JP2001049118A - Heat resistant resin composition and semiconductor device prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat resistant resin composition low in decrease of film properties useful as an interlayer dielectric or the like in the semiconductor field by using a polymer having a specific structural unit and a photo acid generating agent or the like. SOLUTION: This heat resistant resin composition comprises (a) a polymer mainly comprising a structural unit expressed by the formula (R1 is a 2-8 valent C>=2 organic group; R2 is a 2-6 valent C>=2 organic group; R3 is H, an alkali metal ion, ammonium ion or a 1-20C organic group; m is an integer of 3-100,000; n is an integer of 0-2 and in the case of n=2 then R3 may be the same or different; p and q are each an integer of 0-4; p+q>0) and (b) a photo acid generating agent and/or a dissolution adjusting agent, and the thermal weight decreasing rate of the photo acid generating agent and the dissolution adjusting agent at 200 deg.C to 350 deg.C is <=30%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin used for an interlayer insulating film, a surface protection layer and the like in the field of semiconductors, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Heat-resistant resins are used in the field of semiconductors for forming interlayer insulating films, surface protective films (buffer coat films, alpha-ray shielding films) and the like. When the heat-resistant resin composition is used for these applications, it is necessary to perform fine processing for the purpose of forming a through hole. For example,
A solution of a polyamic acid, which is a polyimide precursor, is applied to a substrate, converted into polyimide by heat treatment, then a positive photoresist relief pattern is formed on the polyimide film, and a hydrazine-based etchant is formed using this as a mask. By selectively etching the polyimide film by using the above, the polyimide film can be patterned. However, the above-described patterning of polyimide involves a complicated process because it involves steps such as application and stripping of a photoresist. Further, there is a problem that dimensional accuracy is reduced due to side etching. For these reasons, a photosensitive resin composition which is a heat-resistant resin or a precursor which can be converted into a heat-resistant resin by heat treatment or the like and which itself can be subjected to pattern processing has been studied.

[0003] Since the photosensitive resin composition has a pattern processing accuracy that can be adapted to the pattern formation of the passivation film, first, the pattern processing and curing of the photosensitive resin composition are performed on the passivation film before pattern formation, and then, A method of performing dry etching of the underlying passivation film using this pattern as a mask has been studied (collective opening method). According to this method, the process required for forming the pattern of the passivation film can be omitted, which leads to cost reduction.

[0004] In using the photosensitive resin composition, it is usually applied to a substrate in a solution state, dried, and irradiated with actinic rays through a mask. The negative-type photosensitive resin composition in which the exposed portion remains by development includes polyamic acid obtained by adding a carbon-carbon double bond capable of being dimerized or polymerized by actinic radiation and an amino group or a quaternized salt thereof, Known are those obtained by adding acrylamides to polyamic acid, polyimide precursors having a carbon-carbon double bond group, and those containing a specific oxime compound and a sensitizer.

[0005] However, when switching from the conventional non-photosensitive resin composition patterning process using a positive photoresist to a process using a negative photosensitive resin composition, it is necessary to change the mask of the exposure apparatus, There was a problem that the development equipment had to be changed. In addition, these negative photosensitive resin compositions use an organic solvent for development, but from the viewpoint of preventing environmental pollution and improving the working environment, a photosensitive material that can be developed with an aqueous developer instead of an organic developer is desired. Was rare. For these reasons, a positive photosensitive resin composition that can be alkali-developed has been studied.

[0006] Positive photosensitive resin compositions in which the exposed portions are dissolved by development with an aqueous alkaline solution include o
A polyimide precursor in which a nitrobenzyl group is introduced by an ester bond, a mixture of a polyamic acid ester and an o-quinonediazide compound, or a polyamic acid or a polyamic acid ester having a phenolic hydroxyl group.
Known are a mixture of a quinonediazide compound, a mixture of a polyimide having a phenolic hydroxyl group and an o-quinonediazide compound, and a mixture of polyhydroxyamide and an o-quinonediazide compound.

However, the polyimide precursor having an o-nitrobenzyl group introduced by an ester bond has a problem in that the photosensitive wavelength is mainly 300 nm or less and the sensitivity is low. A mixture of a polyamic acid ester and an o-quinonediazide compound has a problem in that the sensitivity is low and the development time is long because the dissolution rate in an alkali developing solution is low. A mixture of a polyamic acid having a phenolic hydroxyl group and an o-quinonediazide compound,
There is a problem in that it can be applied only to a dilute developer because the solubility in an alkali developer is too large, and that it is difficult to process a fine pattern because an unexposed portion swells with the developer. A mixture of a polyamic acid or polyimide having a phenolic hydroxyl group and an o-quinonediazide compound improved the dissolution rate in an alkali developer, but had a problem in that it was difficult to control the dissolution rate. O- to polyhydroxyamide
The mixture containing a quinonediazide compound also improved the dissolution rate in an alkali developer, but had a problem in that the polymer composition had to be changed in order to further control the dissolution rate.

As a method of heat-treating (curing) the heat-resistant resin composition, there are generally known a method using an inert oven or a furnace and a method using a hot plate. The temperature condition is, for example, 1 hour at 350 ° C. for 1 hour.
There are various stages such as a stage only at 140 ° C. for 30 minutes followed by a stage at 350 ° C. for 1 hour, or even more than 3 stages, and the temperature differs depending on the polymer system.

