JPH11271973A - Photosensitive resin composition and semiconductor device using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure both good i-line transmittance and low residual stress after imidation, to give a high resolution pattern of a good shape and to form a polyimide film having good mechanical characteristics and high heat resistance by incorporating a polyimide precursor having specified repeating units. SOLUTION: A polyimide precursor having repeating units represented by formula I is incorporated. In the formula I, X is a tetravalent org. group, Y is a tri- or higher valent org. group, R<1> is a group represented by formula II, R<2> and R<3> are each hydroxyl or a monovalent org. group and (m) is >=1. In the formula II, Z is a group contg. a photo- or thermopolymerizable C-C double bond. The polyimide precursor can be produced by a known production process and can be synthesized, e.g. by synthesizing a polyamic acid from a tetracarboxylic acid dianhydride and amine compds. including triamine in an org. solvent and allowing a carboxylic acid having a thermo- or photopolymerizable double bond or its anhydride to react with the amino residues of the synthesized polyamic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition in which a polyimide film formed on a silicon wafer has a particularly low residual stress, and a semiconductor device using the same.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been. However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is complicated and diversified, such as forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, and cleaning the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. Particularly, photosensitive polyimide has excellent heat resistance and elimination of impurities. Has attracted particular attention because of its ease of use. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed, but this material has practical photosensitivity. In addition, it has advantages such as high film-forming ability, but has disadvantages such as lack of storage stability and chromium ions remaining in polyimide, and thus has not been put to practical use.

[0004] In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Unexamined Patent Publication No. 60-100143)
And so on. However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties.Because of the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low and the exposure is low. However, the photochemical reaction in the portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low and the shape of the pattern is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

For this reason, a conventional contact / proximity exposure apparatus using parallel rays has been replaced by a 1: 1 projection exposure apparatus called a mirror projection and a reduction projection exposure apparatus called a stepper. The stepper utilizes a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of ultra-high pressure mercury lamps have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, the stepper used has been used. Needs to be shortened. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 365 n).
m).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines, and g-line steppers have low transparency due to the above-mentioned reasons, especially i-line. (Wavelength: 365 nm) because there is almost no transmittance.
With a line stepper, a decent pattern cannot be obtained. In addition, a polyimide film for surface protection is required to be a thicker film corresponding to LOC (lead-on-chip), which is a high-density mounting method of a semiconductor element. The problem gets worse. Therefore, there is a strong demand for a photosensitive polyimide having a high i-line transmittance and a polyimide pattern having a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
It has been increasing year by year, and there has been a problem that the warpage of the silicon wafer on which the polyimide as the surface protective film is formed becomes larger than before due to the difference in thermal expansion coefficient between the polyimide and the silicon wafer. Therefore, there is a strong demand for a photosensitive polyimide having a lower thermal expansion property than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, almost no i-line is transmitted, so that the photosensitive characteristics deteriorate. As a method for improving the i-line transmittance, a polyimide into which fluorine has been introduced (JP-A-8-234433) and a polyimide having a bent molecular chain (JP-A-8-36264) have been proposed. However, polyimide into which fluorine has been introduced has a low adhesive strength to a silicon wafer, and has low reliability when used for a semiconductor device. In addition, since polyimide having a bent molecular chain has weak intermolecular interaction, the heat resistance is lowered and the thermal expansion coefficient is increased, so that the reliability of a semiconductor element is low.

[0008]

The inventions according to the first, second and third aspects have both good i-line transmittance of the photosensitive resin composition and low residual stress after imidization, and have high resolution and good resolution. An object of the present invention is to provide a photosensitive resin composition which can give a shape pattern and obtain a polyimide film having better mechanical properties and high heat resistance. The fourth aspect of the present invention provides a semiconductor element on which a polyimide film having extremely small residual stress after forming a polyimide film and having good mechanical properties and high heat resistance is formed.

