examples of the "aromatic structure" include a phenylene group, a biphenyldiyl group, and a naphthalenediyl group, and among these, a phenylene group is preferable.

The "organic group having an aromatic structure having 6 to 20 carbon atoms" in X ₁ and Y _{1 means} that the above "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" and the above "aromatic structure"Lt; / RTI >

X ₁ and Y ₁ are each independently preferably the following organic groups.

In the above formula, n is 0 to 20, preferably 0 to 10.

The structural unit represented by the above-mentioned formula (1) can be obtained by reacting the above-described biphenol compound with at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound Reaction.

In the present embodiment, the phenol resin (A) substantially has a repeating unit represented by the formula (2).

Here, in the formula (2), m is an integer of 1 to 10000, R ₁₁ and R ₁₂ , p and q, X ₁ and Y ₁ are as defined in formula (1) same.

The resin having the repeating unit structure represented by the formula (2) may be, for example, a resin having a structure represented by the formula (3).

In the formula (3), 1 and m represent a composition ratio, 1 + m = 1, 0? 1 ?, 0?

R _{11 '} , R _12' , R _{11 "} and R _12" each independently represent a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkylether group having 1 to 20 carbon atoms, A saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which are bonded to each other through an ester bond, an ether bond, an amide bond or a carbonyl group However,

p and q are each independently an integer of 0 to 3,

X _{1 '} , Y _1' , X _{1 "} and Y _1" each independently represent an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aliphatic group having 6 or more carbon atoms, which may have a single bond or an unsaturated bond; And an organic group having an aromatic structure of 1 to 20 carbon atoms.

The above structure of the phenol resin (A) can be understood by those skilled in the art from the kind of the biphenol compound and the polymerizable compound to be used.

In one embodiment, the weight average molecular weight (in terms of polystyrene) of the phenol resin (A) is in the range of 1,000 to 100,000, preferably in the range of 2,000 to 50,000, and more preferably in the range of 3,000 to 30,000. The phenol resin (A) having a weight average molecular weight in the above range is excellent in solubility in a solvent and excellent in mechanical properties of a resin film to be obtained.

(Photoacid generator (B))

The photosensitive resin composition of the present embodiment is not particularly limited as long as it is a composition capable of forming a resin pattern in response to radiation including ultraviolet ray, electron beam and X-ray, and may be a negative type or a positive type photosensitive resin composition . The resin composition of the present embodiment having photosensitivity by containing the photoacid generator (B) can be used, for example, as a resist used for manufacturing a semiconductor device.

The photoacid generator (B) used in the photosensitive resin composition of the present embodiment is a compound which generates an acid in response to the irradiated radiation and preferably has a wavelength of 200 to 500 nm, particularly preferably a wavelength of 350 to 450 nm To generate an acid upon irradiation with radiation. Specific examples thereof include an onium salt such as a photosensitive diazoquinone compound, a photosensitive diazonaphthoquinone compound, a diaryliodonium salt, a triarylsulfonium salt or a sulfonium borate salt, a 2-nitrobenzyl ester compound, Imide sulfonate compounds, 2,6-bis (trichloromethyl) -1,3,5-triazine compounds, dihydropyridine compounds and the like. These may be used singly or in combination of two or more kinds. Among them, a photosensitive diazoquinone compound and a photosensitive diazonaphthoquinone compound which are excellent in sensitivity and solvent solubility are preferable. Specific examples thereof include 1,2-benzoquinone diazepine-4-sulfonic acid ester, 1,2-naphthoquinone diazepine-4-sulfonic acid ester, 1,2-naphthoquinone diazin- -Sulfonic acid ester, and the like.

The photoacid generator (B) is used in an amount of 1 to 100% by weight, preferably 3 to 50% by weight, based on 100% by weight of the phenol resin (A).

