JP2001081191A - Heat-treating method for heat resistant resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-treating method for heat resistant resin precursor composition useful for field such as semiconductor or the like suitable for obtaining a pattern excellent in dimensional in-plane homogeneity from a polyimide precursor or polybenzoxazole precursor, by heat-treating in a specific hot plate. SOLUTION: A solution of a heat resistant resin precursor composition formed to a substrate shape is heat-treated with different 4 or more hot plates. The temperature the hot plates differ each other and the treatment is carried out from a hot plate in low temperature to hot plate in high temperature serially raising the temperature, and the solution preferably includes the heat sensitive heat resistant resin precursor composition mainly comprising a structural unit expressed by formula (R1 is a tri to octavalent >=2C organic group; R2 is a bi to hexavalent >=2C organic group; R3 is H, an alkali metal ion, ammonium ion or the like; n is 0-2; p and q are each 0-4; n+q>0; m is 3-100,000).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a heat-resistant resin precursor composition such as a polyimide precursor composition or a polybenzoxazole precursor composition formed on a substrate, which is heat-treated on a hot plate. The present invention relates to a method for improving the uniformity of heat treatment in a substrate by using a large number of hot plates.

[0002]

2. Description of the Related Art In the field of semiconductors, heat-resistant resin precursor compositions are used for forming interlayer insulating films, buffer coat films, alpha-ray shielding films, and the like. In order to use the heat-resistant resin precursor in these applications, it is necessary to perform fine processing. Usually, after forming a pattern, it is converted into a heat-resistant resin by heat treatment (curing).

Conventionally, pattern processing of a heat-resistant resin precursor is performed by applying a photoresist on the heat-resistant resin precursor film, forming a pattern, and etching the heat-resistant resin precursor film using the mask as a mask. Have been. However, this method has problems that the process is complicated and that the pattern accuracy is reduced by the side etching.

On the other hand, it is considered that such a problem can be overcome by imparting photosensitivity to the heat-resistant resin precursor itself.
The development of photosensitive heat-resistant resin precursors has been energetically carried out. As a result, photosensitive heat-resistant resin precursors are now widely used.

In a conventional semiconductor process, first, a passivation film is patterned by resist patterning and dry etching using the resist as a mask, the resist is peeled off, and then a heat-resistant resin precursor patterning is performed. The process of performing cure has been adopted. However, since the photosensitive heat-resistant resin precursor has a pattern accuracy that can be applied to the pattern formation of the passivation film, first, the pattern processing and curing of the photosensitive heat-resistant resin precursor are performed on the passivation film before pattern formation, Next, a method of performing dry etching of the underlying passivation film using the pattern of the heat-resistant resin as a mask is adopted (batch opening method). According to this method, the process required for forming the pattern of the passivation film can be omitted, leading to cost reduction.

When the heat-resistant resin precursor is finely processed, regardless of photosensitivity, a heat-resistant resin precursor composition is first supplied onto a substrate, and usually adjusted to a desired thickness by a spin coating method. A method of volatilizing a solvent by heat treatment has been adopted. This heat treatment is called pre-bake,
Usually, a hot plate is used.

[0007]

The prebake of the heat-resistant resin precursor is different from that of the resist in the following two points.
Care must be taken when handling. (1) A high-boiling solvent such as N-methylpyrrolidone is usually used as a solvent for the heat-resistant resin precursor composition.
It is difficult to evaporate the solvent. (2) The film thickness after pre-baking is about 5 to 20 μm, which is much larger than that of the resist, which is usually about 1 μm. (3) A considerable amount of solvent remains after pre-baking, and this remaining amount has a great influence on the development characteristics and, consequently, the dimensions of the obtained pattern.

On the other hand, the wafer size tends to increase, and currently 8 inches is the mainstream. Therefore, in order to obtain a uniform pattern on the wafer surface, it is important that the pre-bake is performed uniformly on the wafer surface.

Usually, when applying and pre-baking a heat-resistant resin precursor composition such as polyimide, an apparatus similar to a resist is used. However, when the pre-baking of the heat-resistant resin composition was performed using a hot plate of a typical 8-inch wafer apparatus, the evaporation rate of the solvent varied depending on the location in the substrate surface, and the portion where the residual solvent was extremely large It turned out that extremely few parts were mixed. In many cases, the non-uniformity of the residual solvent in the surface of the substrate varies depending on the hot plate used. If there is unevenness in the pre-bake uniformity in the substrate, the developing speed is greatly affected, and the pattern after development also becomes uneven. That is not desirable.