[0009]

The present invention provides a compound represented by the general formula (I):

Embedded image Wherein X is a tetravalent organic group, Y is a trivalent or higher organic group,
¹ is

Embedded image Wherein Z is a group containing a photo- or heat-polymerizable carbon-carbon double bond, R ² and R ³ are hydroxyl groups or 1
Valence organic group, m is 1 or more] and a polyimide precursor having a repeating unit represented by the formula:

[0010] The present invention also provides a photosensitive resin composition containing a polyimide precursor, wherein a silicon wafer having a polyimide film formed using the photosensitive resin composition has a residual stress of 20 MPa or less. The present invention relates to a water-soluble resin composition. In the present invention, X in the general formula (I) is
General formula (II)

Embedded image (Wherein n represents 1 to 15). Furthermore, the present invention relates to a semiconductor device having a polyimide film obtained by applying the above-mentioned photosensitive resin composition on a substrate, drying and coating the substrate, followed by imide ring closure.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The first polyimide precursor used in the photosensitive resin composition of the present invention has a repeating unit represented by the above general formula (I). X in the general formula (I) is preferably a tetravalent organic group, and is preferably a residue of a tetracarboxylic acid or a derivative thereof which can form a polyimide precursor by reacting with an amine. (Benzene ring, naphthalene ring, etc.) one or two
An aromatic group, a chain aliphatic group, a cyclic aliphatic group containing an aliphatic ring, and the like are included. An aromatic group is preferred in terms of heat resistance and the like. Those having 4 to 24 carbon atoms are preferred from the viewpoint of the number of carbon atoms. In the aromatic group, it is preferable that all four binding sites exist on the aromatic ring. These binding sites are divided into two sets of two, and the two binding sites in each set are preferably located at the ortho or peri position of the aromatic ring. The two sets may be from the same aromatic ring, or may be from separate aromatic rings linked through various bonds. In the present invention, since the residual stress is particularly low, the structure represented by the general formula (II) is preferable.

In the general formula (I), Y is a trivalent or higher valent organic group, and two or more, preferably two or more, which can react with a tetracarboxylic acid or a derivative thereof (an acid anhydride, a diester or the like) to form a polyimide precursor. It is a residue of an amine compound having three or more amino groups, and examples thereof include an aromatic group containing an aromatic ring, a chain aliphatic group, and a cyclic aliphatic group containing an aliphatic ring. From the viewpoint of the number of carbon atoms, those having 6 to 18 are preferable.
Here, as the aromatic group, one in which all three binding sites are directly present on the aromatic ring is preferable. In this case,
The two bonding sites forming the amide bond with the tetracarboxylic acid may be present on the same aromatic ring or on different aromatic rings existing through various bonds. Y is preferably a trivalent or tetravalent organic group.

In the general formula (I), 2 represented by R ¹
Of the two groups, a group having a carboxyl group is preferable in that it can be developed with a basic aqueous solution. Z in the general formula (I) is a divalent organic group containing a carbon-carbon double bond that can be photo- or thermally polymerized. Specific examples include a chain or cyclic aliphatic hydrocarbon group having a carbon-carbon double bond, and a group having 2 to 20 carbon atoms is preferable. Examples of this include the following groups.

[0014]

Embedded image (Wherein, R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom or a carbon atom having 1 to 1
0 hydrocarbon group, R ⁷ is a hydrocarbon group having 1 to 10 carbon atoms,
q and p represent 0 or 1)

Among them, Z is a structure ((a) to (g)) bonded to two carbonyl groups present on both sides through two carbon atoms in terms of heat resistance and residual stress. And those in which q is 0 in (h) and (i), among which the group represented by (a) is more preferable,
In (a), those in which both R ⁴ and R ⁵ are hydrogen atoms are most preferred.