(solvent)

The photosensitive resin composition of the present embodiment is used in the form of a varnish obtained by dissolving the above components in a solvent. Examples of the solvent to be used include N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethylether, Diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Butyl lactic acid acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy propionate. They may be used singly or in combination.

The solvent is used in an amount of 50% by weight to 1000% by weight, preferably 100% by weight to 500% by weight, based on 100% by weight of the phenol resin (A). By using a solvent in the above range, it is possible to produce a varnish having excellent handleability in which the resin is sufficiently dissolved.

(Crosslinking agent (C))

The photosensitive resin composition of the present embodiment may contain a cross-linking agent (C) having a group capable of reacting with the phenol resin (A). When a resin film is produced by using the photosensitive resin composition of the present embodiment including the crosslinking agent (C), and the resin film is heated and cured after patterning by exposure and development, the crosslinking agent (C) And is crosslinked with the phenol resin (A) by the action of generated acid or heat. The resin film obtained from the photosensitive resin composition containing the crosslinking agent contains the phenol resin (A) having the above-mentioned structure, whereby deformation of the patterned resin film during heat curing is suppressed. Further, since the obtained cured film has excellent heat resistance, electrical characteristics, and mechanical characteristics, it can be used as a surface protective film and an interlayer insulating film used in semiconductor devices.

As the crosslinking agent (C) usable in the photosensitive resin composition of the present embodiment, it is preferable to use a thermally crosslinkable compound with the phenol resin (A). Examples of the crosslinking agent (C) which can be used include the following compounds:

(1) compounds containing at least one crosslinkable group selected from the group consisting of methylol groups and alkoxymethyl groups: benzene dimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxy Benzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzoate hydroxymethylphenyl, bis (hydroxymethyl) biphenyl, dimethyl bis Bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenylether, bis Methoxymethylphenyl benzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl; Commercial products are commercially available from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 ), NIKARAK MX-270, -280, -290, NIKARAK MS-11, NIKARAK MW-30, -100, -300, -390 and -750 (manufactured by Sanwa Chemical) (Methoxymethyl) benzene, 4,4'-biphenyl dimethanol, 4,4'-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM-BIPC- DML-PCP, DML-PTBP, DML-34X, DML-EP, DML-OCHP, DML-OCHP, DML-OPC, TM-BIP-A (manufactured by Asahi Yuki Kaisha Kogyo Co., DML-BisPC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML- DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6- dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by Honshu Kagaku Kogyo Co., Ltd.), etc. The can. These compounds may be used alone or in combination.

(2) Compounds having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxy hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, bisphenol A ( Or F) glycidyl ethers such as glycidyl ethers, adipic acid diglycidyl esters, o-phthalic acid diglycidyl esters, etc., 3,4-epoxycyclohexylmethyl ( Epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (Methylcyclohexylmethyl) adipate, dicyclopentane diene oxide, bis (2,3-epoxycyclopentyl) ethane, Cellocide 2021 of Daicel Co., (((((1- (4- (2- (4- (oxiran-2-yl) -1,3,4-thiadiazol- (Methylene)) bis (oxiranes)) bis (4-phenylenesulfonyloxy) phenyl) propane- (Such as Techmore VG3101L (manufactured by Printech)), Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.) and Epiol TMP (manufactured by Nichiyu Corporation) Polyglycidyl ethers, 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxiran-2-ylmethoxy) propyl) trisiloxane (for example, DMS-E09 (manufactured by Gelest);

(3) A compound having an isocyanate group: for example, 4,4'-diphenylmethane diisocyanate, tolylene isocyanate, 1,3-phenylene bismethylene diisocyanate , Dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;

(4) a compound having a bismaleimide group such as 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyletherbismaleimide , 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, Maleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis (Phenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene.

The blending amount of the crosslinking agent (C) in the photosensitive resin composition is 1 to 100% by weight, preferably 5 to 50% by weight, based on 100% by weight of the phenol resin (A). When the blending amount is 1% by weight or more, the mechanical strength of the thermosetting film is good, and when it is 100% by weight or less, the stability of the composition in the varnish state is good and the mechanical strength of the obtained thermosetting film is good.

