JP2000143980A - Precursor composition of positive type photosensitive resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of being developed by an alkali, and excellent in resolution by compounding a polyimide precursor having a specific structure, with a new quinonediazide compound. SOLUTION: This composition comprises (A) a polymer consisting essentially of a structural unit of formula I (R1 is a >=2C tri- to octa-valent organic group; R2 is a >=2C di- to hexa-valent organic group; R3 is H or a 1-20C organic group; n is 10-100,000; m is 0-2; p and q are each 0-4, with the proviso that both of p and q are not simultaneously 0), and (B) a quinonediazide compound of formula II (X is a group of formulas III or IV; R4 and R5 are each a 1-10C monovalent organic group; b and c are each 0-2 with the proviso that both of b and c are not simultaneously 0; d and e are each 0-2). The component A can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine compound at a low temperature. The component B is preferably the one having a hydroxy-containing naphthalene skeleton bonded to the sulfonyl group of naphthoquinonediazide by an ester bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive polyimide precursor composition suitable for a surface protective film, an interlayer insulating film and the like of a semiconductor element, in which a portion exposed to ultraviolet light is dissolved in an alkaline aqueous solution.

[0002]

2. Description of the Related Art As a positive type heat-resistant resin precursor composition in which an exposed portion is dissolved by development, a naphthoquinonediazide added to a polyamic acid (JP-A-52-1)
No. 3315), a solution obtained by adding a naphthoquinonediazide to a soluble polyimide having a hydroxyl group (JP-A-64-6).
No. 0630), a polyamide obtained by adding naphthoquinonediazide to a polyamide having a hydroxyl group (JP-A-56-2714).
No. 0 publication).

However, in the case where naphthoquinone diazide is added to ordinary polyamic acid, the desired pattern can be obtained in most cases because the solubility of the carboxyl group of polyamic acid is high due to the dissolution inhibiting effect of naphthoquinone diazide on alkali. There was no problem. In addition, in the case of adding a soluble polyimide resin having a hydroxyl group, although the problems just described have been reduced, the structure is limited in order to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. Points were problems. Also in the case of adding a naphthoquinonediazide to a polyamide resin having a hydroxyl group, there is a problem in that the structure is limited in order to obtain solubility, and the solvent obtained after heat treatment is inferior in solvent resistance.

[0004] In view of the above drawbacks, the present invention provides a polyimide precursor by adding a new naphthoquinonediazide,
The inventors have found that the resolution of the obtained resin composition is greatly improved, and have reached the invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a polyimide-based positive photosensitive resin precursor composition which is alkali developable and has excellent resolution. Is what you do.

[0006]

The present invention provides (a) a polymer having a structural unit represented by the general formula (1) as a main component;
(B) A positive photosensitive resin precursor composition comprising the quinonediazide compound represented by the general formula (2).

[0007]

Embedded image (R1 is a trivalent having at least two or more carbon atoms)
An octavalent organic group, R2 represents a divalent to hexavalent organic group having at least 2 or more carbon atoms, R3 represents hydrogen,
Or an organic group having 1 to 20 carbon atoms. n is 10
An integer up to 100,000, m is an integer from 0 to 2, p,
q shows the integer of 0-4. p and q do not become 0 at the same time. )

Embedded image (R4 and R5 each represent a monovalent organic group selected from carbon atoms of 1 to 10. b and c each represent an integer of 0 to 2. b and c are not simultaneously 0. d and e are 0 to 2 Indicates an integer up to.)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer having a structural unit represented by the general formula (1) as a main component in the present invention is a polymer having an imide ring, an oxazole ring, or another cyclic structure by heating or an appropriate catalyst. It can be By having a ring structure, heat resistance and solvent resistance are dramatically improved.

The general formula (1) represents a polyamic acid having a hydroxyl group. Due to the presence of the hydroxyl group, the solubility in an aqueous alkali solution is better than that of a polyamic acid having no hydroxyl group. In particular, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than solubility in an aqueous alkali solution. Further, by having a fluorine atom in the general formula (1) at 10% by weight or more, when developing with an aqueous alkali solution,
Since moderate water repellency appears at the interface of the film, penetration of the interface can be suppressed. However, when the fluorine atom content exceeds 20% by weight, the solubility in an aqueous alkali solution decreases, the organic solvent resistance of the polymer formed into a cyclic structure by heat treatment decreases, and the solubility in fuming nitric acid decreases. Not preferred. Thus, it is preferable that the fluorine atom is contained in an amount of 10% by weight to 20% by weight.