R ² and R ³ in the general formula (I) are each independently a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkoxy group, an aryloxy group, an aralkyloxy group, A monovalent organic group in which a hydrocarbon group is present via an oxygen atom or a nitrogen atom, such as an allyloxy group, an alkylamino group, an arylamino group, and an aralkylamino group, and a heat- or photopolymerizable carbon-carbon double bond However, a group having a heat- or photo-polymerizable carbon-carbon double bond is preferable since a more favorable photosensitivity can be imparted.

The group having a carbon-carbon double bond capable of being thermally or photopolymerized is a group having a carbon-carbon unsaturated double bond via a covalent bond such as an ester bond or an amide bond or an ionic bond. The organic group is specifically,

Embedded image (However, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ¹⁴ is 2 A monovalent organic group). The alkyl group preferably has 1 to 4 carbon atoms. The divalent organic group represented by R ¹⁴ is preferably an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group. In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (having an alkyl having 1 to 4 carbon atoms) not only realize high sensitivity but also are easy to synthesize and are suitable for the photosensitive resin composition of the present invention. is there.

The polyimide precursor used in the present invention may have a repeating unit other than the repeating unit represented by the general formula (I). In this case, the content of the repeating unit represented by the general formula (I) is preferably from 10 to 100 mol%, and more preferably from 10 to 70 mol%, of all the repeating units from the viewpoints of good photosensitive characteristics, mechanical characteristics and the like. Is more preferable. Examples of the repeating unit other than the repeating unit represented by the general formula (I) include a repeating unit having a general diamine residue such as phenylenediamine as an amine residue.

The polyimide precursor of the present invention can be produced according to various known production methods. For example, in an organic solvent, after synthesizing a polyamic acid from a tetracarboxylic dianhydride and a triamine or a tetraamine, and optionally an amine compound containing a diamine, a dicarboxylic acid further containing a heat or photopolymerizable double bond. It can be synthesized by reacting an acid or its anhydride with an amino group residue of the synthesized polyamic acid. Then, an acrylic compound having an amino group or the like can be blended therein and introduced into the polyimide precursor by ionic bonding.

When a group such as a group polymerizable by heat or light is introduced into a tetracarboxylic acid by a covalent bond to synthesize a polyamic acid ester or a polyamic acid amide, for example, a condensing agent such as dicyclohexylcarbodiimide is used. A method of reacting a hydroxyl group-containing compound with a carboxyl group to introduce various groups, a method of reacting an isocyanate compound, a method of reacting a compound containing a hydroxyl group with a tetracarboxylic anhydride to form a tetracarboxylic diester, and then forming a thionyl chloride. A known method such as a method of reacting with an amine compound after forming an acid chloride by using the above method is used.

Examples of the tetracarboxylic dianhydride used in the above reaction include aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, ethylenebistrimellitate dianhydride, and triethylenebistrimellitate dianhydride. Anhydride, tetraethylene bis trimellitate dianhydride, pentaethylene bis trimellitate dianhydride, hexaethylene bis trimellitate dianhydride, heptaethylene bis trimellitate dianhydride, octaethylene bis trimellitate dianhydride, decaethylene Aromatic tetracarboxylic dianhydride, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid having a chain hydrocarbon group such as bistrimellitate dianhydride Acid dianhydride, 3,3 ', 4,4'-biphenyltetraca Bonn acid dianhydride, 1,2,5,6
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 1,4,5
8-naphthalenetetracarboxylic dianhydride, 2,3
5,6-pyridinetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, sulfonyl diphthalic dianhydride, m-terphenyl-3,
3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexa Fluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride,
2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,
Aromatic tetracarboxylic acids such as 1,1,3,3,3-hexafluoro-2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride Anhydride, the following general formula (III)

Embedded image (Wherein, R ¹⁵ and R ¹⁶ each represent a monovalent hydrocarbon group, which may be the same or different, and s is an integer of 1 or more). Dianhydrides and the like, which are used alone or in combination of two or more. Among these, from the viewpoint of low residual stress, it is preferable to use a tetracarboxylic dianhydride that gives a group represented by the general formula (II).

