JP2002169283A - Photosensitive polymer composition, method for manufacturing pattern, and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive polymer composition having high sensitivity and preferable pattern form and film residual rate in an unexposed part, to provide a method for manufacturing a pattern by which a pattern with high resolution and preferable profile can be obtained and to provide electronic parts having high reliability by using the above composition. SOLUTION: The photosensitive polymer composition contains (a) a polyamide soluble with an alkali aqueous solution and having the repeating unit expressed by general formula (I), (b) a compound which produces acid by light, and (c) a compound having two or more acyloxymethyl groups and phenolic hydroxyl groups in the molecule. In the formula, U is a tetravalent organic group and V is a bivalent organic group. The composition is used for the method for manufacturing the pattern and for the electronic parts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polymer composition, a method for producing a pattern using the composition, and an electronic component. More specifically, the present invention relates to a surface protection film for an electronic component such as a semiconductor device by heat treatment. The present invention relates to a positive-type and heat-resistant photosensitive polymer composition which is a polybenzoxazole-based heat-resistant polymer applicable as an interlayer insulating film and the like, a method for producing a pattern using the composition, and an electronic component.

[0002]

2. Description of the Related Art Conventionally, as a surface protective film or an interlayer insulating film of a semiconductor element, there are advantages such as excellent heat resistance, mechanical properties and electric properties, easy film formation, and a flat surface. Polyimide is widely used. When polyimide is used as a surface protective film or an interlayer insulating film, a process of forming a through hole or the like is mainly performed by an etching process using a positive photoresist. However, there is a problem that the process involves coating and peeling of a photoresist, which is complicated. Accordingly, heat-resistant materials having both photosensitivity have been studied for the purpose of streamlining work steps.

With respect to the photosensitive polyimide composition,
1. A polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207, etc.); A composition (for example, Japanese Patent Publication No. 3-36861) in which a compound containing a carbon-carbon double bond and an amino group and an aromatic bisazide which can be dimerized or polymerized by irradiation with actinic radiation to a polyamic acid is added. Used.

In using the photosensitive polyimide composition, usually, it is applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and the exposed portion is removed with a developing solution to form a pattern. The above compositions 1 and 2 are negative working compositions using an organic solvent for the developer. An organic solvent developer has a large burden on the environment at the time of waste liquid treatment, and in recent years, in consideration of the environment, a photosensitive heat-resistant material that can be developed with an aqueous developer that can easily treat the waste developer has been required. . In addition, in order to switch from an etching process using a positive photoresist to a negative photosensitive polyimide, it is necessary to change a mask and developing equipment of an exposure apparatus. The compositions 1 and 2 have the problems described above.

On the other hand, as a positive photosensitive polyimide,
3. 3. A polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (JP-A-60-37550); Composition containing a polyamic acid ester containing a phenolic hydroxyl group and an o-diazoquinone compound
-204945) and the like. In addition, as a positive heat-resistant material, heat resistance equivalent to polyimide,
4. Photosensitive material using polybenzoxazole having mechanical and electrical properties; Composition containing a polybenzoxazole precursor and an o-diazoquinone compound
-6947, JP-A-9-302221, etc.)
Is also known.

[0006] However, in the case of 3 above, the photosensitive wavelength is mainly 30
Since it is 0 nm or less, the sensitivity is low, and there is a problem that it is difficult to use it particularly with an i-line stepper (single-wavelength light of 365 nm) used recently. The compositions (4) and (5) are more sensitive than the precursor (3), but have a problem that they are not sufficient. As described above, a positive photosensitive heat-resistant material having sufficient sensitivity has not been obtained at present.

[0007]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art. That is, the present invention provides a positive photosensitive polymer composition having a high sensitivity, a good pattern shape and a good residual film ratio in an unexposed portion. The present invention also provides a method for producing a pattern having a high resolution and a good-shaped pattern by using the above composition. Further, the present invention provides a highly reliable electronic component having a precise pattern having a good shape.

[0008]

According to the present invention, there are provided (a) a compound represented by the following general formula (I):

Embedded image (Wherein, U represents a tetravalent organic group, and V represents a divalent organic group), an aqueous alkali-soluble polyamide having a repeating unit represented by the formula: (b) a compound capable of generating an acid by light, and And (c) a photosensitive polymer composition comprising a compound having two or more acyloxymethyl groups and a phenolic hydroxyl group in a molecule.