[0010]

According to the present invention, a heat-resistant resin precursor composition formed on a substrate is prepared by using different 4
A heat treatment method for a heat-resistant resin precursor composition, wherein heat treatment is performed on at least one hot plate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The heat resistance in the present invention means that it can withstand a high temperature of 300 ° C. or more, and means, for example, that a 5% weight loss temperature by thermogravimetry is 400 ° C. or more.

The heat-resistant resin precursor composition of the present invention includes polyamic acid as a polyimide precursor, polyhydroxyamide as a polybenzoxazole precursor, polythiohydroxyamide as a polybenzothiazole precursor, and polybenzimidazole. Examples thereof include, but are not limited to, a precursor that can be a polymer having a polyaminoamide imide ring, an oxazole ring, and other cyclic structures.

The heat treatment of the present invention corresponds to what is generally called pre-bake, and refers to a bake treatment performed before exposure.
It is preferable to carry out in a temperature range of 00 ° C. More preferably, the temperature range is 60C to 150C. And
It is essential to perform pre-bake with four or more different types of hot plates. By using four or more hot plates, the bake unevenness in each hot plate is offset, and the uniformity of the resulting pre-baked film is unprecedentedly superior. Further, the temperature interval is 5 ° C to 50 ° C.
It is preferable to heat-treat at least three types of different temperatures in the range of 60 ° C to 150 ° C. It is important to set the temperature of the hot plate so that the temperature is low in the early stage of baking and the higher the temperature in later processing, in order to perform the evaporation of the solvent etc. gently. preferable. The temperature intervals of the hot plate may be the same or different. The heat treatment time is preferably several seconds to several hours for each hot plate. More preferably, it is performed in 1 minute to 30 minutes.

The heat treatment method of the present invention can be used for any of the polymers corresponding to the general formula (1), and the effect can be obtained. Among them, the following polymers are preferable.

[0015]

Embedded image

(R ⁷ is a tetravalent organic group having at least 2 or more carbon atoms, R ⁸ is a divalent organic group having at least 2 or more carbon atoms, R ⁹ and R ¹⁰ are hydrogen, alkali metal Represents an ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms. R ⁹ and R ¹⁰ may be the same or different.)

[0017]

Embedded image

(R ¹¹ is a trivalent to octavalent organic group having at least 2 or more carbon atoms, R ¹² is a divalent to hexavalent organic group having at least 2 or more carbon atoms, and R ¹³ is Represents hydrogen or an organic group having 1 to 10 carbon atoms.
Is an integer from 3 to 100000, t is 1 or 2,
r and s each represent an integer from 0 to 4, and r + s> 0. )

[0019]

Embedded image

(R ¹⁴ represents a divalent organic group having at least 2 or more carbon atoms, and R ¹⁵ represents a tetravalent organic group having at least 2 or more carbon atoms.
Indicates an integer up to 00. Examples of the polymer having a structural unit represented by the general formula (1) in the present invention include those which can be converted into a polymer having an imide ring, a benzoxazole ring, or another cyclic structure by heating or an appropriate catalyst. .

In the above formula (3), R ⁷ is a tetravalent organic group having at least two or more carbon atoms.
From the heat resistance of the polymer in the present invention, R ⁷ contains an aromatic ring or an aromatic heterocyclic ring and has 4 to 6 carbon atoms.
Valent groups are preferred. Preferred specific examples of R ⁷ 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'
-Residues such as, but not limited to, diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid, and cyclopentanetetracarboxylic acid. Further, R7 may be composed of one of these, or may be a copolymer composed of two or more.