In the general formula (1), R 1 represents a structural component of an acid dianhydride. The acid dianhydride contains an aromatic ring and has 1 to 4 hydroxyl groups. At least 2
It is preferably a trivalent to octavalent organic group having at least two carbon atoms, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

Specifically, those having a structure represented by the general formula (3) are preferable. In this case, R6 and R8 are preferably those containing an aromatic ring in view of the heat resistance of the obtained polymer. Particularly preferred structures include those such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid residues. R7 has 3 to 3 carbon atoms.
A trivalent to hexavalent organic group having a hydroxyl group selected from 20 is preferable. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. As such examples, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis (3-amino-4-aminophenyl) hexafluoropropane, 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4 ′
-Dihydroxybiphenyl, 3,3'-diamino-4,
Examples thereof include those in which the amino group of 4'-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene is bonded.

R9 and R10 are preferably hydrogen and / or an organic group having 1 to 20 carbon atoms. When the carbon number is 20 or more, the solubility in an alkali developing solution is reduced.
o and s represent 1 or 2, and r represents an integer of 1 to 4. When r is 5 or more, the properties of the obtained heat-resistant resin film deteriorate.

In the general formula (1), R1 (COOR3) m (O
H) Among the compounds in which p is represented by the general formula (3), preferred compounds include, for example, those having the structures shown below, but are not limited thereto.

[0014]

Embedded image Further, it can be modified with tetracarboxylic acid or dicarboxylic acid having no hydroxyl group as long as the solubility in alkali, the photosensitive performance and the heat resistance are not impaired. For example, aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and two carboxyl groups thereof were converted to methyl groups or ethyl groups. Diester compounds, butanetetracarboxylic acid, aliphatic tetracarboxylic acids such as cyclopentanetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups,
Examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid. These are preferably modified by not more than 50 mol% of the acid component, more preferably not more than 30 mol%. When the modification is performed at 50 mol% or more, the solubility in alkali and the photosensitivity may be impaired.

In the general formula (1), R2 represents a structural component of a diamine. Among them, preferred examples of R2 include those having an aromatic group and a hydroxyl group in view of the heat resistance of the obtained polymer, and specific examples include bis (amino-hydroxy- Phenyl) hexafluoropropane, having no fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine,
Compounds such as diaminophenol and dihydroxybenzidine and those having structures represented by general formulas (4), (5) and (6) can be mentioned.

Among them, R11 and R1 in the general formula (4)
3, R15 in general formula (5), R18 in general formula (6)
Is preferably an aromatic ring or an organic group having a hydroxyl group from the heat resistance of the obtained polymer. R12 in the general formula (4), R14 and R16 in the general formula (5), and R1 in the general formula (6)
7 is preferably an organic group having an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Further, t and u in the general formula (4) represent integers of 1 or 2, and v in the general formula (5) and general formula (6)
Represents an integer of 1 to 4.

A specific example in which R2 (OH) q in the general formula (1) is represented by the general formula (4) is shown below.

[0018]

Embedded image A specific example in which R2 (OH) q in the general formula (1) is represented by the general formula (5) is shown below.

[0019]

Embedded image Specific examples in which R2 (OH) q in the general formula (1) is represented by the general formula (6) are shown below.

[0020]

Embedded image In the general formula (4), R11 and R13 each have 2 to 2 carbon atoms.
It represents a trivalent to tetravalent organic group having a hydroxyl group selected from 0, and preferably has an aromatic ring from the heat resistance of the obtained polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group,
Dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl)
It represents a hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis (hydroxyphenyl) sulfone group, a hydroxydiphenylether group, a dihydroxydiphenylether group, or the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R12 has 2 to 2 carbon atoms
Represents up to 30 divalent organic groups. A divalent group having an aromatic group is better than the heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group,
Examples thereof include a diphenylpropane group and a diphenylsulfone group, and an aliphatic cyclohexyl group and the like can also be used.