In the present invention, the component (c) may be a compound represented by the general formula (II):

Embedded image (Wherein, X represents a single bond or a divalent organic group, R represents an alkyl group or an alkenyl group, R ¹ and R ² each independently represent an alkyl group or an alkenyl group, and m and n each represent an independent group. And p and q are each independently an integer of 0 to 3).

In the present invention, the group represented by X is

Embedded image Wherein two As each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

The present invention also relates to a photosensitive polymer composition wherein the compound represented by the general formula (II) is bis (2-hydroxy-3-acetoxymethyl-5-methylphenyl) methane. In addition, the present invention relates to (a) component 100
(B) 5 to 100 parts by weight of component (b), and (c)
The present invention relates to the above-mentioned photosensitive polymer composition containing 1 to 30 parts by weight of a component.

The present invention also relates to the photosensitive polymer composition according to any one of the above, further comprising (d) a compound which inhibits the dissolution of the component (a) in an aqueous alkali solution.
In the present invention, the component (d) may be a compound represented by the general formula (III):

Embedded image (Wherein, X ⁻ represents a counter anion, R ³ and R ⁴ each independently represent an alkyl group or an alkenyl group, and a and b each independently represent an integer of 0 to 5). The present invention relates to a photosensitive polymer composition containing an iodonium salt.

Further, the present invention relates to 100 parts by weight of component (a), 5 to 100 parts by weight of component (b), and 1 to 100 parts by weight of component (c).
The present invention relates to the above photosensitive polymer composition containing 30 parts by weight and 0.01 to 15 parts by weight of the component (d). The present invention also provides
The present invention relates to a method for producing a pattern, comprising a step of applying and drying the photosensitive polymer composition according to any one of the above on a support substrate, an exposing step, a developing step, and a heat treatment step.

The present invention also relates to a method for producing a pattern in which the light source used in the exposing step is an i-line. The present invention also relates to an electronic component having a pattern obtained by the above manufacturing method as a surface protective film or an interlayer insulating film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The above general formula (I) in the present invention
Component (a) having a repeating unit represented by the formula (1) is a phenolic hydroxyl group-containing polyamide soluble in an aqueous alkali solution. The aqueous alkaline solution is an aqueous alkaline solution such as an aqueous tetramethylammonium hydroxide solution, an aqueous metal hydroxide solution, and an aqueous organic amine solution. The amide unit containing a hydroxy group represented by the general formula (I) finally has heat resistance,
It is converted into an oxazole compound having excellent mechanical and electrical properties.

The polyamide having a repeating unit represented by the general formula (I) used in the present invention may have the repeating unit, but the solubility of the polyamide in an aqueous alkali solution is derived from phenolic hydroxyl groups. It is preferable that an amide unit containing a hydroxy group is contained in a certain ratio or more.

That is, the following equation

Embedded image (In the formula, U represents a tetravalent organic group, V and W represent a divalent organic group. J and k represent a mole fraction, and the sum of j and k is 1
00 mol%, j is 60 to 100 mol%, and k is 40
~ 0 mol%). Here, the mole fraction of j and k in the equation is j = 8
It is preferable that 0 to 100 mol% and k = 20 to 0 mol%.

The molecular weight of the component (a) is preferably from 3,000 to 200,000, more preferably from 5,000 to 200,000 in terms of weight average molecular weight.
100,000 is more preferred. Here, the molecular weight is a value measured by gel permeation chromatography and converted from a standard polystyrene calibration curve.

In the present invention, the polyamide having a repeating unit represented by the general formula (I) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamine. As the dihalide derivative, a dichloride derivative is preferable.

The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, and the like, which are used in an ordinary acid chlorination reaction of carboxylic acid, can be used.

As a method for synthesizing the dichloride derivative, the dicarboxylic acid derivative is reacted with the above-mentioned halogenating agent in a solvent, or the reaction is carried out in an excess of the halogenating agent, and then the excess is distilled off. it can. As a reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

When these halogenating agents are used in a solvent, the amount of the halogenating agent is based on the amount of the dicarboxylic acid derivative.
1.5 to 3.0 mol is preferable, and 1.7 to 2.5 mol is more preferable. When reacting in a halogenating agent,
4.0 to 50 mol is preferred, and 5.0 to 20 mol is more preferred. The reaction temperature is preferably from -10 to 70 ° C,
-20 ° C is more preferred.