(Silane coupling agent (D))

The photosensitive resin composition of this embodiment may contain a silane coupling agent (D). By including the silane coupling agent (D), when the photosensitive resin composition is applied onto a substrate to obtain a resin film, the adhesion to the substrate is improved.

Examples of the silane coupling agent (D) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryl 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl (meth) acrylate, triethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- A silicon compound obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride, and the like can be mentioned. However, in the case of a silicon compound obtained by reacting a silicon compound having an amino group with 3-isocyanate propyltriethoxysilane and bis (triethoxypropyl) tetrasulfide, But are not limited thereto. The silane coupling agents may be used alone or in combination.

The blending amount of the silane coupling agent (D) in the photosensitive resin composition is 0.1 to 30% by weight, preferably 1 to 20% by weight, based on 100% by weight of the phenol resin (A). By using the silane coupling agent (D) within the above-mentioned range, both the adhesiveness to the substrate and the storage stability of the photosensitive resin composition can be achieved.

(Nonionic surfactant (E))

The photosensitive resin composition of the present embodiment may contain a nonionic surfactant (E). By including the nonionic surfactant (E), the photosensitive resin composition is applied onto a substrate to obtain a resin film with good coatability, and a uniform film thickness can be obtained. In addition, it is possible to prevent residue and pattern floating when the coating film is developed.

The nonionic surfactant (E) used in the photosensitive resin composition is, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton . In the present embodiment, as the nonionic surfactant (E), those containing a fluorine-based surfactant or a silicon-based surfactant are more preferably used, and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorochemical surfactant include Megapak F-171, F-173, F-444, F-470, F-471, F-475, F- 477, F-554, F-556, and F-557 manufactured by Sumitomo 3M Limited, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Ltd., and the like.

When the surfactant is used, the blending amount of the surfactant is preferably 0.01 to 10% by weight based on 100 parts by weight of the alkali-soluble phenol resin.

(Reaction promoter (F))

The photosensitive resin composition of this embodiment may contain a reaction promoter (F). By including the reaction promoter (F), thermal crosslinking between the phenol resin (A) contained in the photosensitive resin composition and the crosslinking agent can be promoted.

As the reaction promoter (F), for example, a hetero-pentane compound containing nitrogen or a compound capable of generating an acid by heat can be used. These may be used alone, or a plurality of them may be used in combination. The nitrogen-containing heteroaromatic compound used as the reaction accelerator (F) includes, for example, pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole . Examples of the compound capable of generating an acid by heat used as the reaction promoter (F) include sulfonium salts, iodonium salts, sulfonates, phosphates, borates and salicylates. In order to more effectively improve the curing property at low temperature, it is more preferable to include one or both of a sulfonate and a borate among the compounds generating an acid by heat, and in consideration of the heat resistance of the cured film characteristics, Is particularly preferable.

(Other additives)

If necessary, additives such as a dissolution accelerator, an antioxidant, a filler, a photopolymerization initiator, a terminal sealing agent and a sensitizer may be added to the photosensitive resin composition of the present embodiment in such a range as not to impair the effect of the present invention Further, it may be used.

(Production method of cured film)

In another aspect of the present embodiment,

A step of applying the above-mentioned photosensitive resin composition of the present invention onto a semiconductor substrate,

A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin layer,

A step of exposing the photosensitive resin layer with an actinic ray,

A step of developing the exposed photosensitive resin layer to obtain a patterned resin layer, and

And a step of heating the patterned resin layer to obtain a cured resin layer. An example of this embodiment will be described below.

(Method of forming coating film)

First, the photosensitive resin composition of the present embodiment is applied to a support or a substrate, such as a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer or the like. Here, the substrate includes, for example, a semiconductor element or a substrate on which a display element is formed on the surface, in addition to the raw substrate. At this time, an adhesive agent such as a silane coupling agent may be previously coated on the support or the substrate in order to ensure water-resistant adhesion between the pattern to be formed and the support. Application of the photosensitive resin composition can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating or the like.