In the general formula (3), R ⁸ is a divalent organic group having at least two or more carbon atoms.
In view of the heat resistance of the polymer in the present invention, R ⁸ contains an aromatic ring or an aromatic heterocyclic ring, and has 6 to 30 carbon atoms.
Are preferred. Preferred specific examples of R ⁸ include paraphenylenediamine, metaphenylenediamine, methylparaphenylenediamine, methylmetaphenylenediamine, dimethylparaphenylenediamine, dimethylmetaphenylenediamine, trimethylparaphenylenediamine, trimethylmetaphenylenediamine, and tetramethyldiphenylenediamine. Methyl paraphenylene diamine, tetramethyl metaphenylene diamine, trifluoromethyl paraphenylene diamine, trifluoromethyl metaphenylene diamine, bis (trifluoro) methyl paraphenylene diamine, bis (trifluoro) methyl metaphenylene diamine, methoxy paraphenylene diamine, Methoxymetaphenylenediamine, trifluoromethoxyparaphenylenediamine, trifluoromethoxymetaphe Diamine, fluoro para-phenylenediamine, fluoro-phenylenediamine, chloro-para-phenylenediamine,
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 (aminodimethylphenyl) ) Propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexafluoropropane, Bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) hexafluoropropane , Diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenylether, Bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethylphenyl) ether, (Amino dimethylphenyl) ether, bis (amino-diethyl phenyl) ether, dimethyl benzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine,
Bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane, bis (aminophenoxyphenyl) sulfone Examples include, but are not limited to, the residue of a compound and the residue of a water-added compound thereof.

R ⁸ may be composed of one or more of these, and may be a copolymer composed of two or more.

In the above general formula (3), R ⁹ and R ^9
10 is hydrogen, alkali metal ion, ammonium ion,
Alternatively, it represents an organic group having 1 to 30 carbon atoms. Carbon number 1-3
The organic group of 0 is preferably an aliphatic organic group, and examples of the organic group include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. . Preferred specific examples include a methyl group, an ethyl group, an isopropyl group,
Butyl group, t-butyl group, ethyl methacrylate group, ethyl acrylate group, propyl methacrylate group, propyl acrylate group, ethyl methacrylamide group, propyl methacrylamide group, ethyl acrylamide group, propyl acrylamide group and the like. It is not limited to these. In addition, R ⁹ and R ¹⁰ 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 ⁹ and R ¹⁰ may be a single kind or a mixture of two or more kinds. Further, R ⁹ and R ¹⁰ may be the same or different.

In order to improve the adhesiveness of the polymer of the present invention, it is possible to copolymerize an aliphatic group having a siloxane bond as R ⁸ as long as the heat resistance is not reduced. Preferred specific examples include, but are not limited to, bis (3-aminopropyl) tetramethyldisiloxane.

In the general formula (4), the residue constituting R ¹¹ represents a structural component of an acid, and this acid component contains an aromatic ring and has 1 to 4 hydroxyl groups. 2-6 carbon atoms
A trivalent to octavalent organic group of 0 is preferred. When R ¹¹ does not contain a hydroxyl group, the R ¹² 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.

[0028]

Embedded image

Further, as a residue containing R ^11, tetracarboxylic acid having no hydroxyl group, tricarboxylic acid, may also be used dicarboxylic acid. Examples of these include:
Aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and diester compounds in which two carboxyl groups are converted to methyl groups or ethyl groups, butanetetra Aliphatic tetracarboxylic acids such as carboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are converted to methyl or ethyl groups, and aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, and naphthalene tricarboxylic acid Can be mentioned.

In the general formula (4), the residue constituting R ¹² represents a structural component of a diamine, and represents a divalent to hexavalent organic group having at least two or more carbon atoms.
Among these, a preferable example of R ¹² is one having an aromatic group and having 1 to 4 hydroxyl groups from the viewpoint of heat resistance of the obtained polymer. When R ¹² does not contain a hydroxyl group, the R ¹¹ 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 following structures. Can be

[0032]

Embedded image

Further, a diamine having no hydroxyl group can be used as the residue containing R ¹² in the general formula (4).
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. They are,
It is preferable to use not more than 40 mol% of the diamine component. 40
If the copolymerization is at least mol%, the heat resistance of the obtained polymer will be reduced.

R ^{13 in the} general formula (4) represents hydrogen or an organic group having 1 to 10 carbon atoms. R ¹³ has 20 carbon atoms
If it exceeds, it will not be dissolved in an alkaline aqueous solution. R ¹³ is preferably an organic group in view of the stability of the obtained photosensitive resin solution, but is preferably hydrogen in view of the solubility of the aqueous alkali solution. That is, it is not preferable that all of R ¹³ are hydrogen or all are organic groups. By controlling the amount of hydrogen and the organic group of R ^13, the dissolution rate in an aqueous alkali solution changes, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. m is an integer from 3 to 100000, t is 1 or 2,
r and s are integers from 0 to 4, and r + s> 0. When r is 5 or more, the properties of the obtained heat-resistant resin film deteriorate.