The reaction between the dichloride derivative and the diamine is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, usually,
Organic bases such as pyridine and triethylamine are used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably from -10 to 30C, and from 0 to 20C.
C is more preferred.

Here, in the general formula (I), the tetravalent organic group represented by U generally means that two hydroxy groups which react with a dicarboxylic acid to form a polyamide structure are each formed of an ortho group of an amine. Is a residue of a diamine having a structure located at a position, preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and having 6 to 40 carbon atoms.
Forty tetravalent aromatic groups are more preferred. As the tetravalent aromatic group, a group in which all four binding sites are present on an aromatic ring is preferable.

Such diamines include 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, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl)- 1,1,1,3,3,3-hexafluoropropane and the like. These compounds can be used alone or in combination of two or more.

In the above formula of the polyamide, the divalent organic group represented by W is generally a residue of a diamine which reacts with a dicarboxylic acid to form a polyamide structure, and forms the U. It is a residue other than a diamine, preferably a divalent aromatic group or an aliphatic group, and preferably has 4 to 40 carbon atoms, and has 2 to 4 carbon atoms.
A valent aromatic group is more preferred.

Such diamines include 4,4 ′
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2 , 6-Naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether,
Aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, and other diamines containing silicone groups, such as LP-7100, X-22-161A
S, X-22-161A, X-22-161B, X-2
2-161C and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names) and the like. These compounds are used alone or in combination of two or more.

In the general formula (I), the divalent organic group represented by V is a residue of a dicarboxylic acid which reacts with a diamine to form a polyamide structure. Preferably, the number of carbon atoms is from 6 to 40, more preferably a divalent aromatic group having from 6 to 40 carbon atoms. As the divalent aromatic group, a group having two binding sites on an aromatic ring is preferable.

Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane and 4,4'- Dicarboxybiphenyl, 4,
4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5- Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 -Cyclopentanedicarboxylic acid, oxalic acid,
Examples thereof include aliphatic dicarboxylic acids such as malonic acid and succinic acid. These compounds can be used alone or in combination of two or more.

The compound which generates an acid by light, which is the component (b) used in the present invention, is a photosensitizer and has a function of generating an acid and increasing the solubility of the irradiated portion in an aqueous alkaline solution. Things. Examples of the type include an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt. There is no particular limitation, but an o-quinonediazide compound is preferred because of its high sensitivity.

The o-quinonediazide compound is, for example, o
-It is obtained by subjecting a quinonediazide sulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazidosulfonyl chlorides include benzoquinone-
1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride and the like can be used.

As the hydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy Benzophenone, 2,3,4,2 ', 3'-pentahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,
10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, o-aminophenol, m-aminophenol, p-aminophenol, 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 and the like can be used.

The o-quinonediazidosulfonyl chloride and the hydroxy compound and / or the amino compound are blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent per 1 mol of the o-quinonediazidosulfonyl chloride. Preferably. A preferred ratio of the dehydrochlorinating agent to o-quinonediazide sulfonyl chloride is 0.95
/ 1 to 1 / 0.95. The preferred reaction temperature is 0 to 40 ° C, and the preferred reaction time is 1 to 10 hours.

As a reaction solvent, a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like is used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

In the photosensitive polymer composition of the present invention,
The blending amount of the component (b) is preferably 5 to 100 parts by weight, and more preferably 8 to 40 parts by weight based on 100 parts by weight of the component (a) from the viewpoint of the dissolution rate difference between the exposed and unexposed parts and the allowable range of sensitivity. Parts by weight are more preferred.

The component (c) used in the present invention is a compound having two or more acyloxymethyl groups and a phenolic hydroxyl group in the molecule. The use of the component (c) increases the dissolution rate of the exposed portion when developing with an alkaline aqueous solution, thereby increasing the sensitivity. In addition, when the film is cured after pattern formation,
Melting of the film can be prevented. As the component (c) has a larger molecular weight, the effect of accelerating the dissolution of the exposed portion decreases,
Generally, compounds having a molecular weight of 1,500 or less are preferred.
As the component (c), a compound represented by the general formula (II) is preferable.