Next, pre-baking is performed at 80 to 140 ° C for about 30 to 600 seconds, and the solvent is removed to form a coating film of the photosensitive resin composition. The thickness of the coating film after removing the solvent is preferably 1 to 500 mu m.

(Exposure step)

Next, the thus obtained coating film is exposed. As the active ray for exposure, for example, X-ray, electron beam, ultraviolet ray, visible ray and the like can be used, but it is preferable that the wavelength is 200 to 500 nm. From the viewpoint of the resolution of the pattern and the ease of handling, it is preferable that the light source wavelength is a region of g-line, h-line or i-line of the mercury lamp, and may be used alone or in combination of two or more rays. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is particularly preferable. After the exposure, the coating film may be heated again at 80 to 140 캜 for about 10 to 300 seconds, if necessary.

(Developing step)

Next, the coated film after the exposure is developed to form a relief pattern. In this developing step, development can be carried out by using a suitable developer, for example, a dipping method, a puddle method, a rotary spraying method, or the like. By the development, an exposed portion (in the case of the positive type) or an unexposed portion (in the case of the negative type) is eluted and removed from the coated film, and a relief pattern can be obtained.

Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and ammonia;

Organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine;

Quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide;

Organic solvents such as cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate can be used, and examples thereof include water-soluble organic solvents such as methanol and ethanol, May be added.

Among these, tetramethylammonium hydroxide aqueous solution is preferable. The concentration of tetramethylammonium hydroxide in the aqueous solution is preferably 0.5 to 10 mass%, more preferably 1 to 5 mass%.

After development, cleaning is carried out with a rinsing liquid, and the developer is removed to obtain a relief pattern. As the rinsing liquid, for example, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethylether, etc. may be used alone or in combination of two or more.

(Heating process)

Finally, the cured relief pattern (cured film) can be obtained by heating the relief pattern obtained as described above. The heating temperature is preferably 150 ° C to 500 ° C, more preferably 150 ° C to 400 ° C. The heating time may be 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a heating oven in which a temperature program can be set, and the like. As the atmospheric gas at the time of performing the heat treatment, air may be used, or an inert gas such as nitrogen or argon may be used. When it is necessary to perform heat treatment at a lower temperature, heating may be performed under a reduced pressure using a vacuum pump or the like.

The relief pattern obtained from the photosensitive resin composition of the present embodiment has little or no deformation in the heating step and the shape of the relief pattern before heating can be maintained and a cured relief pattern of high resolution can be obtained.

(Semiconductor device)

By using the above-mentioned cured relief pattern as a protective film of a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a device having a bump structure, and combining it with a process in a known semiconductor device manufacturing method, A semiconductor device can be manufactured. As described above, since the cured relief pattern of the present embodiment can be manufactured with high resolution, the semiconductor device using the cured relief pattern has excellent electrical reliability.

Although the embodiments of the present invention have been described above, they are examples of the present invention, and various configurations other than the above may be employed. The present invention is not limited to the above-described embodiments, and variations, modifications, and the like within the scope of achieving the objects of the present invention are included in the present invention.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto.

(Synthesis Example 1)

≪ Synthesis of phenol resin (A-1) >

(1.00 mol) of 4,4'-biphenol and 2,6-bis (hydroxymethyl) -p-2-ene were placed in a four-necked glass round bottom flask equipped with a stirrer, a thermometer, a stirrer, After introducing 134.6 g (0.8 mol) of cresol, 6.3 g (0.05 mol) of oxalic acid dihydrate and 327 g of? -Butyrolactone, this round bottomed flask was purged with nitrogen while stirring in an oil bath The polycondensation reaction was carried out at 100 DEG C for 6 hours while refluxing the reaction solution. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 DEG C to obtain a phenol resin represented by the following formula (A-1). The weight average molecular weight of the obtained phenol resin (A-1) was 9,800.