When a heat-resistant resin is used for a semiconductor, the heat-resistant resin remains as a permanent film in the device, so that the physical properties of the cured film after the heat treatment are important. Photosensitizer,
When heat-treating a heat-resistant resin composition containing various compounds such as an acid generator and a dissolution regulator, due to the compound contained, the film properties are higher than those of a heat-resistant resin composition not containing these compounds. Is inferior. Specific examples include a decrease in mechanical properties such as elongation at break, a decrease in adhesion to a substrate, an increase in absorbance, and a decrease in thermogravimetric reduction temperature. In particular, when the heat resistance of the various compounds contained is low, the physical properties of the film significantly decrease.

[0010]

In order to suppress the deterioration of the film properties due to the addition of various compounds, it is conceivable to use a compound having high heat resistance or to lower the heat treatment temperature. However, there is no quantitative knowledge about the heat resistance and heat treatment temperature of the compound to be contained, and in order to obtain a heat-resistant resin composition with a small decrease in film physical properties, a cured film of the heat-resistant resin composition is actually prepared, and the Physical properties had to be measured.

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object of the present invention is to evaluate a heat resistance of a compound to be added to easily prepare a heat-resistant resin with a small decrease in film physical properties. To give.

[0012]

The present invention comprises (a) a polymer having a structural unit represented by the general formula (1) as a main component, and (b) a photoacid generator and / or a dissolution regulator. A heat-resistant resin composition, wherein the photoacid generator and the dissolution regulator have a thermogravimetric reduction rate from 200 ° C. to 350 ° C. of 30%.
It is a heat-resistant resin composition characterized by the following.

[0013]

Embedded image (R ¹ is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 or more carbon atoms, and R ³ is hydrogen or alkali. A metal ion, an ammonium ion or an organic group having 1 to 20 carbon atoms, m is an integer of 3 to 100,000, n is an integer of 0 to 2, and when n is 2, R ³ is the same or different. P and q are integers from 0 to 4, and p + q> 0.)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the heat-resistant resin composition of the present invention include polyimide and its precursor polyamic acid, polybenzoxazole and its precursor polyhydroxyamide, polybenzothiazole and its precursor polythiohydroxyamide, and polybenzo. Imidazole and its precursor polyaminoamidoimide ring, oxazole ring,
Examples of other polymers having a cyclic structure include, but are not limited to, these. Preferably, a polymer represented by the general formula (1) is used.

A thermogravimetric device is used for the thermogravimetric reduction measurement. The thermogravimetric loss from room temperature to 350 ° C. was tracked,
The thermogravimetric reduction rate from 00 ° C to 350 ° C is determined. For example, in the case of an o-naphthoquinonediazidosulfonic acid ester compound, a decrease in thermogravity due to the o-naphthoquinonediazide site is observed at around 150 ° C., but the decomposition at this time does not significantly affect the physical properties of the film after the heat treatment. The thermogravimetric reduction rate that affects the physical properties is set to 200 ° C. as a reference (measurement start) temperature.

It is preferred that the photoacid generator and the dissolution regulator have a thermogravimetric reduction ratio of 200% to 350 ° C of 40% or less. If it is more than this, the effect of thermal decomposition of the photoacid generator and the dissolution regulator is large, and the physical properties of the film after the heat treatment are significantly reduced. More preferably, the thermal weight loss rate is 30%
It is as follows. Evaluation of film physical properties after curing includes preparing a cured film on a silicon wafer or glass substrate, mechanical properties such as elongation at break, adhesion to the substrate, thermal properties such as thermogravimetric reduction temperature, and electrical properties. Measure etc.

The solvent used in the present invention includes N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide,
Polar aprotic solvents such as dimethyl sulfoxide,
Solvents such as ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene alone , Or a mixture thereof.

In order to enhance the adhesiveness to the substrate, a silane coupling agent, a titanium chelating agent and the like can be used in combination with the silicone diamine. These adhesion aids are added in the same manner as the silicone diamine. Silane coupling agents such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, titanium chelating agents,
It is preferable to add 0.5 to 10 parts by weight of the aluminum chelating agent to the polymer.

By treating the substrate, it is possible to further improve the adhesiveness. Solution obtained by dissolving 0.5 to 20 parts by weight of the above-described coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, then 50 ° C to 300 ° C
The reaction between the substrate and the coupling agent proceeds by applying a temperature up to

The material of the substrate in the present invention includes, for example, metal, glass, semiconductor, metal oxide insulating film, silicon nitride and the like. Preferably, a silicon wafer is used.If necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, or an alcohol such as ethanol for the purpose of improving the wettability between the composition and the substrate. And ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powder of polyimide can also be added.

In the present invention, the polymer represented by the general formula (1) can be a polymer having an imide ring, an oxazole ring or another cyclic structure by heating or an appropriate catalyst. By having a ring structure, heat resistance and solvent resistance are dramatically improved. In the general formula (1),
The residue constituting R ¹ represents a structural component of an acid, and is a divalent to octavalent organic group having at least two or more carbon atoms. From the viewpoint of the heat resistance of the polymer in the present invention,
R ¹ is preferably a divalent to octavalent organic group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms.

In the general formula (1), the residue constituting R ² represents a structural component of a diamine, and is a divalent to hexavalent organic group having at least two or more carbon atoms. From the viewpoint of the heat resistance of the polymer in the present invention, R ² is preferably a divalent to hexavalent organic group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms.