In the general formula (II), 2 represented by X
Examples of the valent group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a carbon atom having 6 to 30 carbon atoms such as a phenylene group. Arylene group, a group obtained by substituting a part or all of the hydrogen atoms of these hydrocarbon groups with a halogen atom such as a fluorine atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, and the like.
The following general formula

Embedded image (Wherein each X ′ independently represents a single bond, an alkylene group (for example, having 1 to 10 carbon atoms), an alkylidene group (for example, having 2 to 10 carbon atoms), a hydrogen atom thereof Selected from a group in which part or all of is substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc. And when there are a plurality of such groups, they may be the same or different from each other, and m is from 1 to 10).

In the general formula (II), the group represented by X is

Embedded image (Wherein two A's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) is preferred because of its high effect.

The compound represented by the general formula (II) includes bis (2-hydroxy-3-acetoxymethyl-5)
-Methylphenyl) methane, bis (2-hydroxy-3)
-Ethylcarbonyloxymethyl-5-methylphenyl) methane, bis (2-hydroxy-3-propylcarbonyloxymethyl-5-methylphenyl) methane, bis (2-hydroxy-3-butylcarbonyloxymethyl-5-methylphenyl) ) Methane, bis (2-hydroxy-3-acetoxymethyl-5-methylphenyl) ethane, bis (2-hydroxy-3-ethylcarbonyloxymethyl-5-methylphenyl) ethane, 3,3′-bis (acetoxymethyl) ) -4,4′-Dihydroxybiphenyl, 3,3′-bis (ethylcarbonyloxymethyl) -4,4′-dihydroxybiphenyl, 4,4′-
Dihydroxy-3,3 ', 5,5'-tetrakis (acetoxymethyl) biphenyl, 4,4'-dihydroxy-
3,3 ′, 5,5′-tetrakis (ethylcarbonyloxymethyl) biphenyl, bis (4-hydroxy-3-
Acetoxymethylphenyl) methane, bis (4-hydroxy-3-ethylcarbonyloxymethylphenyl) methane, bis [4-hydroxy-3,5-bis (acetoxymethyl) phenyl] methane, bis [4-hydroxy-
3,5-bis (ethylcarbonyloxymethyl) phenyl] methane and the like. Of these, bis (2-hydroxy-3-acetoxymethyl-5-methylphenyl) methane is particularly preferred because of its high effect.

In the photosensitive polymer composition of the present invention,
The amount of the component (c) is 1 to 100 parts by weight of the component (a) in view of the development time and the allowable width of the unexposed portion residual film ratio.
30 parts by weight is preferable, and 5 to 20 parts by weight is more preferable.

In the present invention, the component (d) used as required is a compound which inhibits the solubility of the component (a) in an aqueous alkaline solution. As such component (d), onium salts, diaryl compounds and tetraalkylammonium salts are preferred. As onium salts,
Iodonium salts such as diaryliodonium salts; sulfonium salts such as triarylsulfonium salts; phosphonium salts; and diazonium salts such as aryldiazonium salts. Examples of the diaryl compound include a diaryl urea, a diaryl sulfone, a diaryl ketone, a diaryl ether, a diaryl propane, and a diaryl hexafluoropropane in which two aryl groups such as diaryl hexafluoropropane are bonded via a bonding group.
A phenyl group is preferred. Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group, an ethyl group, or the like.

Among them, diaryl iodonium salts, diaryl urea compounds, diaryl sulfone compounds, tetramethylammonium halide compounds, etc., which show good dissolution inhibiting effects, are exemplified. Examples of the diaryl urea compounds are diphenyl urea, dimethyl diphenyl Urea and the like can be mentioned, and as the tetramethylammonium halide compound, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide and the like can be mentioned.

In particular, the general formula (III)

Embedded image (Wherein, X ⁻ represents a counter anion, R ³ and R ⁴ each independently represent an alkyl group or an alkenyl group, and a and b each independently represent an integer of 0 to 5). Diaryliodonium salt compounds are preferred. As the anion,
Examples thereof include nitrate ion, boron fluoride ion, perchlorate ion, trifluoromethanesulfonic acid ion, p-toluenesulfonic acid ion, thiocyanate ion, chlorine ion, bromine ion, and iodine ion.