In the general formula (5), R14 and R16 represent a divalent organic group having 2 to 20 carbon atoms. An aromatic divalent group is better than the heat resistance of the obtained polymer. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Examples thereof include aliphatic cyclohexyl groups and the like. R1
5 represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis ( Hydroxyphenyl) sulfone group, hydroxydiphenyl ether group,
Represents a dihydroxydiphenyl ether group or the like. Also,
Aliphatic groups such as hydroxycyclohexyl and dihydroxycyclohexyl can also be used.

In the general formula (6), R17 has 2 to 2 carbon atoms.
20 represents a divalent organic group selected from 20. From the heat resistance of the obtained polymer, a divalent group having an aromatic group is good,
Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group.In addition, an aliphatic cyclohexyl group or the like may be used. Can be. R18 represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the viewpoint of heat resistance of the obtained polymer. Specifically, hydroxyphenyl, dihydroxyphenyl, hydroxynaphthyl, dihydroxynaphthyl, hydroxybiphenyl, dihydroxybiphenyl, bis (hydroxyphenyl) hexafluoropropane, bis (hydroxyphenyl) propane, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenylether group, a dihydroxydiphenylether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

Further, it can be modified with another diamine component in the range of 1 to 40 mol%. Examples of these include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone and their aromatics. Examples thereof include compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom. Such examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and aromatics thereof. Aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom, may be mentioned. When such a diamine component is copolymerized in an amount of 40 mol% or more, the heat resistance of the obtained polymer decreases.

R3 in the general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. R3 is preferably an organic group from the viewpoint of the stability of the obtained positive photosensitive resin precursor solution, but is preferably hydrogen in view of the solubility of the aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amount of hydrogen and the organic group of R3, the dissolution rate in an alkaline aqueous solution changes, so that a positive photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. A preferred range is that 10% to 90% of R3 is a hydrogen atom. If the carbon number of R3 exceeds 20, it will not be dissolved in an alkaline aqueous solution. From the above, it is preferable that R3 contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

In the general formula (1), m represents the number of carboxyl groups, and represents an integer from 0 to 2. In the general formula (1), n represents the number of repeating structural units of the polymer of the present invention, and preferably ranges from 10 to 100,000.

Further, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized at R1 and R2 as long as the heat resistance is not reduced. Specifically, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, or the like is used as a diamine component in an amount of 1 to 10;
The positive photosensitive resin composition of the present invention, for example, one obtained by copolymerization with mol% may be composed of only the structural unit represented by the general formula (1), or may be copolymerized with another structural unit. It may be a polymer or a blend. In this case, it is preferable that the content of the structural unit represented by the general formula (1) is 90 mol% or more. The type and amount of the structural unit used in the copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

The photosensitive resin precursor of the present invention is synthesized by a known method. For example, tetracarboxylic acid 2 at low temperature
A method of reacting an anhydride with a diamine compound (CES
Roog et al., Journal Polymer Sci.
ence, Part A-3, 1373 (196
5)), a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol and then reacting the diester with an amine in the presence of a condensing agent (Japanese Patent Application Laid-Open No. 61-72022). To obtain a diester, and then the remaining dicarboxylic acid is converted to an acid chloride and reacted with an amine (JP-A-55-30207).

In the present invention, the naphthoquinonediazide compound represented by the general formula (2) is preferably a compound in which a naphthalene skeleton having a hydroxyl group and a sulfonyl acid of naphthoquinonediazide are bonded by an ester. Examples of the sulfonyl group of naphthoquinonediazide include a 4-naphthoquinonediazidosulfonyl group and a 5-naphthoquinonediazidosulfonyl group. The 4-naphthoquinonediazidosulfonyl group has an absorption in the i-line region of a mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinonediazidosulfonyl group has an absorption extending to the g-line region of the mercury lamp and is suitable for g-line exposure. Are suitable. In the present invention, any of a 4-naphthoquinonediazidosulfonyl group and a 5-naphthoquinonediazidosulfonyl group can be preferably used.However, a 4-naphthoquinonediazidosulfonyl group or a 5-naphthoquinonediazidosulfonyl group is selected depending on the wavelength of light to be exposed. Is preferred. Also, a 4-naphthoquinonediazidosulfonyl group and a 5-naphthoquinonediazidosulfonyl group can be introduced together in the same molecule, or a photosensitive agent having a 4-naphthoquinonediazidosulfonyl group introduced as a photosensitive group and a 5-naphthoquinonediazidosulfonyl group. Photosensitive agents having a group introduced as a photosensitive group may be mixed and used.