Examples of the above triamine or tetraamine include, for example, 4,4'-diaminodiphenyl ether-
3-carbonamide, 3,4'-diaminodiphenylether-4-carbonamide, 3,4'-diaminodiphenylether-3'-carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,
4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-
Triamines such as 3'-sulfonamide and 3,3'-diaminodiphenylether-4-sulfonamide;
3 ', 4,4'-biphenyltetraamine, 3,3',
And tetraamines such as 4,4'-tetraaminobiphenyl ether. Along with these triamines or tetraamines, diamines can be used as amine components to such an extent that i-ray transmittance, heat resistance and the like are not reduced.

The diamine is not particularly limited. For example, 4,4'- (or 3,4'-, 3,3'-, 2,
4 '-, 2,2'-) diaminodiphenyl ether,
4,4'- (or 3,4'-, 3,3'-, 2,4 '
-, 2,2 '-) diaminodiphenylmethane, 4,4'
-(Or 3,4'-, 3,3'-, 2,4'-, 2,
2'-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-)
Diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 4,4'-methylene-bis- (2,6-
Diethylaniline), 4,4'-methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4 ′
-Benzophenonediamine, bis- {4- (4'-aminophenoxy) phenyl} sulfone, 1,1,1,3,
3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4 ' -Diaminodiphenylmethane, 3,3 ',
5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis {4- (3'-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl)
And aromatic diamines such as propane. Further, in order to impart developability in a basic aqueous solution, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenyl ether-2
-A diamine having a carboxyl group such as a carboxylic acid can also be used. These are used alone or in combination of two or more.

Further, the following general formula (IV)

Embedded image (Wherein, R ¹⁷ and R ¹⁸ each represent a divalent hydrocarbon group and may be the same or different, and R ¹⁹ and R ²⁰ each represent a monovalent hydrocarbon group, and may each be the same or different. Often, t is an integer of 1 or more.) It is also possible to use an aliphatic diamine such as diaminopolysiloxane.

The amount of the amine compound which gives an amine residue of the general formula (I) such as triamine and tetraamine is as follows:
It is preferably in the range of 10 to 100 mol% of the total amount of all amines, and more preferably in the range of 10 to 70 mol%. If this amount is less than 10 mol%, the photosensitive properties tend to decrease, and the mechanical and thermal properties of the polyimide film tend to decrease.

As the organic solvent used in the above reaction, a polar solvent which completely dissolves the polyimide precursor to be produced is preferable. For example, N-methyl-2-pyrrolidone, N, N
-Dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone and the like.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used. For example, acetone, diethyl ketone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
Examples include tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These organic solvents can be used alone or
Used in combination of more than one type.

As the dicarboxylic acid or anhydride containing a carbon-carbon double bond capable of being photopolymerized or thermally polymerized used in the above reaction, an anhydride of a dicarboxylic acid having a structure shown by way of example in the general formula Z, for example, , Maleic anhydride, citraconic anhydride, phenylmaleic anhydride, itaconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride,
Bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, isobutenylsuccinic anhydride, arylsuccinic anhydride, isobutenyl glutaric anhydride and the like can be mentioned.

The acrylic compound having an amino group, which is used when a photo- or heat-polymerizable double bond is further introduced into the carboxyl group of the carboxylic acid residue of the polyamic acid via an ionic bond, includes, for example, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate , N, N-dimethylaminopropyl acrylate,
N, N-diethylaminopropyl acrylate, N, N
-Dimethylaminoethylacrylamide, N, N-dimethylaminoethylacrylamide and the like. These are used alone or in combination of two or more.

The amount of the acrylic compound having an amino group to be used is preferably 1 to 200% by weight with respect to the amount of the polyimide precursor before being compounded.
More preferably, it is 150% by weight. If the amount is less than 1% by weight, the light sensitivity tends to be poor,
If it exceeds 200% by weight, heat resistance and mechanical properties of the film tend to be inferior.