Examples of the diaryliodonium salt include diphenyliodonium nitrate and bis (pt
tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, diphenyliodonium bromide, diphenyliodonium chloride,
Diphenyl iodonium iodide and the like can be used.

Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate and diphenyliodonium-8-anilinonaphthalene-1-sulfonate are mentioned as those having high effects and being preferred.

The amount of the component (d) is preferably 0.01 to 30 parts by weight, more preferably 0.01 to 10 parts by weight, per 100 parts by weight of the component (a), in view of sensitivity and the allowable range of the developing time. Parts by weight, more preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight. The photosensitive polymer composition of the present invention comprises the component (a), the component (b), and the component (c).
It can be obtained by dissolving the components and, if necessary, the component (d) in a solvent.

As the solvent, for example, N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, γ
-Aprotic polar solvents such as butyrolactone are preferred, and these are used alone or in combination of two or more.

Further, in order to improve coating properties, a solvent such as diethyl ketone, diisobutyl ketone, methyl amyl ketone, ethyl lactate, propylene glycol monomethyl ether acetate or the like can be used in combination. The amount of the solvent is not particularly limited, but is generally adjusted so that the amount of the solvent in the composition is 20 to 90% by weight.

The photosensitive polymer composition of the present invention may further contain, if necessary, an organic silane compound, an aluminum chelate compound or the like as an adhesion aid. Examples of the organic silane compound include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyl And triethoxysilane. Examples of the aluminum chelate compound include aluminum tris (acetylacetonate), aluminum acetylacetate diisopropylate and the like.

The photosensitive polymer composition of the present invention can be formed into a pattern of polybenzoxazole through the steps of coating and drying on a supporting substrate, exposing, developing, and heating. In the step of coating on a supporting substrate and drying, the photosensitive polymer composition is coated on a supporting substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride by using a spinner or the like. After spin coating using, it is dried using a hot plate, oven or the like.

Next, in the exposure step, the photosensitive polymer composition coated on the supporting substrate is irradiated with actinic rays such as ultraviolet rays, visible rays and radiation through a mask. In the developing step, a pattern is obtained by removing the exposed portion with a developing solution. Preferred examples of the developer include an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is 0.1 to
It is preferably 10% by weight. Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. Each of these may be added 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.

Then, in the heat treatment step, a heat-resistant polybenzoxazole pattern having an oxazole ring and other functional groups is obtained by subjecting the obtained pattern to a heat treatment preferably at 150 to 450 ° C.

The photosensitive polymer composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and specifically, surface protective films and interlayer insulating films of semiconductor devices, multilayer wiring boards. Can be used to form an interlayer insulating film and the like.
The semiconductor device 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.

An example of the manufacturing process of the semiconductor device of the present invention 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 polyimide 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 polymer composition by a spin coating method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is drawn on a predetermined portion. A pattern is formed by developing with an aqueous solution, and heated to form a polybenzoxazole film. This polybenzoxazole film protects the conductor layer from external stress, α-rays, and the like, and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive polymer composition of the present invention.

[0059]

The present invention will be described below with reference to examples. Example 1 4,4'-Dicarboxydiphenyl ether in a 0.5 liter flask equipped with stirrer and thermometer
7 g (0.084 mol) and N-methylpyrrolidone (N
MP), the flask was cooled to 0 ° C., and 20.0 g (0.168 mol) of thionyl chloride was added dropwise while maintaining the reaction temperature at 10 ° C. or lower. After the dropwise addition, the mixture was stirred at around 10 ° C. for 30 minutes. , 4,4'-Dicarboxydiphenyl ether dichloride solution (α) was obtained.

Then, 0.5 g equipped with a stirrer and a thermometer was used.
In a liter flask, add 100 parts of N-methylpyrrolidone.
g, and 2,3.4 g (0.10 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane was added thereto, followed by dissolution with stirring. After that, 26.6 g of pyridine were added. The solution was cooled, and the temperature was kept at 0 to 10 ° C., and
The solution (α) of dicarboxydiphenyl ether dichloride was added dropwise over 30 minutes, and then 30 ° C at around 30 ° C.
Stirred for minutes. The reaction solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure at 40 ° C. for 2 days to obtain polyhydroxyamide.