In the general formula (2), b and c each represent an integer of 0 to 2. b and c do not become 0 at the same time. If it is larger than 2, the hydrophobicity will increase, so that it will not be dissolved even after exposure to an alkali developing solution, and a pattern may not be obtained.

In the general formula (2), R4 and R5 represent a monovalent organic group selected from C1 to C10, preferably an alkyl group. When the number of carbon atoms is 11 or more, the solubility in an aqueous alkaline solution is reduced. d and e show the integer of 0-2.

Examples include, but are not limited to, the following:

[0032]

Embedded image The resolution is improved by using such a photosensitive agent.
Further, the molecular weight of the naphthoquinonediazide compound is 1500
When the above is reached, the naphthoquinonediazide compound does not thermally decompose sufficiently in the subsequent heat treatment, so that problems such as reduced heat resistance of the obtained film, reduced mechanical properties, reduced adhesiveness may occur. . From such a viewpoint, a preferable molecular weight of the naphthoquinonediazide compound is 300 to 1500. More preferably,
350-1200.

The photosensitive agent may have only the structure represented by the general formula (2) or a mixture with another structure.

If necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ethanol and the like may be used for the purpose of improving the wettability between the positive photosensitive precursor composition and the substrate. Alcohols, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide can also be added.

Further, in order to enhance the adhesion to an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent, etc. are added to the varnish of the positive photosensitive resin precursor composition in an amount of 0.5 to 10% by weight. Alternatively, the underlying substrate can be pre-treated with such a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, etc., a titanium chelating agent, and an aluminum chelating agent are added to the polymer in the varnish in an amount of 0.5 to 10%. % By weight.

When treating the substrate, the above-mentioned coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like. The solution in which 5 to 20% by weight is dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, the reaction between the substrate and the coupling agent proceeds by applying a temperature of 50 ° C. to 300 ° C. after that.

Next, a method for forming a heat-resistant resin pattern using the positive photosensitive precursor composition of the present invention will be described.

A positive photosensitive precursor composition is applied on a substrate. Substrates include silicon wafers, ceramics,
Gallium arsenide is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like.
It is applied so as to have a thickness of 150 μm.

Next, the substrate coated with the positive photosensitive precursor composition is dried to obtain a positive photosensitive precursor composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 to 150 degrees for 1 minute to several hours.

Next, the positive type photosensitive precursor composition film is irradiated with actinic radiation through a mask having a desired pattern to expose the film. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm), h-line (405 nm), and g of a mercury lamp are used.
Preferably, a line (436 nm) is used.

The formation of the heat-resistant resin pattern is achieved by removing the exposed portion using a developer after exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred. In some cases, N-methylpyrrolidone,
Polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate. , Cyclopentanone,
Ketones such as cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several kinds. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 to 500 ° C. This heat treatment is performed for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise or while selecting a certain temperature range and continuously increasing the temperature. For example, 1
Heat treatment is performed at 30 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant resin film formed by the positive photosensitive precursor composition according to the present invention is used for applications such as a passivation film of a semiconductor, a protective film of a semiconductor element, and an interlayer insulating film of a multilayer wiring for high-density mounting. .

[0045]

The present invention will be described below with reference to examples and techniques, but the present invention is not limited to these examples.

Method for Measuring Characteristics Measurement of Viscosity Measurement was performed at 25 ° C. using an E-type viscometer manufactured by Tokimec.

Measurement of film thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.
Was used and the measurement was performed at a refractive index of 1.64.

Synthesis Example 1 Synthesis of naphthoquinone compound (1) 7.21 g (0.05%) of 1-naphthol under a stream of dry nitrogen
Mol) and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride in 450 g of 1,4-dioxane and brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane was used.
g was added dropwise so that the temperature inside the system did not become 35 ° C. or higher. After the addition, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain a naphthoquinone compound (1).

[0049]

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Synthesis Example 2 Synthesis of naphthoquinone compound (2) 7.21 g (0.05%) of 2-naphthol under a stream of dry nitrogen
Mol) and 13.43 g (0.05 mol) of 5-naphthoquinonediazidosulfonyl chloride in 450 g of 1,4-dioxane and brought to room temperature. Here, triethylamine 5.06 mixed with 50 g of 1,4-dioxane was used.
Using g, a naphthoquinone compound (2) was obtained in the same manner as in Synthesis Example 1.