In the general formula (1), R ³ is hydrogen, an alkali metal ion, an ammonium ion or a group having 1 to 20 carbon atoms.
Up to organic groups. At this time, when n is 2, R ³ may be the same or different.

The heat-resistant resin composition of the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. Is also good. 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 polymer obtained by the final heat treatment.

The polymer having the structural unit represented by the general formula (1) as a main component is synthesized by a known method. That is, when R ³ is hydrogen, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-
Reaction in a polar solvent containing methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide or the like as a main component, or a solvent containing γ-butyrolactone as a main component It is synthesized by a known method, for example.

When R ³ is an alkyl group, after reacting a tetracarboxylic dianhydride with an alcohol compound,
An acid chloride is synthesized using thionyl chloride or the like and then selectively combined with a suitable diamine, or selectively combined with a diamine using a suitable dehydrating agent such as dicyclohexylcarbodiimide, and these are combined with N-methyl- A polar solvent containing 2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide or the like as a main component,
It is synthesized by a known method such as a reaction in a solvent containing γ-butyrolactone as a main component.

The effect of the present invention can be obtained by any of the polymers corresponding to the general formula (1). Among them, the following polymers are preferable.

[0028]

Embedded image (R ⁴ is a tetravalent organic group having at least 2 or more carbon atoms, R ⁵ is a divalent organic group having at least 2 or more carbon atoms, R ⁶ and R ⁷ are hydrogen, alkali metal ion, ammonium Represents an ion or an organic group having 1 to 30 carbon atoms. R ⁶ and R ⁷ may be the same or different.)

[0029]

Embedded image (R ⁸ is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R ⁹ is a divalent to hexavalent organic group having at least 2 or more carbon atoms, R ¹⁰ is hydrogen, or Represents an organic group having 1 to 20 carbon atoms, m is 3 to 10
An integer up to 0000, t is 1 or 2, r, s is an integer from 0 to 4, and r + s> 0. )

[0030]

Embedded image (R ¹¹ represents a divalent organic group having at least 2 or more carbon atoms, and R ¹² represents a tetravalent organic group having at least 2 or more carbon atoms.) In the general formula (2), R 4 represents A tetravalent organic group having at least two or more carbon atoms is shown. In view of the heat resistance of the polymer in the present invention, R ⁴ is preferably a tetravalent organic group containing an aromatic or aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ⁴ include 3,3 ′,
4,4′-biphenyltetracarboxylic acid, 3,3 ′,
4,4′-diphenylethertetracarboxylic acid, 3,
3 ', 4,4'-diphenylhexafluoropropanetetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, pyromellitic acid , Butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and the like, but are not limited thereto. Also, R
4 may be composed of one of these, or 2
Copolymers composed of more than one kind may be used.

In the general formula (2), R ⁵ is a divalent organic group having at least two or more carbon atoms. In view of the heat resistance of the polymer according to the invention, R ⁵ is preferably a divalent organic group containing an aromatic or aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ⁵ include paraphenylenediamine, metaphenylenediamine, methylparaphenylenediamine, methylmetaphenylenediamine, dimethylparaphenylenediamine, dimethylmetaphenylenediamine, trimethylparaphenylenediamine, trimethylmetaphenylenediamine, and tetramethylparaphenylenediamine. Phenylenediamine, tetramethylmetaphenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymeta Phenylenediamine, trifluoromethoxyparaphenylenediamine, trifluoromethoxymetaphenylene Diamine, fluoroparaphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonyl Metaphenylenediamine, diaminodiphenylmethane, bis (aminomethylphenyl) methane,
Bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl)
Methane, bis (aminodiethylphenyl) methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotrifluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (amino Dimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane Bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) Safluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, Diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl)
Ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis Examples include, but are not limited to, residues of compounds such as (aminophenoxyphenyl) methane and bis (aminophenoxyphenyl) sulfone, and residues of its water-added compounds. Further, R ⁵ may be composed of one of these, or may be a copolymer composed of two or more.

In the above general formula (2), R ⁶ and R ⁷
Represents hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms. 1-30 carbon atoms
The organic group is preferably an aliphatic organic group, and the organic group contained therein is a hydrocarbon group, a hydroxyl group, a carbonyl group,
Examples include, but are not limited to, a carboxyl group, a urethane group, a urea group, and an amide group. Preferred specific examples include methyl, ethyl, isopropyl, butyl, t-butyl, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, propyl methacryl Examples include, but are not limited to, an amide group, an ethylacrylamide group, and a propylacrylamide group.
In addition, R ⁶ and R ⁷ are more preferably hydrogen, an alkali metal ion, or an ammonium ion, and most preferably hydrogen, from the viewpoint of easy desorption and rapid conversion to polyimide.

The above R ⁶ and R ⁷ may be a single kind or a mixture of two or more kinds. Further, R ⁶ and R ⁷ may be the same or different.

The polymer having the structural unit represented by the general formula (3) as a main component may or may not have a hydroxyl group, but preferably has a hydroxyl group. When it has a hydroxyl group, its solubility in an aqueous alkali solution is better than that of a polyamic acid having no hydroxyl group due to the presence of the hydroxyl group. In particular, among the hydroxyl groups, phenolic hydroxyl groups are preferable from the viewpoint of solubility in an aqueous alkaline solution.

