JP2000313743A - Polyimide precursor, production of polyimide, photosensitive resin composition, production of pattern and electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyimide capable of exhibiting excellent heat resistance and low thermal expansibility and having a low residual stress when used as a surface protective film for silicon wafers by heating a specific polyimide precursor having high i radiation transmitting properties. SOLUTION: This polyimide precursor has a recurring unit represented by formula I [R and R' are each H or a monovalent organic group; X is represented by formula II (R1 to R4 are each H or a monovalent organic group); Y is a bi- or a polyalent organic group]. When the precursor is heated at 80-450 deg.C, the skeletal structure is changed and the formation of an aromatic ring and imide cyclization are carried out to produce a polyimide. The polyimide precursor is obtained by reacting a tetracarboxylic dianhyride represented by formula III (e.g. bicyclo [2.2.2]octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride) with a diamine capable of providing the structure of Y in formula I (e.g. 4,4'- diamino-2,2'-dimethylbiphenyl) in a polar solvent such as N-methyl-2-pyrrolidone at -20 to +40 deg.C for 1-10 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyimide precursor, a method for producing a polyimide, a photosensitive resin composition, a method for producing a pattern using the composition, and an electronic component. More specifically, a polyimide precursor having a high i-line transmittance and capable of producing a polyimide having a low residual stress,
The polyimide production method, high i-ray transmittance using this polyimide precursor, high-speed developability, high resolution and high dimensional accuracy photosensitive resin composition, a pattern production method using this composition and Related to electronic components.

[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. While having the advantages of high sensitivity and high film-forming ability, it lacks storage stability and has disadvantages such as chromium ions remaining in polyimide,
It did not reach practical use.

[0005] 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.

[0006] However, these photosensitive polyimide precursors use a basic skeleton as an aromatic monomer having excellent heat resistance and mechanical properties. Due to the absorption of the polyimide precursor itself, light transmittance in the ultraviolet region is low. However, there is a problem that the photochemical reaction in the exposed portion cannot be performed sufficiently effectively, resulting in low sensitivity or deterioration of the pattern shape.

In recent years, with the increase in the degree of integration of semiconductors, processing rules have become increasingly smaller, and there is a tendency for higher resolution to be required. For this reason, a 1: 1 projection exposure machine called a mirror projection and a reduction projection exposure machine called a stepper have been used instead of a conventional contact / proximity exposure machine using parallel rays.

A 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, steppers have been used as g-l
Although a g-line stepper using visible light (wavelength: 435 nm) called ine has been the mainstream, it is necessary to shorten the wavelength of the stepper to be used in order to further meet the demand for finer processing rules. For this reason, currently used exposure machines are shifting from g-line steppers (wavelength: 435 nm) to i-line steppers (wavelength: 365 nm).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines, and g-line steppers have low transparency, especially for i-line (Wavelength: 365 nm), there is almost no transmittance, and a proper pattern cannot be obtained with an i-line stepper.

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. Low-problem problems are exacerbated. 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.

Generally, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of a rigid structure, i-line is hardly transmitted, so that the photosensitive characteristics are deteriorated. In addition, by making the molecular structure flexible, it is possible to reduce the stress applied to the silicon wafer, reduce the warpage, and transmit the i-line. However, in this case, the heat resistance required for the polyimide surface protective film is required. Is not satisfied.

As a method for improving the transmittance of i-rays, a fluorine-introduced polyimide (JP-A-8-2344) is used.
No. 33) and a polyimide having a bent molecular chain (Japanese Patent Application Laid-Open No. 8-36264). However, polyimide into which fluorine has been introduced has a problem that adhesion to a silicon wafer is weak and reliability when used for a semiconductor element is low. In addition, polyimide having a bent molecular chain has a problem that the reliability of a semiconductor device is low because the intermolecular interaction is weak, the heat resistance is reduced, and the thermal expansion coefficient is increased.