In the general formula (5), R ¹⁴ represents a divalent organic group having at least two carbon atoms. From the heat resistance of the polymer in the present invention, R ¹⁴ 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 ¹⁴ 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. Further, R ¹⁴ may be composed of one of these, or may be a copolymer composed of two or more.

In the general formula (5), R ¹⁵ represents a tetravalent organic group having at least two carbon atoms. In view of the heat resistance of the polymer in the present invention, R ¹⁵ 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 ¹⁵ 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. In addition, R ¹⁵ 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 (5) 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.

[0038] In order to impart photosensitivity to the polyimide precursor composition of the general formula (3) R ⁹ and R ¹⁰ components methacrylic acid ethyl, acrylic acid ethyl, propyl methacrylate groups, acrylate propyl group, A compound represented by the general formula (2) using an ethyl methacrylamide group, a propyl methacrylamide group, an ethyl acrylamide group, a propyl acrylamide group, and / or newly containing an ethylenically unsaturated double bond and an amino group It can also be contained.

In the above formula (2), R ⁴ , R ⁵ and R ⁶ represent an organic group having 1 to 30 carbon atoms. The organic group is preferably an aliphatic organic group. Examples of the organic group include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. Further, in order to improve the photosensitive performance, R ⁴ ,
Preferably, at least one of R ⁵ and R ⁶ contains an ethylenically unsaturated double bond.

Preferred specific examples of the general formula (2) include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminopropyl Acrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminoethyl acrylamide, diethylaminoethyl acrylamide, and the like. Not.

The compound represented by the general formula (2) may be a single compound or a mixture of two or more compounds.

The polymer in the present invention has the general formula (1)
Or a copolymer or a blend with other structural units. At that time, it is preferable that the content of the structural unit represented by the general formula (1) is 80% or more. The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not significantly impair the heat resistance of the polymer obtained by the final heat treatment.

The polyimide precursor represented by the general formula (1), particularly the general formula (3) is synthesized by a known method.
That is, when R ⁹ and R ¹⁰ are hydrogen, a tetracarboxylic dianhydride and a diamine are selectively combined,
These are polar solvents mainly containing N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide and the like, and γ-butyrolactone as a main component. It is synthesized by a known method such as a reaction in a solvent.

When R ⁹ and R ¹⁰ are alkyl groups, after reacting a tetracarboxylic dianhydride with an alcohol compound, an acid chloride is synthesized using thionyl chloride or the like, and then an appropriate diamine is selected. , Or selectively combined with a diamine using a suitable dehydrating agent such as dicyclohexylcarbodiimide, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
It is synthesized by a known method such as a reaction in a polar solvent containing N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide or the like as a main component or a solvent containing γ-butyrolactone as a main component.

Further, general formula (1), particularly general formula (3)
The polymer having a structural unit represented by the following formula as a main component can be a photoinitiator or a photosensitizer, or a combination of a photoinitiator and a photosensitizer.

The photoinitiator suitable for the present invention is represented by aromatic amines such as N-phenyldiethanolamine and N-phenylglycine, aromatic ketones such as Michler's ketone, and 3-phenyl-5-isoxazolone. Cyclic oxime compound, 1-phenylpropanedione-
Linear oxime compounds represented by 2- (o-ethoxycarbonyl) oxime, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, dibenzyl ketone and fluorenone; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and the like. Examples include, but are not limited to, thioxanthone derivatives.

Examples of the sensitizer suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone; aminocoumarins such as 7-diethylaminobenzoylcoumarin; and 3,3'-carbonylbis (diethylaminocoumarin); In some cases, aromatic ketones such as benzanthrone and phenanthrenequinone can be preferably used as long as they are generally used as a photocurable resin, or other materials used as a charge transfer agent for electrophotography.

The photoinitiator and the sensitizer are used in an amount of 0.01 to 30% by weight, more preferably 0.1 to 30% by weight based on the precursor composition of the present invention.
It is preferable to add 〜20% by weight. If the ratio is outside this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered. These photoinitiators and sensitizers can be used alone or in combination of two or more.