In the general formula (3), the residue constituting R ⁸ represents a structural component of an acid, and represents a trivalent to octavalent organic group having at least two or more carbon atoms. The acid component is preferably a trivalent to octavalent organic group having 2 to 60 carbon atoms and having an aromatic ring and having 1 to 4 hydroxyl groups. When R ⁸ does not contain a hydroxyl group, the R ⁹ component desirably contains 1 to 4 hydroxyl groups. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond. Examples of such a structure include those having the following structures, but the present invention is not limited thereto.

[0036]

Embedded image Further, as a residue containing R ^8, tetracarboxylic acid having no hydroxyl group, tricarboxylic acid, may also be used dicarboxylic acid. Examples of these include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid,
Aromatic tetracarboxylic acids such as diphenylsulfonetetracarboxylic acid, diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and carboxyls thereof Examples thereof include diester compounds in which two groups are converted to a methyl group or an ethyl group, and aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid.

In the general formula (3), the residue constituting R ⁹ represents a structural component of diamine. Among these, as a preferred example of R ⁹ , those having an aromatic group and having 1 to 4 hydroxyl groups are preferable in view of the heat resistance of the obtained polymer. When R ⁹ does not contain a hydroxyl group, the R ⁸ component desirably contains 1 to 4 hydroxyl groups. Further, the hydroxyl group is preferably located at a position adjacent to the amide bond.

Specific examples include compounds such as bis (aminohydroxyphenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, diaminophenol and dihydroxybenzene, and those having the structures shown below. Can be

[0039]

Embedded image Further, a diamine containing no hydroxyl group can be used as the residue containing R ⁹ in the general formula (3). 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. These diamine compounds are used alone or in combination of two or more. These are preferably used in an amount of 40 mol% or less of the diamine component. When the copolymerization is at least 40 mol%, the heat resistance of the obtained polymer is reduced.

R ^{10 in the} general formula (3) represents hydrogen or an organic group having 1 to 20 carbon atoms. More preferably, it is an organic group having 1 to 10 carbon atoms. The number of carbon atoms in R ¹⁰ is not dissolved in an alkaline aqueous solution exceeds 20. R ¹⁰ is preferably an organic group in view of the stability of the obtained photosensitive resin solution, but is preferably hydrogen in view of solubility in an aqueous alkaline solution.
That is, it is not preferable that all of R ¹⁰ be hydrogen or all organic groups. The amount of hydrogen and organic group R ¹⁰ by controlling the so dissolution rate into the alkaline aqueous solution is changed, it is possible to obtain a photosensitive resin composition having an appropriate dissolution rate by this adjustment. m is 3 to 10
T is 1 or 2, r, s is an integer from 0 to 4, and r + s> 0. r
Is 5 or more, the properties of the resulting heat-resistant resin coating deteriorate.

It is also possible to control the amount of the remaining carboxyl groups by imidizing a part of the carboxyl groups. As an imidation method, a known method may be used as long as the imidization can be performed. The imidation ratio at this time is preferably 1% or more and 50% or less. If the imidization ratio exceeds 50%, the absorption of the polymer to actinic radiation used for exposure increases, and the sensitivity decreases.

In the general formula (4), R ¹¹ represents a divalent organic group having at least two or more carbon atoms. From the heat resistance of the polymer in the present invention, R ¹¹ is preferably a divalent organic group containing an aromatic or aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ¹¹ include diphenyl ether-3,3′-dicarboxylic acid,
Diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, isophthalic acid, benzophenone-3,3'-dicarboxylic acid, benzophenone-3,4'-dicarboxylic acid, benzophenone-
4,4′-dicarboxylic acid, diphenylsulfone-3,
3'-dicarboxylic acid, diphenylsulfone-3,4'-
Residues such as, but not limited to, dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid. In addition, R ¹¹ may be composed of one of these, or may be a copolymer composed of two or more.

In the general formula (4), R ¹² represents a tetravalent organic group having at least two or more carbon atoms. In view of the heat resistance of the polymer according to the invention, R ¹² is preferably a tetravalent organic group containing an aromatic or aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ¹² include 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, and 3,4′-diamino-
Residues such as, but not limited to, 3,4'-dihydroxydiphenyl ether. Also, R12
May be composed of one of these, or may be a copolymer composed of two or more.

The polybenzoxazole precursor represented by the general formula (4) is synthesized by a known method. That is, it can be obtained by a method such as condensation of dihydroxydiamine and halogenated dicarboxylic acid, or condensation of dihydroxydiamine and dicarboxylic acid in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide.

The polymers represented by the general formulas (2), (3) and (4) are desirably as transparent as possible to the actinic radiation to be exposed. Therefore, 365
The absorbance of the polymer in nm is preferably 0.1 or less per 1 μm. It is more preferably 0.08 or less. If it exceeds 0.1, the sensitivity to exposure to actinic radiation of 365 nm decreases.

The heat-resistant resin composition of the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. Is also good. 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 polymer obtained by the final heat-treated film.

The polymer having a structural unit represented by the general formula (1) as a main component can be imparted with photosensitivity by adding a photoacid generator. In particular, it is preferably used in a polymer mainly containing the structural units represented by the general formulas (3) and (4). Examples of the photoacid generator include diazonium salts, diazoquinonesulfonic acid amides, diazoquinonesulfonic acid esters, diazoquinonesulfonic acid salts,
Nitrobenzyl esters, onium salts, halides,
Halogenated isocyanates, halogenated triazines, bisarylsulfonyldiazomethanes, disulfones, and other compounds that decompose upon irradiation with light to generate an acid are exemplified. In particular, an o-quinonediazide compound is desirable because it has an effect of suppressing the water solubility of an unexposed portion. Such compounds include 1,2-benzoquinone-2-azido-4-sulfonic acid ester or sulfonic acid amide, 1,2-naphthoquinone-2-diazido-5-sulfonic acid ester or sulfonic acid amide, -Naphthoquinone-2-diazide-4-sulfonic acid ester or sulfonic acid amide. These include, for example, 1,2-benzoquinone-2-azido-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and the like. By subjecting o-quinonediazidosulfonyl chlorides to a polyhydroxy compound or a polyamino compound in the presence of a dehydrochlorination catalyst.