15.00 g of polyhydroxyamide and tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-4-sulfonyl chloride were combined with 1 / g
2.25 g of an orthoquinonediazide compound reacted at a molar ratio of 2.9, 1.5 g of bis (2-hydroxy-3-acetoxymethyl-5-methylphenyl) methane, and a 50% methanol solution of ureapropyltriethoxysilane in 0. 0%.
30 g was stirred and dissolved in 23.00 g of N-methylpyrrolidone. This solution was filtered under pressure using a Teflon (registered trademark) filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer by a spinner, and dried by heating on a hot plate at 110 ° C. for 3 minutes to obtain a 7.6 μm coating film. An i-line stepper (manufactured by Hitachi, Ltd.) is used as an exposure machine for this coating film, and a reticle is applied to the coating film.
Exposure was performed at 500 mJ / cm ² . Next, paddle development was performed for 35 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. From the pattern observation, the appropriate exposure was determined to be 350 mJ / cm ^2, and a pattern having a good shape was formed at this exposure. The residual film ratio of the unexposed portion was 79%. Under an atmosphere of nitrogen,
After heat treatment at 50 ° C. for 1 hour, a polybenzoxazole film pattern having a good shape was obtained.

Example 2 Polyhydroxyamide 15.00 prepared in Example 1
g, 2.25 g of an orthoquinonediazide compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazide-4-sulfonyl chloride in a molar ratio of 1 / 2.9, bis (2-hydroxy-3 1.5 g of -ethylcarbonyloxymethyl-5-methylphenyl) methane and 50 g of ureapropyltriethoxysilane.
0.30 g of a 30% methanol solution was dissolved in 23.00 g of N-methylpyrrolidone with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 110 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of 7.5 μm. Using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine,
Exposure was performed at 0 to 500 mJ / cm ² . Subsequently, paddle development was performed for 50 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and washed with pure water to obtain a relief pattern. From the pattern observation, the appropriate exposure was determined to be 350 mJ / cm 2, and a pattern having a good shape was formed at this exposure. The residual film ratio of the unexposed portion was 80%. When the obtained pattern was heated at 350 ° C. for 1 hour in a nitrogen atmosphere, a pattern of a polybenzoxazole film having a good shape was obtained.

Example 3 Polyhydroxyamide prepared in Example 1 15.00
g, 2.25 g of a compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazido-4-sulfonyl chloride in a molar ratio of 1 / 2.9, bis (2-hydroxy-3-acetoxy) 1.5 g of methyl-5-methylphenyl) methane, 0.15 g of diphenyliodonium nitrate and 0.30 g of a 50% by weight methanol solution of ureapropyltriethoxysilane were added to NMP2.
The mixture was dissolved in 3.00 g with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 110 ° C. for 3 minutes on a hot plate to obtain a 7.7 μm positive photosensitive resin composition. Was obtained. The photosensitive polyimide precursor coating film was exposed at 100 to 500 mJ / cm ² via a reticle using an i-line reduction projection exposure apparatus (LD-5010i manufactured by Hitachi, Ltd.). Then, 2.38 of tetramethylammonium hydroxide
Paddle development was performed for 80 seconds using a weight% aqueous solution as a developing solution, followed by washing with pure water to obtain a pattern. By pattern observation, the appropriate exposure was determined to be 300 mJ / cm ^2, and a pattern having a good shape was formed at this exposure. The residual film ratio of the unexposed portion was 82%. When this pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a pattern of a polybenzoxazole film having a good shape was obtained.

Comparative Example 1 The polyhydroxyamide obtained in Example 1 15.00
g, 2.25 g of an orthoquinonediazide compound obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazido-4-sulfonyl chloride in a molar ratio of 1 / 2.9, and 50% of ureapropyltriethoxysilane. 0.30 g of a 30% methanol solution was dissolved in 23.00 g of N-methylpyrrolidone with stirring. 3 μm of this solution
The photosensitive polymer composition was obtained by filtration under pressure using a Teflon filter having pores.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 110 ° C. for 3 minutes on a hot plate to obtain a coating film of 7.5 μm. Using an i-line stepper (manufactured by Hitachi, Ltd.) as an exposure machine,
Exposure was performed at 0 to 500 mJ / cm ² . Next, paddle development was performed for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a pattern. By pattern observation, the appropriate exposure was determined to be 450 mJ / cm ² . The residual film ratio of the unexposed portion was 80%.