[0014]

The inventions according to claims 1 and 2 exhibit good i-line transmittance and exhibit reverse Diels-A
An object of the present invention is to provide a polyimide precursor which exhibits excellent heat resistance and low thermal expansion properties by aromatization and imidization of a bicyclo skeleton portion by an lder reaction, and has low residual stress when used as a silicon wafer surface protective film.

[0015] The invention of claim 3 shows good i-line permeability before imidization, and excellent after imidation due to aromatization and imidation of the bicyclo skeleton portion by reverse Diels-Alder reaction. An object of the present invention is to provide a method for producing a polyimide, which exhibits heat resistance and low thermal expansion, and which can obtain a polyimide having a low residual stress when used as a silicon wafer surface protective film.

The invention according to claims 4 and 5 is characterized in that it has a high i-line transmittance, a high speed developability, a high resolution and a high dimensional accuracy, and aromatization of a bicyclo skeleton by an inverse Diels-Alder reaction and imidization. The present invention relates to a photosensitive resin composition exhibiting excellent heat resistance and low thermal expansion after imidization and having low residual stress when used as a silicon wafer surface protective film.

The invention according to claims 6, 7 and 8 has high i-line transmittance, high-speed developability, high resolution and high dimensional accuracy,
And by the aromatization and imidation of the bicyclo skeleton part by the reverse Diels-Alder reaction, after imidization, it shows excellent heat resistance and low thermal expansion, and has a low residual stress when used as a silicon wafer surface protective film. Related to manufacturing method. The invention according to claims 9 and 10 relates to an electronic component having a surface protective film or an interlayer insulating film exhibiting excellent heat resistance and low thermal expansion, and having excellent reliability.

[0018]

According to the present invention, there is provided a compound represented by the general formula (1):

Embedded image (Wherein, R and R ′ each independently represent a hydrogen atom or a monovalent organic group, and X represents

Embedded image Y represents a divalent or higher valent organic group, and R ¹ , R ² , R
³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group). Further, the present invention provides the above-mentioned general formula (1)
It relates to a polyimide precursor wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms.

In the present invention, the polyimide precursor is heated to obtain the following formula (2)

Embedded image The present invention relates to a method for producing a polyimide, which comprises forming an aromatic ring due to a skeletal structural change represented by formula (1) and closing the imide.

The present invention also relates to a photosensitive resin composition containing the above-mentioned polyimide precursor. The present invention also provides
Further, the present invention relates to the photosensitive resin composition containing a photopolymerization initiator or a compound that generates an acid by light. In addition, the present invention relates to a method for producing a pattern including a step of applying and drying the photosensitive resin composition on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. The present invention also relates to a method for producing a pattern, wherein the exposing step is performed using i-line as an exposure light source.

Further, according to the present invention, the support substrate has a diameter of 12 mm.
The present invention relates to a method for manufacturing a pattern which is a silicon wafer of inches or more. The present invention also relates to an electronic component having a layer of a pattern obtained by the above-mentioned manufacturing method. Furthermore, the present invention relates to an electronic component in which the pattern layer is a surface protective film or an interlayer insulating film.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor of the present invention is a compound having a repeating unit represented by the above general formula (1). This polyimide precursor has a high i structure.
Aromatization and imidation of the bicyclo skeleton portion by the inverse Diels-Alder reaction represented by the above formula (2) progress by heating and produce a polyimide having excellent heat resistance and low thermal expansion having a linear transmittance. Things.

In the polyimide precursor of the general formula (1), the groups represented by R and R 'are a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and is an alkyl group having 1 to 20 carbon atoms, and 3 to 2 carbon atoms.
Hydrocarbon groups such as cycloalkyl group, phenyl group, benzyl group, etc., allyl group, acryloxyalkyl group (alkyl group having 1 to 20 carbon atoms), methacryloxyalkyl group (carbon atom of alkyl group Is an organic group having a carbon-carbon unsaturated double bond. The groups represented by these R and R ′ vary the type and ratio of the preferred groups depending on whether the photosensitive resin composition using the polyimide precursor is a positive type or a negative type, a solvent development type or an alkali development type. be able to.