Examples of the polyhydroxy compound include 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'-tetrahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,1,1-
Tris (4-hydroxyphenyl) ethane, 1- [1-
(4-hydroxyphenyl) isopropyl] -4-
[1,1-bis (4-hydroxyphenyl) ethyl] benzene, methyl gallate, ethyl gallate and the like.

Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide and the like.

Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3′-dihydroxybenzidine.

The photoacid generator used in the present invention is preferably any of the above-mentioned photoacid generators, as long as the compound has a thermogravimetric reduction ratio of 200% to 350 ° C of 30% or less. Can be used. In particular,
Methyl 3,4,5-trihydroxybenzoate, 4,4 ′
-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol,
4,4 ', 4 "-ethylidene trisphenol, 4,6-
Bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol and 4,4,4 ', 4'-tetrakis [(1-methylethylidene) bis (1,4-cyclohexylidene)] phenol. And at least one hydroxyl group is an 1,2-naphthoquinonediazide-4-sulfonyl group or a 1,2-naphthoquinonediazide-5-sulfonyl group, but is not limited thereto.

The o-quinonediazide compound is blended in an amount of preferably 5 to 100 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the polymer represented by the general formula (1). If the amount is less than 5 parts by weight, sufficient sensitivity cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance of the resin composition may be reduced. Therefore, it is preferable that the addition amount of the o-quinonediazide compound is a necessary minimum.

The dissolution controlling agent in the present invention is a compound generally used as a dissolution controlling agent in a positive resist such as a polyhydroxy compound, a sulfonamide compound, a urea compound and the like. As long as the compound has a reduction rate of 30% or less, any compound can be preferably used. Specifically, methyl 3,4,5-trihydroxybenzoate,
4 '-[1- [4- [1- (4-hydroxyphenyl) -1-
Methylethyl] phenyl] ethylidene] bisphenol,
4,4 ', 4 "-ethylidene trisphenol, 4,6-
Bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4,4 ′, 4′-tetrakis [(1-methylethylidene) bis (1,4-cyclohexylidene)] phenol, or An o-quinonediazide compound in which at least one hydroxyl group of these compounds is a 1,2-naphthoquinonediazide-4-sulfonyl group or a 1,2-naphthoquinonediazide-5-sulfonyl group is included, but is not limited thereto.

The dissolution regulator is preferably blended in an amount of 1 to 100 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the polymer represented by the general formula (1). If the amount is less than 1 part by weight, sufficient effects cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance of the resin composition may be reduced. Therefore, it is preferable that the amount of the dissolution regulator is minimal.

Next, a method for evaluating the physical properties of the cured film (elongation at break, adhesion to the substrate, temperature at which the thermogravimetric loss occurs) will be described.

The measurement of the thermogravimetric reduction temperature in the present invention will be described. The measurement is performed using a thermogravimeter (TGA-50 (manufactured by Shimadzu Corporation)). The sample size is 5-20 mg,
More preferably, it is 10 to 20 mg, and the heating rate is 5 to 20 mg.
The temperature is measured at room temperature to a temperature of 350 ° C. or more at a rate of 10 ° C./minute, preferably 10 ° C./minute, under a nitrogen stream. From the measurement results,
The thermogravimetric reduction rate from 200 ° C. to 350 ° C. is calculated.

Samples for measuring the elongation at break are 1 to 30
A freestanding cured film of μm is prepared. More preferably 5
２０20 μm. The heat-resistant resin composition of the present invention is applied to a substrate. A silicon wafer is preferably used for the substrate. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating thickness can be adjusted depending on the coating method, the solid content concentration of the composition, and the viscosity, and the coating is usually applied so that the film thickness after drying is 1 to 150 μm. More preferably, it is 5 to 40 μm. Subsequently, the substrate coated with the heat-resistant resin composition is dried to obtain a heat-resistant resin composition film. Drying is preferably performed in the range of 50 ° C. to 180 ° C. using an oven, a hot plate, infrared rays, etc.
It is more preferable to carry out in the range of 0 ° C to 150 ° C. The drying time is preferably from one minute to several hours. Next, 200 ° C
To 500 ° C. This heat treatment is performed for 5 minutes to 5 hours while selecting a temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 ° 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 is peeled off from the substrate by immersing it in hydrofluoric acid for 1 to 15 minutes and air-dried. The obtained self-standing film is cut into a strip having a width of 0.5 to 3 cm and a length of 5 to 15 cm, and the elongation at break is measured using Tensilon RTM100 (manufactured by Orientec).