The second polyimide precursor used in the present invention has a residual stress of 2% in a silicon wafer having a polyimide film formed using a photosensitive resin composition containing the same.
It is below 0 MPa. If the residual stress exceeds 20 MPa, the silicon wafer will be warped, causing defects in the semiconductor device manufacturing process and inferior reliability as a semiconductor device. Such a residual stress is obtained, for example, by adding the repeating unit represented by the general formula (I) to 10% of all repeating units.
This can be achieved by providing a polyimide precursor having at least mol%.

The first and second polyimide precursors used in the present invention preferably have a transmittance of 3% or more, preferably 10% or more, at a film thickness of 365 nm per 10 μm of the polyimide precursor film. More preferably, 2
More preferably, it is 0% or more. When the transmittance is less than 3%, the photosensitive properties of the photosensitive resin composition tend to decrease, and the resolution and patternability tend to deteriorate. Such transmittance can be achieved, for example, by making the repeating unit represented by the general formula (I) 10 mol% or more in all the repeating units.

The photosensitive resin composition of the present invention contains the above-mentioned first or second polyimide precursor, but may contain a photoinitiator as needed. Examples of the photoinitiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone,
Ethyl anthraquinone, 4,4, -bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl,
Diphenyl disulfide, phenanthrenequinone, 2-
Isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal)
-4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl)
Oximino-1,3-diphenylpropanedione, 1
-Phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone,
3,3, -carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6
-Difluoro-3- (pyr-1-yl) phenyl] titanium and the like. These are used alone or in combination of two or more.

The amount of the photoinitiator to be used is preferably 0.01 to 30% by weight, based on the amount of the polyimide precursor containing a repeating unit represented by the general formula (I).
More preferably, the content is set to 05 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain an addition polymerizable compound, if necessary. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol methacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Data pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyl toluene, 4-vinyl pyridine, N- vinylpyrrolidone, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2
-Hydroxypropane, methylenebisacrylamide,
N, N-dimethylacrylamide, N-methylolacrylamide and the like can be mentioned. These are used alone or in combination of two or more.

The amount of the addition polymerizable compound used is preferably 1 to 200% by weight based on the amount of the polyimide precursor containing a repeating unit represented by the general formula (I). When the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developer tend to be inferior, and when it exceeds 200% by weight, the mechanical characteristics of the film tend to be inferior.

The photosensitive resin composition of the present invention can contain an azide compound, if necessary. As azide compounds, for example,

Embedded image

Embedded image And the like. These are used alone or in combination of two or more.

The amount of the azide compound used is preferably 0.01 to 30% by weight based on the amount of the polyimide precursor containing the repeating unit represented by the general formula (I).
More preferably, the content is 0.05 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2- Examples include naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor used is preferably 0.01 to 30% by weight based on the amount of the polyimide precursor containing the repeating unit represented by the general formula (I). More preferably, it is 0.05 to 10% by weight. The amount used is 0.01% by weight
If it is less than 30, the stability during storage tends to be inferior, and 30
If the amount is more than 10% by weight, light sensitivity and mechanical properties of the film tend to be poor.

The photosensitive resin composition of the present invention is applied onto a base material such as a silicon wafer, a metal substrate, a ceramic substrate or the like by an immersion method, a spray method, a screen printing method, a spin coating method or the like. By heating and drying, a coating film having no tackiness can be obtained. Although there is no particular limitation on the thickness of this coating film, from the viewpoint of circuit characteristics and the like, it is 4 to 50 μm.
m, more preferably 6 to 40 μm, particularly preferably 10 to 40 μm, and most preferably 20 to 35 μm. After irradiating actinic rays or actinic rays on the coating film through a mask on which a desired pattern is drawn, for example, by irradiating it with a pattern, the unexposed portion is developed and dissolved with an appropriate developing solution to be removed. Thereby, a desired relief pattern can be obtained.