In the general formula (1), Y represents a moiety other than the amino group of the diamine generally used as a raw material.
It is a valent organic group, and is preferably an aromatic group having one or more aromatic rings such as a benzene ring or a naphthalene ring. The polyimide precursor of the present invention generally has the following general formula (3)

Embedded image (However, the meaning of the symbol in the formula is the same as the meaning of the symbol in the general formula (1)), a tetracarboxylic dianhydride or a derivative thereof, a diamine providing a structure represented by Y, and According to the above, other compounds forming a side chain can be used as a raw material.

The tetracarboxylic dianhydride represented by the general formula (3) includes, for example, bicyclo [2.2.
2] octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride, 7,8-dimethylbicyclo [2.
2.2] octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride, 7,8-diethylbicyclo [2.2.2] octa-2,5-diene-2, 3,5
6-tetracarboxylic dianhydride, 7,8-dipropylbicyclo [2.2.2] octa-2,5-diene-2,
3,5,6-tetracarboxylic dianhydride, 7,8-diphenylbicyclo [2.2.2] octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride, etc. No.

The diamine is not particularly limited. For example, 2,2'-difluorobenzidine, 2,2 ', 6
6'-tetrafluorobenzidine, 2,2'-bis (trifluoro) benzidine, 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'-) diaminodiphenylsulfone, 4,4'- (or 3,4'-, 3,3'-, 2,
4 '-, 2,2'-) diaminodiphenyl sulfide,
Paraphenylenediamine, metaphenylenediamine, p
-Xylylenediamine, m-xylylenediamine, o-
Trizine, o-tolidine sulfone, 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) propane, 3,3′-diamino-4,
4'-dihydroxybiphenyl, 4,4'-diamino-
3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4 −
Amino-3-hydroxyphenyl) sulfone, bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl)
Hexafluoropropane, 3,4-diaminobenzoic acid and the like can be mentioned, and these are used alone or in combination of two or more.

Among the diamines, a diamine having a structure represented by the following formula is preferred from the viewpoint of heat resistance, high i-line transmittance and low thermal expansion.

Embedded image (In the formula, each R ″ independently represents a hydrogen atom, a carboxyl group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms.)

The polyimide precursor of the present invention uses the above-mentioned tetracarboxylic dianhydride as an essential raw material.
At the same time, another tetracarboxylic dianhydride can be used in combination. Specific examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-
Benzophenone tetracarboxylic dianhydride, 3,3 ',
4,4′-diphenylethertetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic 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, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 6,6′-dimethyl-3,3 ′, 4,4′- Aromatic tetracarboxylic dianhydrides such as biphenyltetracarboxylic dianhydride are exemplified.

Of these tetracarboxylic dianhydrides which can be used in combination, preferred is 6,6'-dimethyl-3,3 ', 4,4'-biphenyltetracarboxylic acid from the viewpoint of i-ray permeability. Acid dianhydride, 3,3 ', 4,4'-
Diphenylsulfonetetracarboxylic dianhydride, 2,
3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. When these tetracarboxylic dianhydrides are used in combination, the amount is not particularly limited,
The amount of the tetracarboxylic dianhydride represented by the general formula (3) is 40 to 40% based on the total amount of the tetracarboxylic dianhydride.
It is preferable to be 100% by weight from the viewpoint of i-line transmittance.

The organic solvent used in the reaction is preferably a polar solvent which completely dissolves the polyimide precursor to be produced. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide ,
Dimethyl sulfoxide, tetramethyl urea, hexamethyl phosphoric acid triamide, γ-butyrolactone and the like can be mentioned.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can 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.

Among the polyimide precursors of the present invention, polyamic acid (that is, R and R ′ in the general formula (1))
Is a hydrogen atom) can be obtained by subjecting the tetracarboxylic dianhydride and a diamine to a ring-opening polyaddition reaction in an organic solvent. In this case, the amounts of the tetracarboxylic dianhydride and the diamine are preferably 0.7 / 1 to 1 / 0.7 in the former / latter (mol).