The adhesion to the substrate is determined according to JIS-K-5400.
Is evaluated according to the crosscut tape method. That is, a heat-resistant resin film is formed on a substrate in the same manner as the sample for measuring the elongation at break. Cuts that penetrate the obtained heat-resistant resin film and reach the substrate are cut in a grid pattern, an adhesive tape is peeled off the grid, and the adhesion of the coating film after peeling is visually observed. At this time, the heat-resistant resin film was
Exposure is performed at 0 ° C., 100% RH and 2 atm, and the relationship between the exposure time and the adhesiveness is determined. Before this processing, 50
After time processing, 200 hours processing, 400 hours processing 4
Each time, the same sample is subjected to an adhesion test. In the test results, the ratio of adhesion to the substrate without peeling is described in 10 stages.

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

The photosensitive resin composition of the present invention is applied on a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The thickness of the coating varies depending on the coating method, the solid concentration of the composition, the viscosity, and the like, but the coating is usually applied so that the thickness after drying is 0.1 to 150 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50 ° C to 150 ° C for 1 minute to several hours. If necessary, 80 ° C for 2 minutes followed by 120 ° C for 2 minutes, etc.
Drying can be done in stages or more.

Next, the film is exposed to actinic radiation through a mask having a desired pattern and exposed. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X rays.
In the present invention, the i-line (365n
m), h-line (405 nm) and g-line (436 nm) are preferably used.

The pattern of the heat-resistant resin is formed by removing the exposed portion using a developing solution after the exposure.

The resolution of the pattern at the time of development is improved,
When the allowable range of the developing conditions is increased, a step of performing a baking process before the development may be adopted. The temperature is preferably in the range of 50 to 180 ° C., particularly preferably 60 to 180 ° C.
A range of 150 ° C. is more preferred. The time is preferably from 10 seconds to several hours. If the ratio is out of this range, the reaction may not proceed or all the regions may not be dissolved.

In order to form a pattern of the heat-resistant resin composition, development processing is performed. When the heat-resistant resin composition is negative-type photosensitive, a relief pattern is obtained by removing an unexposed portion with a developer, and when the heat-resistant resin composition is positive-type photosensitive, removing an exposed portion with a developer.

A suitable developer can be selected according to the structure of the polymer. Ammonia, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, Triethylamine, diethylamine, methylamine, dimethylamine,
Aqueous solutions of compounds exhibiting alkalinity such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine can be preferably used.

Further, as a developing solution, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethyl Phosphortriamide alone or methanol,
Ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene,
Poor solvents for the composition such as ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, and ethyl acetate. And a mixture of these compounds alone or in combination of several types can also be preferably used.

In the development, the above developer is applied to the coating film surface as it is.
Alternatively, emit in the form of a mist, immerse in a developer,
Alternatively, it can be performed by a method such as applying ultrasonic waves while dipping.

Next, it is preferable to wash the relief pattern formed by development with a rinsing liquid. As the rinsing liquid, when an aqueous alkali solution is used as a developer, water can be preferably used. At this time, ethanol,
Rinsing treatment may be carried out by adding isopropyl alcohols, esters such as propylene glycol monomethyl ether acetate, or acids such as carbon dioxide, hydrochloric acid, and acetic acid to water.

When rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3
-Methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 ° C. to 500 ° C. This heat treatment is carried out 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. As an example, heat treatment is performed at 130 ° 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.

As described above, the heat-resistant resin composition of the present invention is preferably used for a semiconductor device as a surface protective film (passivation film, buffer coat film, α-ray shielding film), an interlayer insulating film, and the like.

[0073]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments. <Evaluation method> 1. Thermogravimetry of the photoacid generator and the dissolution regulator The measurement was performed using a thermogravimeter TGA-50 (manufactured by Shimadzu Corporation). A sample of 10 to 20 mg was placed in a platinum cell, and the temperature was measured from room temperature to 800 ° C. under a nitrogen stream at a rate of temperature increase of 10 ° C./min. Based on the measurement results, the thermogravimetric reduction rate from 200 ° C to 350 ° C was calculated.

2. A heat-resistant resin film was formed on a silicon wafer having a breaking elongation of 6 inches. The obtained heat-resistant resin film is coated with hydrofluoric acid (manufactured by Wako Pure Chemical Industries)
For 7 minutes to separate from the silicon wafer and air-dry to obtain a free-standing film. It was cut into a strip having a width of 1 cm and a length of about 9 cm, and the elongation at break was measured using Tensilon RTM100 (manufactured by Orientec).

3. Adhesion of Cure Film to Substrate The adhesion was carried out according to the cross-cut tape method of JIS-K-5400. A heat-resistant heat-resistant resin film was formed on a 6-inch silicon wafer. Using a cutter knife, 100 square grid-like cuts were made on the obtained heat-resistant resin film at an interval of 1 mm. The cut was made to penetrate the coating and reach the substrate. A cellophane adhesive tape (JIS-Z-1522) having a width of 18 mm was attached on the grid so that the length of the adhesive portion was about 50 mm, and the tape was completely adhered to the coating by rubbing with an eraser. One minute after the tape was applied, one end of the tape was grasped and momentarily peeled off perpendicular to the coating. As an evaluation result, a ratio of adhesion to the substrate without peeling was used. In other words, if no peeling has occurred, "1"
0 ", and" 0 "when all were peeled.

The adhesion test was performed using a pressure cooker (P
CT) Tester PC-242S (manufactured by Hirayama Industry Co., Ltd.)
At 120 ° C., 100% RH and 2 atm, to determine the relationship between the exposure time and the adhesiveness.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride 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 ethyl acetate and cooled to -15 ° C. Ethyl acetate 50
22.1 g of trimellitic anhydride chloride dissolved in g
(0.11 mol) was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 0 ° C. for 4 hours.