[0051]

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Synthesis Example 3 Synthesis of naphthoquinone compound (3) 2,7-dihydroxynaphthalene under a stream of dry nitrogen
00 g (0.05 mol) and 26.86 g (0.1 mol) of 4-naphthoquinonediazidosulfonyl chloride
It was dissolved in 450 g of 4-dioxane and brought to room temperature. Here, naphthoquinone compound (3) was obtained in the same manner as in Synthesis Example 1 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

[0053]

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Synthesis Example 4 Synthesis of naphthoquinone compound (4) 7.21 g (0.05%) of 1-naphthol under a stream of dry nitrogen
Mol), 8.95 g (0.033 mol) of 5-naphthoquinonediazidosulfonyl chloride and 4.47 g (0.017 mol) of 4-naphthoquinonediazidosulfonyl chloride in 450 g of 1,4-dioxane and brought to room temperature. . Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35 ° C. or higher. After the addition, the mixture was stirred at 30 ° C. for 2 hours.
The triethylamine salt was filtered, and the filtrate was poured into water.
Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried with a vacuum drier to obtain a naphthoquinone compound (4).

[0055]

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Synthesis Example 5 Synthesis of acid anhydride (1) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) under a stream of dry nitrogen
18.3 g (0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of gamma-butyrolactone (GBL) and cooled to -15 ° C.
Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added to the reaction solution at a temperature of 0 g.
The solution was dropped so as not to exceed ° C. After the completion of the dropwise addition, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated using a rotary evaporator, and then added to 1 liter of toluene to obtain an acid anhydride (1).

[0057]

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Synthesis Example 6 Synthesis of hydroxyl group-containing diamine compound (1) 18.3 g (0.05 mol) of BAHF was added to 100 parts of acetone.
The resulting solution was dissolved in propylene oxide (17.4 g, 0.3 mol) and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise thereto. After dropping,
The reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo.

30 g of the solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any more, and the reaction was terminated. After completion of the reaction, the mixture was filtered to remove the palladium compound as a catalyst, and concentrated by a rotary evaporator to obtain a diamine compound (1). The obtained solid was used for the reaction as it was.

[0060]

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Synthesis Example 7 Synthesis of Hydroxy Group-Containing Diamine (2) 15.4 g of 2-amino-4-nitrophenol (0.1 g)
Mol) in acetone 50 ml, propylene oxide 30 g
(0.34 mol) and cooled to -15 ° C. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic chloride in 60 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

This precipitate was dissolved in 200 ml of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon containing hydrogen gas was attached thereto, and stirring was continued at room temperature until the balloon of hydrogen gas did not shrink any more, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to a half volume with a rotary evaporator. Ethanol is added here and recrystallized,
Crystals of the desired compound were obtained.

[0063]

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Synthesis Example 8 Synthesis of hydroxyl-containing diamine (3) 15.4 g of 2-amino-4-nitrophenol (0.1
Mol) in acetone, 100 ml of propylene oxide
Dissolved in 7.4 g (0.3 mol) and cooled to -15 ° C. Here, 20.4 g of 4-nitrobenzoyl chloride
(0.11 mol) dissolved in 100 ml of acetone was gradually added dropwise. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration. Thereafter, crystals of the target compound were obtained in the same manner as in Synthesis Example 6.

[0065]

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Example 1 57.4 g (0.095 mol) of the diamine compound (1) obtained in Synthesis Example 6 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane in a stream of dry nitrogen were used.
24 g (0.005 mol) were dissolved in 350 g of GBL. Here, 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added to GBL
It was added together with 40 g, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours.

A naphthoquinone compound (1) was added to the obtained solution.
20.0 g was added together with 10 g of GBL to obtain a varnish A of a photosensitive polyimide precursor composition.

On a 6-inch silicon wafer, a varnish A of a photosensitive polyimide precursor was prebaked to a thickness of 9 μm.
Then, using a hot plate (SKW-636 manufactured by Dainippon Screen) at 80 ° C. for 3 hours.
By pre-baking at 120 ° C for 3 minutes
A photosensitive polyimide precursor film was obtained. Next, an exposure machine (Nikon i-line stepper NSR-1755-i7A)
The reticle with the pattern cut is set in
I-ray exposure was performed at 00 mJ / cm2 (intensity of 365 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds. Then, it was allowed to stand still for 125 seconds at 0 rotation, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. As a result of observing the pattern after development, a pattern of 5 μm required as a buffer coat for semiconductor was resolved, and the pattern shape was not a problem.