Further, among the polyimide precursors of the present invention,
Polyamic acid ester (that is, one or both of R and R ′ in the general formula (1) are monovalent organic groups) is obtained by dissolving the diamine and a dehalogenating agent such as pyridine in an organic solvent. After reacting by dropping a tetracarboxylic diester dihalide dissolved in an organic solvent, the mixture is poured into a poor solvent such as water, and the precipitate is filtered off and dried. The ratio (molar ratio) of the total amount of the diamine and the tetracarboxylic diester dihalide is preferably in the range of 0.6 / 1 to 1 / 0.6 in the former / the latter, and is preferably in the range of 0.7 / 1.
The range of /1/1/0.7 is more preferable. The reaction temperature is-
The temperature is preferably from 20 to 40C, and the reaction time is preferably from 1 to 10 hours. The ratio of the dehalogenating agent to the tetracarboxylic diester dihalide is 1.8 for the former / the latter (molar ratio).
/ 1 to 2.2 / 1 are preferred, and 1.9 / 1 to 2.2.
A range of 1/1 is more preferable. The tetracarboxylic diester dihalide can be obtained by reacting a tetracarboxylic dianhydride with the alcohol compound having the structure of R or R 'to react a tetracarboxylic diester obtained with thionyl chloride.

The molecular weight of the polyimide precursor of the present invention is not particularly limited.
Preferably it is 000. The molecular weight was measured by gel permeation chromatography,
It can be determined in terms of standard polystyrene.

The method for producing a polyimide according to the present invention can be synthesized by heating the above polyimide precursor and closing the imide ring. In this heating, the reaction of the above formula (2) by the reverse Diels-Alder reaction occurs together with the imide ring closure. The heating conditions are not particularly limited, but the heating temperature is preferably from 80 to 450 ° C. If the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the generated polyimide tends to deteriorate. The heating time is 10
It is preferably set to 100 minutes. This heating time
If the time is less than 10 minutes, the ring-closure reaction tends not to proceed sufficiently. If the time exceeds 100 minutes, the produced polyimide tends to deteriorate, and the workability tends to decrease.

The photosensitive resin composition of the present invention contains the above-mentioned polyimide precursor. Photosensitivity can be imparted to the composition by various methods. For example, a method of imparting photosensitivity by introducing a group having a carbon-carbon unsaturated bond into a side chain of the polyimide precursor itself to give a structure crosslinked by light, an amino capable of ionic bonding with the polyimide precursor A method of compounding a compound having a carbon-carbon unsaturated bond and an amino group, such as acrylates, by adding one or two carbon-carbon unsaturated double bonds.
Known methods such as a method of mixing two or more reactive monomers to impart photosensitivity and a method of mixing a photosensitizer such as a photoacid generator or a photobase generator are known.

In the case of producing a negative photosensitive resin composition in the photosensitive resin composition of the present invention, generally, a polyimide precursor itself or a compound to be added has a carbon-carbon unsaturated bond. At the same time, it is preferable to contain a photopolymerization initiator. As the photopolymerization initiator,
For example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4, -bis (diethylamino)
Benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 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) oxyimino-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, azide compounds and the like. These are used alone or in combination of two or more.

The amount of the photopolymerization initiator used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyimide precursor. . If this amount is less than 0.01 part by weight, the light sensitivity tends to be poor, and if it exceeds 30 parts by weight,
The mechanical properties of the film tend to be poor.

Among the methods for imparting photosensitivity, amino acrylate used to introduce a carbon-carbon unsaturated double bond 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 amino acrylate is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, based on 100 parts by weight of the polyimide precursor.

Examples of the addition-polymerizable compound having a carbon-carbon unsaturated double bond which can be used when preparing a negative photosensitive resin composition include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, and the like. Tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4- Butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexane All methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 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 parts by weight based on 100 parts by weight of the polyimide precursor. When the amount is less than 1 part by weight, the photosensitive characteristics including solubility in a developer tend to be inferior, and when it exceeds 200 parts by weight, the mechanical characteristics of the film tend to be inferior.