This solution was concentrated by a rotary evaporator, and was added to 1 liter of toluene to obtain an acid anhydride. This is shown below. The resulting material did not show a clear melting point up to 350 ° C.

[0079]

Embedded image Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of BAHF was added to acetone 10
0ml, propylene oxide 17.4g (0.3mo
1) and cooled to -15 ° C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at −15 ° C. for 4 hours, and then returned to room temperature. The solution was concentrated by a rotary evaporator, and the obtained solid was recrystallized from a solution of tetrahydrofuran and ethanol.

The solid collected by recrystallization was mixed with 100 parts of ethanol.
dissolved in 300 ml of tetrahydrofuran and 5 ml of
2 g of palladium-carbon was added and stirred vigorously.
Here, hydrogen was introduced by a balloon, and the reduction reaction was performed at room temperature. After about 4 hours, the reaction was terminated when it was confirmed that the balloon was no longer deflated. 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. This is shown below.
The obtained solid was used for the reaction as it was.

[0081]

Embedded image Synthesis Example 3 18.3 g of BAHF (0.05 mol) under a stream of dry nitrogen
l) was dissolved in 100 ml of N, N-dimethylacetamide and cooled to -5 ° C. To this, 26.4 g (0.3 mol) of glycidyl methyl ether was added, and 21.1 g (0.1 mol) of trimellitic anhydride chloride was dissolved in 50 g of acetone.
It was dropped so as not to exceed. After the completion of the dropwise addition, the temperature of the solution was raised to 10 ° C., and stirring was continued for 1 hour, and thereafter, the solution was stirred at 20 ° C. for 1 hour. Thereafter, 9.01 g (0.04 mol) of diaminodiphenyl ether and 1,3-bis (3-
2.5 g of aminopropyl) tetramethyldisiloxane
(0.01 mol) was added and stirring was continued at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a precipitate of polyhydroxyamidamic acid. The precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours. 10 g of this dried polyhydroxyamidamic acid (polyimide oxazole precursor) solid was added to GBL1
The resultant was dissolved in 8.6 g to obtain a varnish A as a photosensitive heat-resistant resin precursor.

Synthesis Example 4 18.3 g (0.05 mol) of BAHF was added to ethanol 1
Dissolved in 50 ml and cooled to 5 ° C. To this, 11.2 g (0.1 mol) of potassium-t-butoxide was gradually added. Further, 21.8 g of t-butyl dicarbonate
(0.1 mol) was added gradually and stirring was continued for 2 hours.
A diamine compound in which the hydroxyl group of AHF was protected with a t-butoxycarbonyl group was obtained. This solution was poured into 1 liter of water to obtain a precipitate. This precipitate was collected by filtration and dried in a vacuum dryer at 30 ° C. for 20 hours.

Under a stream of dry nitrogen, 27.5 g of BAHF
(0.075 mol) and diamine 1 in which the hydroxyl group of BAHF synthesized above was protected with a t-butoxycarbonyl group.
3.4 g (0.25 mol) was dissolved in 150 ml of N, N-dimethylacetamide and cooled to -5 ° C. Here, 52.8 g of glycidyl methyl ether (0.6 m
ol) and 20.3 g of isophthalic dichloride
A solution of (0.1 mol) dissolved in 100 g of acetone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C., and stirring was continued for 1 hour, and thereafter, the solution was stirred at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a precipitate of polyhydroxyamidamic acid. The precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours. 10 g of the dried solid of polyhydroxyamic acid (polybenzoxazole precursor) was dissolved in 18.6 g of GBL,
Varnish B as a photosensitive heat-resistant resin precursor was obtained.

Synthesis Example 5 20.0 g (100 mmol) of 4,4′-diaminodiphenyl ether was placed in a 1-liter four-necked flask under a stream of dry nitrogen.
l) was dissolved in 350 g of GBL. Here, Synthesis Example 1
71.4 g (100 mmol) of the acid anhydride synthesized in
BL was added together with 40 g, and reacted at 20 ° C. for 1 hour.
Then, the reaction was carried out at 50 ° C. for 4 hours. Further, 23.8 g of N, N-dimethylformamide dimethyl acetal (20
0 mmol) and stirred at 50 ° C. for 5 hours to obtain a partially esterified varnish C.

Synthesis Example 6 Under a dry nitrogen stream, 24.2 g (40 mmol) of the diamine compound synthesized in Synthesis Example 2 was placed in a 1-liter four-necked flask with N
Dissolved in 100 g of MP and 11.8 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (40 mmol)
l) was added and the mixture was stirred at 80 ° C for 3 hours. N, N-
8.8 g of dimethylformamide diethyl acetal (6
0 mmol) and stirred at 80 ° C. for 2 hours to obtain a partially esterified varnish D.