(In the formula (A-1), the bonding hands bonding to the biphenol structure are bonded to either one of the two benzene rings)

(Synthesis Example 2)

≪ Synthesis of phenol resin (A-2) >

In a four-neck glass round bottom flask equipped with a thermometer, a stirrer, a feed inlet, and a dry nitrogen gas inlet tube, 186.2 g (1.00 mol) of 4,4'-biphenol and 133.0 g of 1,4-bis (methoxymethyl) (0.05 mol) of diethyl sulfate, and 327 g of? -butyrolactone were introduced into a round bottom flask while nitrogen was being flowed. The reaction solution was refluxed in an oil bath at 100 ° C Was subjected to a polycondensation reaction for 6 hours. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 DEG C to obtain a phenol resin represented by the following formula (A-2). The weight average molecular weight of the obtained phenol resin (A-2) was 12,300.

(In the formula (A-2), the bonding hand bonded to the biphenol structure is bonded to either one of the two benzene rings)

(Synthesis Example 3)

≪ Synthesis of phenol resin (A-3) >

In a four-neck glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 186.2 g (1.00 mol) of 4,4'-biphenol and 4,4'-bis (methoxymethyl) After introducing 193.9 g (0.8 mol) of phenyl, 7.7 g (0.05 mol) of diethyl sulfate and 582 g of y-butyrolactone, the reaction solution was refluxed in an oil bath while flowing nitrogen through the flask And a polycondensation reaction was carried out at 100 DEG C for 6 hours. Next, after the obtained reaction solution was cooled to room temperature, 323 g of acetone was added and stirred and mixed until it became homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 DEG C to obtain a phenol resin represented by the following formula (A-3). The weight average molecular weight of the obtained phenol resin (A-3) was 7,000.

(In the formula (A-3), the bonding hands bonding to the biphenol structure are bonded to either one of the two benzene rings)

(Synthesis Example 4)

≪ Synthesis of phenol resin (A-4) >

186.2 g (1.00 mol) of 2,2'-biphenol, 2,6-bis (hydroxymethyl) -p-1-ene were placed in a four-neck glass round bottom flask equipped with a thermometer, stirrer, After introducing 134.6 g (0.8 mol) of cresol, 6.3 g (0.05 mol) of oxalic acid dihydrate and 327 g of? -Butyrolactone, this round bottom flask was purged with nitrogen while refluxing the reaction solution in an oil bath Followed by polycondensation reaction at 100 DEG C for 6 hours. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 캜 to obtain a phenol resin represented by the following formula (A-4). The weight average molecular weight of the obtained phenol resin (A-4) was 7,700.

(In the formula (A-4), the bonding hand bonded to the biphenol structure is bonded to either one of the two benzene rings)

(Synthesis Example 5)

≪ Synthesis of phenol resin (A-5) >

234.2 g (1.00 mol) of fluoroglucide and 133.0 g (0.8 mol) of 1,4-bis (methoxymethyl) benzene were placed in four glass round bottom flasks equipped with a thermometer, a stirrer, 7.7 g (0.05 mol) of diethyl sulfate and 375 g of y-butyrolactone were introduced into a round-bottomed flask while flowing nitrogen, and the reaction solution was refluxed for 6 hours at 100 ° C. A polycondensation reaction was carried out. Next, the obtained reaction solution was cooled to room temperature, 500 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 DEG C to obtain a phenol resin represented by the following formula (A-5). The weight average molecular weight of the obtained phenol resin (A-5) was 22,000.