The negative photosensitive resin composition 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 to be used is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the polymer compound.
More preferably, the amount is from 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the stability during storage tends to be poor, and if it exceeds 30 parts by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

On the other hand, when a positive photosensitive resin composition is produced, generally, a polyimide precursor having a group soluble in an aqueous alkali solution, such as a carboxyl group or a phenolic hydroxyl group, is used. It is preferable to use a compound that generates an acid by the reaction. The compound that generates an acid by light is a photosensitizer, and has a function of generating an acid and increasing the solubility of a portion irradiated with light in a developing solution (aqueous alkaline solution). Examples of the type include an o-quinonediazide compound, an allyldiazonium salt, a diallyliodonium salt, and a triallylsulfonium salt. There is no particular limitation, but an o-quinonediazide compound is preferred because of its high sensitivity. The o-quinonediazide compound can be obtained, for example, by subjecting an o-quinonediazide sulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating catalyst. Compounds that generate an acid by light are
From the viewpoint of film thickness and sensitivity after development, polyimide precursor 10
It is preferably used in an amount of 5 to 100 parts by weight, more preferably 10 to 40 parts by weight, based on 0 parts by weight.

The photosensitive resin composition of the present invention can be obtained in the form of a solution by dissolving the polyimide precursor and other components in a solvent. As the solvent, for example,
N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone,
An aprotic polar solvent such as cyclopentanone is used alone or in combination of two or more.

The photosensitive resin composition of the present invention may further contain an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid, etc. in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate.

The photosensitive resin composition of the present invention is applied onto a substrate 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, and most of the solvent is removed. 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. Further, since the photosensitive resin composition of the present invention can form a film having a low residual stress, it is suitable for application to a large-diameter wafer such as a silicon wafer having a diameter of 12 inches or more. On this coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion or the exposed portion is developed and dissolved with an appropriate developing solution, By removing, a desired pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for i-line exposure using an i-line stepper or the like.
A contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, other ultraviolet rays, a visible light source, X-rays, and an electron beam can also be used.

As the developing solution, for example, a good solvent (N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), mixed solvents of the above good solvents and poor solvents (lower alcohols, ketones, water, aromatic hydrocarbons, etc.), and alkaline developers. When the polyimide precursor has alkali solubility, an alkaline solution can be used. As the alkaline aqueous solution, for example, an aqueous solution of 5% by weight or less such as sodium hydroxide, potassium hydroxide, sodium silicate, and tetramethylammonium hydroxide, preferably an aqueous solution of 1.5 to 3.0% by weight is used. However, a more preferred developer is a 1.5 to 3.0% by weight aqueous solution of tetramethylammonium hydroxide.
Further, a surfactant or the like can be added to the above-mentioned developer for use. Each of these is blended in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

After the development, it is preferable to rinse with water or a poor solvent, if necessary, and to dry at about 100 ° C. to make the pattern stable. The resulting pattern can be made into a heat-resistant, low-stress relief pattern film by heating. The heating temperature at this time is 150
To 500 ° C, more preferably 200 to 400 ° C. If the heating temperature is less than 150 ° C., the mechanical properties and thermal properties of the obtained film tend to decrease, and if it exceeds 500 ° C., the mechanical properties and thermal properties of the 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.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and more specifically, for surface protection films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

As an example of the electronic component of the present invention, an example of a semiconductor device manufacturing process will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, the surface protective film is coated with the photosensitive resin composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to an alkaline aqueous solution. To form a pattern and heat to form a resin film of a relief pattern. This resin film protects the conductor layer from external stress, α rays, etc.
The obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0057]

The present invention will be described below with reference to examples. (Example 1) 4,4'-Diamino-2,2'-dimethylbiphenyl and N-methyl-2-pyrrolidone (NMP) were added to a 100 ml separable flask equipped with a stirrer, and dissolved by stirring at room temperature. To this solution was added bicyclo [2.2.2] octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride,
After stirring for an hour, a viscous polyimide precursor solution was obtained. Here, bicyclo [2.2.2] octa-2,5-diene-2,3,5,6-tetracarboxylic dianhydride synthesizes the corresponding tetracarboxylic acid and then reacts with acetic anhydride to effect dehydration ring closure. In this way, they were synthesized. Tetracarboxylic acids are described in the literature (R. Meissner,
X. Garcias, S. Mecozzi, and J. Rebek, Jr., J. Am.
Chem. Soc., 119, 77 (1997).)
The 1,3-cyclohexadiene-2,3-dicarboxylic acid derivative obtained by partially reducing the Diels-Alder adduct with catalytic zero-valent titanium and then reacting the acetylenedicarboxylic acid bis
Diels-Alder reaction was performed with 4-methoxybenzyl ester, and the ester moiety was hydrolyzed for synthesis.