Example 2 15.1 g (0.025 mol) of the diamine compound (2) obtained in Synthesis Example 7 and 4.5 g (0.0225 mol) of 4,4′-diaminodiphenyl ether in a stream of dry nitrogen.
And 0.63 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane in GBL1
Was dissolved in 00 g. Here, 16.1 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (0.
(050 mol) together with 33 g of GBL at room temperature, and reacted at room temperature for 1 hour and then at 50 ° C. for 4 hours.

In 50 g of this polymer solution, 7.6 g of the naphthoquinone compound (2) was dissolved to obtain a varnish B of a photosensitive polyimide precursor composition.

The varnish B was exposed in the same manner as in Example 1, and developed in the same manner as in Example 1 except that the varnish B was allowed to stand at 0 rotation for 170 seconds. As a result of observing the pattern after development, a pattern of 5 μm was resolved, and there was no problem with the pattern shape.

Example 3 A polymer was prepared in the same manner as in Example 1 except that 23.0 g (0.095 mol) of the diamine compound (3) obtained in Synthesis Example 8 was used instead of the diamine compound (1). 9.5 g of the naphthoquinone compound (3) was added to 50 g of the polymer solution.
Is dissolved to form a varnish C of the photosensitive polyimide precursor composition.
I got

Using varnish C, exposure was carried out in the same manner as in Example 1, and development was carried out in the same manner as in Example 1 except that the film was allowed to stand at 0 rotation for 80 seconds.

As a result of observing the pattern after development,
Was resolved, and there was no problem with the pattern shape.

Example 4 19.0 g (0.095 mol) of 4,4'-diaminodiphenyl ether and 1,3-bis (3-
1.24 g of aminopropyl) tetramethyldisiloxane
(0.005 mol) was dissolved in 350 g of GBL. Here, 71.4 g of the acid anhydride (1) obtained in Synthesis Example 5
(0.1 mol) together with 40 g of GBL,
For 1 hour and then at 50 ° C. for 4 hours.

To 50 g of the polymer solution, 20.0 g of the naphthoquinone compound (1) was added together with 10 g of GBL to obtain a varnish D of a photosensitive polyimide precursor composition.

Using a varnish D, exposure was performed in the same manner as in Example 1.
Development was carried out in the same manner as in Example 1, except that the sample was allowed to stand at 0 rotation for 120 seconds. As a result of observing the pattern after development, a pattern of 5 μm was resolved, and there was no problem with the pattern shape.

Example 5 A varnish E of a photosensitive polyimide precursor composition was obtained by dissolving 7.6 g of the naphthoquinone compound (4) in 50 g of the polymer solution obtained in Example 3. Using a varnish E, exposure was performed in the same manner as in Example 1, and the sample was allowed to stand at 0 rotation for 110 seconds.
Development was carried out in the same manner as in Example 1.

As a result of observing the pattern after development,
Was resolved, and there was no problem with the pattern shape.

Comparative Example 1 A varnish F of a photosensitive polyimide precursor composition was obtained by dissolving 10 g of the polymer obtained in Example 1 and 2 g of the naphthoquinone compound (5) shown below in 45 g of GBL. Coating, pre-baking, exposure, and development were performed on a 6-inch silicon wafer in the same manner as in Example 1. The pattern after development is 15
The pattern of μm was resolved. Compared to Example 1,
Resolution was low.

[0082]

Embedded image

Comparative Example 2 10 g of the polymer obtained in Example 2 and 2 g of the naphthoquinone compound (6) shown below were dissolved in 45 g of GBL to obtain a varnish G of a photosensitive polyimide precursor composition. Coating, pre-baking, exposure, and development were performed on a 6-inch silicon wafer in the same manner as in Example 2. The pattern after development is 15
The pattern of μm was resolved. As compared with Example 2,
Resolution was low.

[0084]

Embedded image

Comparative Example 3 Example 3 was repeated using 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride instead of the acid anhydride (1) of Example 4. A polymer was synthesized in the same manner as in Example 4.