(In the formula (A-5), the bonding hand bonded to the biphenol structure is bonded to either one of the two benzene rings)

(Synthesis Example 6)

≪ Synthesis of phenol resin (A-6) >

186.2 g (1.00 mol) of 4,4'-biphenol, 86.5 g (0.8 mol) of p-cresol and 24.0 g of formaldehyde were added into four glass round bottom flasks equipped with a thermometer, a stirrer, (0.09 mol) of oxalic acid dihydrate and 308 g of? -butyrolactone were introduced, and then the round bottom flask was purged with nitrogen while refluxing the reaction solution in an oil bath at 100 ° C. Was subjected to a polycondensation reaction for 6 hours. Next, the obtained reaction solution was cooled to room temperature, 411 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 캜 to obtain a phenol resin represented by the following formula (A-6). The weight average molecular weight of the obtained phenol resin (A-6) was 11,000.

(In the formula (A-6), the bonding hand bonded to the biphenol structure is bonded to either one of the two benzene rings)

(Synthesis Example 7)

≪ Synthesis of phenol resin (A-2) >

186.2 g (1.00 mol) of 4,4'-biphenol and 140.0 g (0.8 mol) of p-xylene dichloride were placed in a four-necked glass round bottom flask equipped with a thermometer, a stirrer, 7.7 g (0.05 mol) of diethyl persulfate and 327 g of y-butyrolactone were introduced into the round bottom flask while flowing nitrogen, and the resulting mixture was refluxed in an oil bath at 100 ° C. for 6 hours under reflux The reaction was carried out. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until homogeneous. Thereafter, the reaction solution in a round bottom flask was dropped and mixed in 10 L of water to precipitate a resin component. Next, the precipitated resin component was separated by filtration and recovered, followed by vacuum drying at 60 DEG C to obtain a phenol resin represented by the following formula (A-2). The weight average molecular weight of the obtained phenol resin (A-2) was 13,500.

(In the formula (A-2), the bonding hand bonded to the biphenol structure is bonded to either one of the two benzene rings)

(Preparation of photosensitive resin composition)

For each of Examples 1 to 11 and Comparative Examples 1 and 2, a photosensitive resin composition was prepared as follows. First, each component blended according to Table 1 was dissolved in? -Butyrolactone (GBL) so that the viscosity after the combination was about 500 mPa 占 퐏, stirred in a nitrogen atmosphere, filtered with a polyethylene filter having a pore diameter of 0.2 占 퐉 Thereby obtaining a varnish-type photosensitive resin composition. Details of each component in Table 1 are as follows. The units in Table 1 are parts by mass.

≪ (A) Phenol resin >

(A-1) The phenol resin obtained in Synthesis Example 1

(A-2) The phenol resin obtained in Synthesis Example 2 or Synthesis Example 7

(A-3) The phenol resin obtained in Synthesis Example 3

(A-4) The phenol resin obtained in Synthesis Example 4

(A-5) The phenol resin obtained in Synthesis Example 5

(A-6) The phenol resin obtained in Synthesis Example 6

(A-7) Phenol novolac resin (PR-50731, manufactured by Sumitomo Bakelite Co., Ltd., weight average molecular weight (Mw) in terms of polystyrene = 11,000)

(A-8) phenol biphenyl aralkyl resin (MEH-7851, manufactured by Meiwa Kasei K.K., weight average molecular weight (Mw) in terms of polystyrene = 2,000)

≪ (B) Photo acid generator >

(B-1) a naphthoquinone compound having a structure represented by the following formula (B-1)

(B-2) a naphthoquinone compound having a structure represented by the following formula (B-2)

(B-3) CPI-210S (manufactured by SANA PRO)

≪ (C) Crosslinking agent >

(C-1) NIKARAK MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

(C-2) TML-BPA (manufactured by Honshu Kagaku Co., Ltd.)

(C-3) Celllock 2021P (Daicel Co., Ltd.)

<(D) Silane coupling agent>

(D-1) KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)

(D-2) KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.)

(D-3) KBM-846 (manufactured by Shin-Etsu Silicone Co., Ltd.)