Next, this solution was heated at 70 ° C. for 5 hours,
The viscosity was adjusted to 100 poise (solid content: 25% by weight), and a solution of a polyimide precursor was formed. The solution was filtered, filtered and spin-coated on a silicon wafer to form a polyamic acid film. The viscosity was measured using an E-type viscometer at a temperature of 25 ° C. and a rotation speed of 2.5 rpm. Generation of amide bond was confirmed by the absorption of the absorption of NH bond at around 3300 cm ^-1 in IR spectrum, and 1600 cm ^-1 vicinity amide CO bond. The weight average molecular weight of the polyimide precursor was 70,000. Next, using a hot plate, heating was performed at 90 ° C. for 150 seconds to form a coating film, and then in a diffusion furnace (conditions: 100 ° C. × 30 minutes, 200 ° C. × 3).
(0 minute, 350 ° C. × 60 minutes) to form a polyimide film. The formation of the imide bond was 1780 in the IR spectrum.
cm ^-1 was confirmed by absorption near imide CO, formation of an aromatic ring was confirmed by the absorption of the aromatic CC bond at around 1400 cm ^-1 in IR spectrum.

Comparative Example 1 A polyimide film was formed in the same manner as in the above example using 4,4′-diamino-2,2′-dimethylbiphenyl and pyromellitic dianhydride.

Comparative Example 2 Using 4,4′-diamino-2,2′-dimethylbiphenyl and oxyphthalic dianhydride, a polyimide film was formed in the same manner as in the above example.

The i-ray transmittance of each of the polyimide precursors prepared in Example 1 and Comparative Examples 1 and 2 was measured, and the residual stress applied to the silicon wafer and the glass transition temperature (Tg) of the polyimide film after thermosetting were measured. Table 1 shows the measurement results. The i-line transmittance was determined by spin coating the obtained resin solution of each polyimide precursor, drying at 75 ° C. for 100 seconds, and further drying at 90 ° C. for 100 seconds. The coating film (20 μm) obtained was measured with a spectrophotometer. It was measured. The residual stress was measured by forming a polyimide film on a 5-inch wafer and using a Tencor Co., Ltd. stress measuring device (FLX-2320).

[0062]

[Table 1] According to the results shown in Table 1, the polyimide precursor of Example 1 has high i-line transmittance, low residual stress after coating on a silicon wafer, and excellent heat resistance. Is clear.

Example 2 10 g of the polyimide precursor solution obtained in Example 1 was added to 2,6-bis (4′-
Azidobenzal) -4-carboxycyclohexanone
0.027 g, 4,4'-bis (diethylamino) benzophenone 0.027 g and 1-phenyl-2-
(O-ethoxycarbonyl) oxyiminopropane-1
0.054 g of -one was added, and dimethylaminopropyl methacrylate equivalent to the carboxyl group of the polyimide precursor was further added, followed by stirring and mixing to obtain a uniform photosensitive resin composition solution. The obtained photosensitive resin composition solution was filtered through a filter, and each solution was spin-coated on a silicon wafer by dropping. Then, at 90 ° C. for 150 hours using a hot plate.
After heating for about 2 seconds to form a coating film of about 20 μm, the pattern was masked and exposed with an i-line stepper. Add another 100
At 60 ° C. for 60 seconds, and paddle-developed using a mixed solution of N-methyl-2-pyrrolidone / water (75/25 (weight ratio)), and developed at 100 ° C. for 30 minutes, 200 ° C. for 30 minutes, 350 ° C. When heated at 60 ° C. for 60 minutes to obtain a polyimide pattern, holes of 10 μm were resolved and the pattern shape was good.