To 50 g of this polymer solution, 20.0 g of the naphthoquinone compound (1) was added together with 10 g of GBL to obtain a varnish H of a photosensitive polyimide precursor composition. Example 1
Application, prebaking, exposure, and development were performed on a 6-inch silicon wafer in the same manner as described above. The pattern after development is 15μm
Was resolved. The resolution was lower than in Example 1.

[0087]

According to the present invention, it is possible to obtain a positive photosensitive resin precursor composition having excellent resolution, which can be developed with an aqueous alkali solution.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 26, 1999 (1999.10.
26)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

In the above general formula (1), R1 is a tricarboxylic acid
Acid, represents a structural component of a tetracarboxylic acid, these
Is preferably a trivalent to octavalent organic group having an aromatic ring and having 1 to 4 hydroxyl groups and having at least 2 or more carbon atoms. A valent or tetravalent organic group is more preferred.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

[0014]

Embedded image Further, it can be modified with tetracarboxylic acid or dicarboxylic acid having no hydroxyl group as long as the solubility in alkali, the photosensitive performance and the heat resistance are not impaired. For example, aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, and diphenylsulfonetetracarboxylic acid, and two carboxyl groups thereof were converted to methyl groups or ethyl groups. Diester compounds, butanetetracarboxylic acid, aliphatic tetracarboxylic acids such as cyclopentanetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups,
Examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid. These are preferably modified by not more than 50 mol% of the acid component, more preferably not more than 30 mol%. When the modification is performed at 50 mol% or more, the solubility in alkali and the photosensitivity may be impaired.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/312 H01L 21/312 DF Term (Reference) 2H025 AA02 AA06 AA10 AB16 AC01 AD03 BE01 CB25 CB26 EA10 FA01 FA03 FA17 FA29 4J002 CM041 EQ036 ER006 GP03 4J038 DH001 GA03 GA06 JB18 NA18 PB09 4J043 PA02 PA05 PC065 RA06 SA06 SB01 SB02 TA13 TB01 TB02 UA121 UA122 UA131 UA262 UB011 UB061 UB401 VA021 VA041 VA06 A02A01 Z06

Claims (5)

[Claims] 1. A positive electrode comprising (a) a polymer having a structural unit represented by the general formula (1) as a main component, and (b) a quinonediazide compound represented by the general formula (2). -Type photosensitive resin precursor composition. Embedded image (R1 is a trivalent having at least two or more carbon atoms)
An octavalent organic group, R2 represents a divalent to hexavalent organic group having at least 2 or more carbon atoms, R3 represents hydrogen,
Or an organic group having 1 to 20 carbon atoms. n is 10
An integer up to 100,000, m is an integer from 0 to 2, p,
q shows the integer of 0-4. p and q do not become 0 at the same time. ) (R4 and R5 represent a monovalent organic group selected from carbon atoms of 1 to 10. b and c each represent an integer of 0 to 2. b and c are not simultaneously 0. d and e are 0 to 2 Indicates an integer up to.) 2. The method according to claim 1, wherein R1 (COOR3) m (O
H) p is represented by General formula (3), The positive photosensitive resin precursor composition of Claim 1 characterized by the above-mentioned. Embedded image (R6 and R8 each represent a trivalent to tetravalent organic group selected from C2 to C20; R7 represents a trivalent to hexavalent organic group having a hydroxyl group selected from C3 to C20; R9, R1
0 represents hydrogen and / or an organic group having 1 to 20 carbon atoms. o and s represent 1 or 2, and r represents an integer of 1 to 4. ) 3. The positive photosensitive resin precursor composition according to claim 1, wherein R2 (OH) q in the general formula (1) is represented by the general formula (4). Embedded image (R11 and R13 each represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R12 represents 2 carbon atoms.
And a divalent organic group selected from -30 to 30. t and u each represent an integer of 1 or 2. ) 4. The positive photosensitive resin precursor composition according to claim 1, wherein R2 (OH) q in the general formula (1) is represented by the general formula (5). Embedded image (R14 and R16 each represent a divalent organic group having 2 to 20 carbon atoms, and R15 represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Shows an integer up to 4.) 5. The positive photosensitive resin precursor composition according to claim 1, wherein R2 (OH) q in the general formula 1 is represented by the general formula (6). Embedded image (R17 represents a divalent organic group selected from C2 to C20, and R18 represents a trivalent to hexavalent organic group having a hydroxyl group selected from C3 to C20. W is from 1 to 4. Indicates an integer up to.)