<(E) Surfactant>

(E-1) F444 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

<(F) Thermal acid generator, thermal base generator>

(F-1) San-aide SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.)

(F-2) UCAT SA506 (manufactured by SANA PRO)

&Lt; (G) Phenol compound >

(G-1) Fluoroglucide

(G-2) Biphenol

<(H) Solvent>

(H-1)? -Butyrolactone

<Evaluation of phenol resin-1 (measurement of softening point)>

The softening point of the phenolic resin of (A-1) to (A-8) was measured according to JIS K 2207. The device used was ASP-M2SP manufactured by Maytech. The results are shown in Table 1. From the viewpoint of pattern retaining performance at the time of final curing, the higher the softening point, the better.

&Lt; Evaluation of phenol resin-2 (Evaluation of alkali solubility) >

The phenol resins (A-1) to (A-8) were dissolved in gamma-butyrolactone to obtain a resin solution. The obtained solution was coated on a 4-inch silicon wafer using a spin coater, and then pre-baked on a hot plate at 120 캜 for 3 minutes to obtain a coating film having a thickness of about 3 탆. The obtained coating film was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution at 23 占 폚 for 3 minutes to confirm the solubility of the coating film. The results are shown in Table 1.

[Table 1]

&Lt; Patterning evaluation-1 (Examples 1 to 8, 10 to 11, and Comparative Examples 1 and 2)

Each of the photosensitive resin compositions obtained above was applied to an 8-inch silicon wafer using a spin coater and then pre-baked with a hot plate at 120 캜 for 3 minutes to obtain a coating film having a film thickness of about 9.0 탆. The coating film was passed through a mask made by Dotpan Enterprise Co., Ltd. (test chart No. 1: negative and positive patterns with widths of 0.88 to 50 μm were drawn), and an exposure amount was measured using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) And investigated.

Next, using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the development time was adjusted so that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 占 퐉, And then rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated in a pattern exposed with an energy of the minimum exposure dose + 100 mJ / cm ² at which a via hole pattern of 100 m square was formed. The results are shown in Table 2 as pattern resolution (μm). The resolution is preferably as small as possible in fabricating the fine wiring.

&Lt; Patterning evaluation-2 (Example 9) >

Each of the photosensitive resin compositions obtained above was applied to an 8-inch silicon wafer using a spin coater and then pre-baked with a hot plate at 120 캜 for 3 minutes to obtain a coating film having a film thickness of about 9.0 탆. The coating film was passed through a mask made by Dotpan Enterprise Co., Ltd. (test chart No. 1: negative and positive patterns with widths of 0.88 to 50 μm were drawn), and an exposure amount was measured using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) And investigated.

Next, baking treatment was carried out at 100 DEG C for 2 minutes on a hot plate. Next, using a 2.38% aqueous solution of tetramethylammonium hydroxide as a developing solution, the exposed portion was removed by dissolution by performing a puddle development for 30 seconds × 2 times, followed by rinsing with pure water for 10 seconds. The resolution of the line pattern was evaluated in a pattern exposed with an energy of the minimum exposure dose + 100 mJ / cm ² at which a line of 5 m was formed. The results are shown in Table 2 as pattern resolution (μm). The resolution is preferably as small as possible in fabricating the fine wiring.

&Lt; Evaluation of resolution after curing (Examples 1 to 11 and Comparative Examples 1 and 2) >

The wafer on which the pattern obtained in the above-described patterning evaluations -1 and -2 was formed was placed in a heating oven and heated from room temperature to 200 캜 at a rate of 5 캜 / min while flowing nitrogen, and then subjected to heat treatment at 200 캜 for 60 minutes And cooled to room temperature. The wafer on which the pattern with the heating was formed was subjected to microscopic observation to evaluate the resolution of the line. The results are shown in Table 2 as the resolution (μm) after curing. The resolution is preferably as small as possible in forming a fine pattern.