Examples 1 to 9, Comparative Examples 1 to 5 To 14.3 g of varnish A, as an orthonaphthoquinonediazidosulfonic acid ester, MG-300 (1 mol of methyl 3,4,5-trihydroxybenzoate was added in an amount of 1,2 g).
1 g of an ester obtained by reacting 3 mol of -naphthoquinone-2-diazide-5-sulfonyl chloride (manufactured by Toyo Gosei Kogyo KK) was dissolved. The obtained varnish was spin-coated on a 6-inch silicon wafer, and dried at 80 ° C. for 4 minutes to prepare a resin film having a predetermined thickness for each measurement. Inert oven (Nishiyama Seisakusho)
For 30 minutes at 200.degree. C. under nitrogen flow and 6 at 350.degree.
Heat treatment was performed for 0 minutes. Using the prepared cured film, elongation at break and adhesion to a substrate were measured (Example 1). MG
The procedure was performed in the same manner as in Example except that 4,4′-methylenebisphenol (p, p′-BPF) was used instead of −300 (Comparative Example 1). As an acid generator to be added, 200
MG- having a thermogravimetric reduction rate of 1% from 350 ° C to 350 ° C
When 300 is used, the elongation at break and the decrease in adhesion to the substrate are small, whereas the p, thermodynamic weight reduction rate is 100%.
When p'-BPF was used, the elongation at break and the decrease in adhesion to the substrate were large. Therefore, the thermal weight loss rate is 30%
When the following photoacid generators and dissolution regulators were used, a heat-resistant resin composition having a small decrease in film properties was obtained.

Examples 1 to 7 and Comparative Examples 2 to 5 are shown in Tables 1 and 2, respectively. Photosensitizer (MG-300, B
isP-RS-200, TekP-300, p, p'-
(BPF-200) was added in an amount of 20% by weight based on the weight of the solid content of the polymer, and the dissolution regulator (BisP-RS, p, p ') was added.
-BPF, BisZ) was added at 10% by weight with respect to the polymer solid content weight. In the table, BisP-R
S: 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-benzenediol, BisP-RS-2
00: 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 2 mol per 1 mol of BisP-RS
l, an ester obtained by reacting TekP-300:
1 mol of 4,4,4 ′, 4′-tetrakis [(1-methylethylidene) bis (1,4-cyclohexylidene)] phenol is mixed with 3 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. The ester obtained by the reaction, p, p'-BPF: 4,4'-methylenebisphenol, p, p'-BPF-200: p, p'-
It shows an ester obtained by reacting 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride with 1 mol of BPF, BisZ: 4,4′-cyclohexylidenebisphenol.

The adhesion to the substrate is indicated by the pressure cooker (PCT) processing time when the cured film starts to peel off from the substrate. In other words, the larger the value of this time, the better the adhesion to the substrate. The curing conditions in each example were as follows: 200 ° C. for 30 minutes under a nitrogen stream;
At 350 ° C. for 60 minutes.

Example 8 To 20 g of varnish D, 1.4 g of TekP-300 and Bis
0.7 g of P-RS was added and dissolved. Using a coater developer SKW-636 (manufactured by Dainippon Screen Co., Ltd.), the obtained varnish was coated on a 6-inch silicon wafer processed for a memory device so that the film thickness after prebaking was 10 μm. Spin coated. Then, drying was performed at 120 ° C. for 4 minutes using a vacuum adsorption type hot plate of SKW-636. Next, the coating
It was set on a line stepper NSR-1755-i7A (manufactured by Nikon) and exposed through a reticle from which a desired pattern was cut. The exposure amount was 1100 ms.

2.3 of tetramethylammonium hydroxide
Using an 8% aqueous solution, penetration development was performed twice for 60 seconds.
The development was performed using a SKW-636 developing device. Then, the substrate was rinsed with ultrapure water for 20 seconds and spin-dried with a spinner.
When the pattern was observed using an optical microscope, a desired pattern was favorably obtained. The obtained exposed and developed wafer was cured using an inert oven (manufactured by Nishiyama Seisakusho) under a nitrogen atmosphere. The curing conditions were 200 ° C. for 30 minutes and 350 ° C. for 1 hour.

As a result of a thermal cycle test, the memory device manufactured through the post-process was satisfactory without peeling off, and it was found that the heat-resistant resin of the present invention was preferably used for a semiconductor device.

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

According to the present invention, by specifying the heat resistance of the compound to be added to the heat-resistant resin composition, it is possible to easily provide a heat-resistant resin having a small decrease in film physical properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/037 501 G03F 7/037 501 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA10 AA20 AB16 BE00 BJ00 CB25 CB26 CB41 CB43 CB45 CC20 4J002 CM041 EQ036 GQ05 4J043 PA02 PA04 QB33 QB34 QB52 RA05 SA06 SA25 SA31 SA42 SA43 SA47 SA52 SA53 SA54 SA62 SA63 SA64 SA66 SA71 SA72 SA81 TA03 TA12 UA12 TA32 TA32 TA01 TA32 UA361 UA381 UB011 UB021 UB031 UB121 UB122 UB301 UB302 ZB50

Claims (3)

[Claims] 1. A heat-resistant resin composition comprising (a) a polymer having a structural unit represented by the general formula (1) as a main component and (b) a photoacid generator and / or a dissolution regulator. A heat-resistant resin composition wherein the photoacid generator and the dissolution regulator have a thermogravimetric reduction ratio from 200 ° C. to 350 ° C. of 30% or less. Embedded image (R ¹ is a divalent to octavalent organic group having at least 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having at least 2 or more carbon atoms, R ³ is hydrogen, alkali A metal ion, an ammonium ion or an organic group having 1 to 20 carbon atoms, m is an integer from 3 to 100,000, n is an integer from 0 to 2, and when n is 2, R ³ is the same or different. P and q are integers from 0 to 4, and p + q> 0.) 2. The heat resistant resin composition according to claim 1, wherein said photoacid generator is an o-quinonediazide compound. 3. A semiconductor device using the heat-resistant resin composition according to claim 1.