[0069]

The photosensitive polymer composition of the present invention has a high sensitivity, a high resolution, a good pattern shape and a good residual film ratio in unexposed areas, and has excellent heat resistance. Further, according to the method for producing a pattern of the present invention, a pattern having a high resolution and a good shape can be obtained by using the composition having high sensitivity. Further, the electronic component of the present invention has high reliability by having a polybenzoxazole pattern having a good shape as a surface protective film or an interlayer insulating film.

[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 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window,
7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 503 503Z H01L 21/027 H01L 21/312 D 21/312 21/30 502R (72) Inventor Masataka Nunomura 4-3-1, Higashi-cho, Hitachi, Ibaraki Hitachi Chemical DuPont Microsystems, Inc. Yamazaki Development Center (72) Inventor Takanori Anzai 13-1, Higashi-cho, Hitachi, Ibaraki Hitachi Chemical Dupont Microsystems Co., Ltd. Yamazaki Development Center (72) Inventor Nagatoshi Fujieda 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Dupont Microsystems Co., Ltd. Yamazaki Development Center F-term (reference) 2H025 AA01 AA02 AA03 AA10 AB16 AB17 AC01 AD03 BE07 CB24 CC20 4J002 CL071 EB116 EB 118 EJ067 EQ016 EQ036 EV077 EV227 EV296 FD206 GP03 5F058 AC06 AC07 AC10 AF04 AG01 AH02 AH03

Claims (11)

[Claims] (1) (a) General formula (I) (Wherein, U represents a tetravalent organic group, and V represents a divalent organic group), an aqueous alkali-soluble polyamide having a repeating unit represented by the formula: (b) a compound capable of generating an acid by light, and And (c) a photosensitive polymer composition containing a compound having two or more acyloxymethyl groups and a phenolic hydroxyl group in a molecule. The component (c) is represented by the general formula (II): (Wherein, X represents a single bond or a divalent organic group, R represents an alkyl group or an alkenyl group, R ¹ and R ² each independently represent an alkyl group or an alkenyl group, and m and n each represent an independent group. And p and q are each independently an integer of 0 to 3.) The photosensitive polymer composition according to claim 1, wherein (3) a group represented by X: (Wherein two A's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). 4. The photosensitive polymer composition according to claim 3, wherein the compound represented by the general formula (II) is bis (2-hydroxy-3-acetoxymethyl-5-methylphenyl) methane. 5. The composition of (b) with respect to 100 parts by weight of the component (a).
The photosensitive polymer composition according to any one of claims 1 to 4, wherein 5 to 100 parts by weight of the component and 1 to 30 parts by weight of the component (c) are blended. 6. The method according to claim 1, further comprising (d) a compound which inhibits the dissolution of the component (a) in an aqueous alkali solution.
6. The photosensitive polymer composition according to any one of items 1 to 5. (7) The component (d) has the general formula (III): (Wherein, X ⁻ represents a counter anion, R ³ and R ⁴ each independently represent an alkyl group or an alkenyl group, and a and b each independently represent an integer of 0 to 5). 7. The photosensitive polymer composition according to claim 6, comprising an iodonium salt. (8) 100 parts by weight of the component (a) and (b)
5 to 100 parts by weight of component, 1 to 30 parts by weight of component (c),
The photosensitive polymer composition according to claim 6, wherein (d) component is added in an amount of 0.01 to 15 parts by weight. 9. A pattern production method comprising the steps of applying the photosensitive polymer composition according to any one of claims 1 to 8 on a support substrate, drying, exposing, developing, and heating. Law. 10. A light source used in the step of exposing,
The method for producing a pattern according to claim 9, wherein the pattern is i-line. 11. An electronic component comprising a pattern obtained by the method according to claim 9 as a surface protective film or an interlayer insulating film.