<Fabrication of Semiconductor Device>

Each of the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 was coated with a simulated element wafer having an aluminum circuit on its surface so as to have a final thickness of 5 m and then patterned and cured. Thereafter, the lead frame for 16-pin DIP (dual in-line package) was divided for each chip size, mounted using a conductive paste, and then encapsulated with an epoxy resin for semiconductor encapsulation (EME-6300H made by Sumitomo Bakelite Co., Ltd.) .

&Lt; Reliability Evaluation of Semiconductor Device-1 (Electrical Connectivity) >

The electrical connections of each of the ten semiconductor devices obtained by the above-described method are checked,

A &quot;, &quot; A &quot;, &quot; A &quot;, &quot;

And B, in which there was an electrical connection failure in at least one of the ten semiconductor devices, was evaluated.

&Lt; Reliability Evaluation of Semiconductor Device-2 (Moisture Resistance) >

Each of the ten semiconductor devices obtained by the above-described method was treated for 168 hours under the condition of 85 占 폚 / 85% humidity, then immersed in a 260 占 폚 solder bath for 10 seconds and then subjected to high- 2.3 atm, 100% relative humidity) to check electrical connections.

A &quot;, &quot; A &quot;, &quot; A &quot;, &quot;

And B in which electrical connection failure was observed in at least one of the ten semiconductor devices was evaluated.

Table 2 below shows examples and comparative examples.

[Table 2]

The coating films formed of the phenol resins (A-1) to (A-6) of the Examples showed good alkali solubility. The softening point of the coating film was 180 DEG C or more. Thus, these phenol resins are useful as resists used, for example, in the production of semiconductor devices.

In addition, the coating film formed of the photosensitive resin composition containing the phenol resins (A-1) to (A-6) of the examples had good patterning formability. In addition, the semiconductor device having the cured film had no defects in electrical connectivity and was not defective due to corrosion of the aluminum circuit after storage under high temperature and high humidity. Therefore, the cured film is expected to be useful as an interlayer insulating film of a semiconductor device.

Industrial availability

A semiconductor device comprising a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film made of the photosensitive resin composition, a cured film of the resin film, and the cured film, and a semiconductor device using the photosensitive resin composition Thereby providing a method of manufacturing the device.

Claims (14)

A phenol resin (A) having a biphenol structure,
A photo acid generator (B)
A solvent,
Wherein the phenol resin (A) has a structural unit derived from at least one compound selected from the group consisting of a biphenol compound and an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound ,
Wherein the phenolic resin (A) has a repeating structural unit represented by the formula (2)
Wherein the phenol resin (A) has a weight average molecular weight in terms of polystyrene of 7000 to 30000, and is used for a surface protective film or an interlayer insulating film of a semiconductor device.

(In the formula (2)
m is an integer of 2 to 10000,
R ₁₁ and R ₁₂ are each independently selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or unsaturated An alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded through an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3,
X ₁ and Y ₁ are each independently a divalent substituent selected from the group consisting of a single bond or an organic group represented by the formula (3)
Provided that Y &lt; ₁ &gt; is bonded to either one of the two benzene rings)

(In the formula (3), n is 0 to 20) The method according to claim 1,
Wherein the photoacid generator (B) is a compound which generates an acid upon irradiation with radiation having a wavelength of 200 to 500 nm. The method according to claim 1,
Further comprising a cross-linking agent (C) having a group capable of reacting with the phenol resin (A). The method according to claim 1,
A photosensitive resin composition for forming a resist, which further comprises a silane coupling agent (D). The method according to claim 1,
A photosensitive resin composition for forming a resist, which further comprises a nonionic surfactant (E). The method according to claim 1,
A photosensitive resin composition for forming a resist, which further comprises a reaction promoter (F). A resin film comprising the photosensitive resin composition for forming a resist as set forth in any one of claims 1 to 6. A cured film of the resin film according to claim 7. A semiconductor device comprising the cured film according to claim 8. delete delete delete delete delete