[0064]

The polyimide precursor of the present invention has a good i
It has excellent heat resistance and low thermal expansion due to aromatization and imidization of the bicyclo skeleton part by reverse Diels-Alder reaction, and has low residual stress when used as a silicon wafer surface protective film. is there.

According to the production method of the present invention, a good i-line permeability is exhibited before imidization, and reverse Diels-Ald
By the aromatization and imidation of the bicyclo skeleton part by the er reaction, a polyimide having excellent heat resistance and low thermal expansion after imidization and having low residual stress when used as a silicon wafer surface protective film is obtained.

The photosensitive resin composition of the present invention has high i-line transmittance, high-speed developability, high resolution and high dimensional accuracy, and is capable of aromatizing a bicyclo skeleton by reverse Diels-Alder reaction and imidizing imide. By imidation, after imidization, it exhibits excellent heat resistance and low thermal expansion, and has low residual stress when used as a silicon wafer surface protective film.

According to the pattern manufacturing method of the present invention, the high i
Excellent heat resistance and low thermal expansion after imidization by aromatization and imidization of bicyclo skeleton by reverse Diels-Alder reaction due to linear transparency, high-speed developability, high resolution and high dimensional accuracy. And a pattern with low residual stress when used as a silicon wafer surface protective film is obtained. The electronic component of the present invention has a surface protective film or an interlayer insulating film exhibiting excellent heat resistance and low thermal expansion, and is excellent in reliability.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1: Semiconductor substrate, 2: Protective film, 3: 1st conductor layer,
4 ... interlayer insulating film layer, 5 ... photosensitive resin layer, 6A, 6B, 6
C: window, 7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01L 21/30 569E F-term (Reference) 2H025 AA00 AA02 AA04 AA10 AA13 AA20 AB16 AC01 AC08 AD01 AD03 BC13 BC31 CB25 FA29 4J011 QB17 QB18 SA02 SA16 SA20 SA22 SA25 SA34 SA42 SA61 SA63 SA64 SA78 SA80 SA83 SA86 UA01 UA02 VA01 WA01 4J043 PA02 PA04 PA15 PA19 QB31 RA06 RA34 SA06 SA54 SA71 SB01 SB02 TA22 TB01 TB02 UA121 UA122 UA131 UA1 UA2 UA1 UA2 UA1 UB301 UB302 VA011 VA021 VA101 XA14 XA16 XA18 XA19 YA06 YB47 ZB22 5F046 CA08 JA04 JA22 LA01 LA12 LA18

Claims (10)

[Claims] 1. A compound of the general formula (1) (Wherein, R and R ′ each independently represent a hydrogen atom or a monovalent organic group, and X represents Y represents a divalent or higher valent organic group, and R ¹ , R ² , R
³ and R ⁴ each independently represent a hydrogen atom or a monovalent organic group). 2. In the general formula (1), R ¹ , R ² , R ³
The polyimide precursor according to claim 1, wherein R ⁴ and R ⁴ are hydrogen atoms. 3. The polyimide precursor according to claim 1 or 2, which is heated to obtain the following formula (2). A method for producing a polyimide, comprising forming an aromatic ring by changing the skeletal structure shown in (1) and closing the imide. 4. A photosensitive resin composition comprising the polyimide precursor according to claim 1. 5. The photosensitive resin composition according to claim 4, further comprising a photopolymerization initiator or a compound capable of generating an acid by light. 6. A method for producing a pattern, comprising a step of applying and drying the photosensitive resin composition according to claim 4 on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. 7. The method according to claim 6, wherein the step of exposing is performed using i-line as an exposure light source. 8. The method according to claim 6, wherein the supporting substrate is a silicon wafer having a diameter of 12 inches or more. 9. An electronic component having a layer of a pattern obtained by the method according to claim 6, 7, or 8. 10. The electronic component according to claim 9, wherein the pattern layer is a surface protective film or an interlayer insulating film.