The photosensitive resin composition of the present invention is particularly suitably designed for an i-ray stepper.
For example, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, a KrF stepper, other ultraviolet rays, a visible light source,
X-rays, electron beams and the like can also be used.

As a developing solution, for example, a good solvent (N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), a mixed solvent of the above good solvent and a poor solvent (lower alcohol, ketone, water, aromatic hydrocarbon, etc.), a basic solution ( Aqueous solution of tetramethylammonium hydroxide, aqueous solution of triethanolamine, etc.).

After the development, it is preferable to perform rinsing with water or a poor solvent, if necessary, and dry at about 100 ° C. to make the pattern stable. In addition, a patterned high heat-resistant polyimide can be formed by imide ring closing, usually heating, of this relief pattern. The heating temperature at this time is preferably from 150 to 500C, more preferably from 200 to 400C. If the heating temperature is lower than 150 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease,
If the temperature exceeds 0 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease.

The heating time at this time is 0.05 to 1
Preferably, it is 0 hours. This heating time is 0.0
If the time is less than 5 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and if the time exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease. After the photosensitive resin composition of the present invention is coated on a semiconductor element substrate and dried, the polyimide film obtained by imide ring closure is used as a surface protective film for semiconductors, an interlayer insulating film of a multilayer wiring board, and the like. You. The obtained semiconductor element has a very low residual stress and is highly reliable because it has a polyimide film having good mechanical properties and high heat resistance.

[0046]

The present invention will be described below with reference to examples. Synthesis Examples 1 to 7 In a 100 ml flask equipped with a stirrer and a thermometer, Table 1 was prepared.
And the amine component and N-methyl-2-pyrrolidone (NMP) shown in Table 2 were added and dissolved by stirring at room temperature. The acid component shown in Tables 1 and 2 was added to this solution, and the mixture was stirred for 30 hours. A viscous polyimide precursor solution was obtained. Further, a dicarboxylic acid anhydride or an amine compound containing a photopolymerizable double bond was added to the solution, and the mixture was stirred for 30 hours to obtain a target polyimide precursor solution. This solution was heated at 70 ° C. for 5 hours, the viscosity was adjusted to 100 poise (solid content: 25% by weight), and the polyimide precursor solution (PAA-1 to PAA-1)
PAA-7). The amounts of the amine component, the acid component, the dicarboxylic anhydride component containing a double bond and N-methyl-2-pyrrolidone are shown in Tables 1 and 2.

The viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd.)
, EHD type) at a temperature of 25 ° C and a rotation speed of 2.
It was measured at 5 rpm. A solution obtained by drying the obtained polyimide precursor solutions (PAA-1 to PAA-7)
According to the KBr method, an infrared absorption spectrum (JEOL Ltd.)
Manufactured by JIR-100) was measured.
At around 1600 cm ^-1 , the absorption of C = O of the amide group and 330
The absorption of NH was confirmed at around 0 cm ^-1 .

[0048]

[Table 1]

[0049]

[Table 2]

The abbreviations of each component in Tables 1 and 2 are shown below. OBTA: Octamethylene bis trimellitate dianhydride DBTA: Decamethylene bis trimellitate dianhydride DECA: 4,4'-diaminodiphenyl ether-3
-Carbonamide BPTA: 3,3 ', 4,4'-biphenyltetraamine MLA: Maleic anhydride NBDA: 5-Norbornene-2,3-dicarboxylic anhydride BPDA: Biphenyltetracarboxylic dianhydride DDE: Diamino Diphenyl ether MDAP: dimethylaminopropyl methacrylate

Examples 1-5 and Comparative Examples 1-2 Each of the polyimide precursors (PAA) obtained in Synthesis Examples 1-7
−1 to PAA-7), 0.027 g of 2,6-bis (4′-azidobenzal) -4-carboxycyclohexanone (CA), 4,4′-bis (diethylamino) benzophenone (EAB) 0.027 g and 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one (PDO) 0.054 g are added, mixed with stirring, and provided for Examples 1 to 5 and Comparative Examples 1 and 2. A uniform photosensitive resin composition solution was obtained.

The obtained photosensitive resin composition solution was filtered through a filter, and each solution was spin-coated on a silicon wafer. Next, using a hot plate, the coating was heated at 100 ° C. for 150 seconds to form a 23 μm coating film, and then subjected to pattern masking and exposure with an i-line stepper. This was further heated at 100 ° C. for 60 seconds, and paddle-developed using a mixed solution of N-methyl-2-pyrrolidone / water (75/25 (weight ratio)). 20
By heating at 0 ° C. for 30 minutes and at 350 ° C. for 60 minutes, a polyimide relief pattern was obtained. An infrared absorption spectrum of a part of the obtained polyimide relief pattern was measured by the KBr method. As a result, characteristic absorption of the imide was confirmed at around 1780 cm ^-1 .

The transmittance of each of the polyimide precursors (PAA-1 to PAA-7) obtained in Synthesis Examples 1 to 7, the residual stress of the polyimide obtained above on a silicon wafer, and the resolution of the relief pattern are as follows. And the results of these evaluations are shown in Table 3. The transmittance was determined by spin coating the resin solution of each of the obtained polyimide precursors (PAA-1 to PAA-7) at 85 ° C. for 3 minutes, and further for 1 minute.
The coating film (10 μm) obtained by drying at 05 ° C. for 3 minutes was
It was measured with a spectrophotometer. The residual stress was measured by forming a polyimide film on a 6-inch wafer and using a Tencor Co., Ltd. stress measuring device (FLX-2320). The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

[0054]

[Table 3]

Next, the above Examples 1 to 5 and Comparative Examples 1 to 5
The relief pattern obtained in 2 at 100 ° C. for 30 minutes,
The polyimide pattern was obtained by heating at 200 ° C. for 30 minutes and under a nitrogen atmosphere at 350 ° C. for 60 minutes. The polyimide patterns obtained from the relief patterns of Examples 1 to 5 had almost the same dimensional accuracy as the mask dimensions. The polyimide patterns obtained from the relief patterns of Comparative Examples 1 and 2 had openings larger than the mask dimensions and had poor dimensional accuracy.

[0056]

The photosensitive resin compositions according to the first, second and third aspects have both good i-line transmittance and low residual stress after imidization, and provide a high resolution and a good shape pattern. A polyimide film having good mechanical properties and high heat resistance can be obtained. The semiconductor element according to the fourth aspect has extremely low residual stress after the formation of the polyimide film, and has high reliability in which a polyimide film having good mechanical properties and high heat resistance is formed.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI H01L 21/312 H01L 21/30 502R 21/768 21/90 S

Claims (4)

[Claims] 1. A compound of the general formula (I) Wherein X is a tetravalent organic group, Y is a trivalent or higher organic group,
¹ is (Wherein Z is a group containing a carbon-carbon double bond capable of being polymerized by light or heat), R ² and R ³ are a hydroxyl group or a monovalent organic group, and m is 1 or more. A photosensitive resin composition comprising a polyimide precursor having a repeating unit represented by the formula: 2. A photosensitive resin composition containing a polyimide precursor, wherein a silicon wafer having a polyimide film formed using the photosensitive resin composition has a residual stress of 2%.
A photosensitive resin composition having a pressure of 0 MPa or less. 3. X in the general formula (I) is represented by the general formula (I
I) The photosensitive resin composition according to claim 1, wherein n is 1 to 15. 4. A semiconductor device comprising a polyimide film obtained by coating the photosensitive resin composition according to claim 1, 2 or 3 on a substrate, drying the substrate, and then closing the imide.