Further, general formula (1), particularly general formula (4),
The polymer represented by the general formula (5) may contain a quinonediazide compound. As the quinonediazide compound, a compound in which sulfonyl acid of naphthoquinonediazide is bonded to a phenolic hydroxyl group by an ester is preferable. As such compounds, preferably used are compounds such as naphthoquinone diazide sulfonic acid ester of tetrahydroxybenzophenone, naphthoquinone diazide sulfonic acid ester of bisphenol A, naphthoquinone diazide sulfonic acid ester of gallic acid, and naphthoquinone diazide sulfonic acid ester of naphthol. But other esters of phenols,
Alternatively, naphthoquinonediazidesulfonic acid esters such as hydroxyphthalimide and hydroxybenzotriazole, naphthoquindiazidesulfonic acid esters with oximes such as benzaldoxime, and the like can be used. Naphthoquindiazide sulfonic acid has 4
There are a compound having a sulfonyl group bonded at the 5-position and a compound having a sulfonyl group bonded at the 5-position. In the present invention, either compound can be used.

When the molecular weight of the naphthoquinonediazide compound exceeds 1200, the naphthoquinonediazide compound does not thermally decompose sufficiently in the subsequent heat treatment, so that the resulting film has reduced heat resistance, reduced mechanical properties, and reduced adhesiveness. Such problems may occur. From such a viewpoint, the molecular weight of naphthoquinonediazide is preferably from 300 to 1200. More preferably, from 350 to 1
000.

In order to improve the photosensitive performance of the composition of the present invention,
A photoreactive monomer can be used as appropriate.

Examples of the photoreactive monomer include 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and propylene. Glycol dimethacrylate,
Examples include, but are not limited to, methylenebismethacrylamide, methylenebisacrylamide, and the like.

The photoreactive monomer is used in an amount of 1 to 1 with respect to the polymer.
It is preferable to add in the range of 30% by weight. If the ratio is outside this range, care must be taken because the photosensitivity is reduced and the mechanical properties of the polyimide polymer are reduced. These photoreactive monomers can be used alone or in combination of two or more.

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

In order to improve the adhesion between the coating of the composition of the present invention or the heat-resistant resin coating after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion assistant include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organic silicon compounds such as methacryloxypropyltrimethoxysilane, or aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate) or titanium chelate compounds such as titanium bis (acetylacetonate) are preferable. Used.

If necessary, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone and methyl may be used to improve the wettability between the composition of the present invention and a substrate. Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powder of polyimide can also be added.

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.

Next, a heat treatment method for a heat-resistant resin precursor using the method of the present invention will be described.

The heat-resistant resin precursor of the present invention is applied to a substrate. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating film thickness, the coating method, the solid content concentration of the composition,
Although it can be adjusted by the viscosity, it is usually applied so that the film thickness after drying becomes 0.1 to 150 μm. Next, the substrate coated with the heat-resistant resin precursor is dried to obtain a heat-resistant resin precursor film. For drying, it is preferable to use a hot plate. The drying conditions are preferably in the above range.

Next, exposure is performed using a mask having a desired pattern. The exposure amount is 50 to 1000 mJ /
A range of cm ² is preferred. A particularly preferred range is 100 to
It is 600 mJ / cm ² .

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.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. A suitable developer can be selected according to the structure of the polymer, but ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine An aqueous solution of an alkaline compound such as methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine can be preferably used.

In the polymer of the present invention, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl Acetamide, dimethyl sulfoxide, hexamethylphosphortriamide, etc. alone or in methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl- A mixed solution of the composition with a poor solvent such as 3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, and ethyl acetate can also be preferably used.

Further, with respect to the polymers represented by the general formulas (4) and (5), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl Polar solvents such as acetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; cyclopentanone, cyclohexanone; and isobutyl ketone methyl isobutyl ketone May be added alone or in combination of several kinds.

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 a rinsing liquid, when rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, which has good miscibility with a developing solution, Ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

In the case of the polymers represented by the general formulas (4) and (5), it is desirable to rinse with water. Also,
Rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

The polymer of the relief pattern obtained by the above-described treatment is a precursor of a polyimide-based polymer having heat resistance, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment is preferably performed at 135 to 500 ° C.,
More preferably, it is performed at 450 ° C. The heat treatment is usually performed stepwise or continuously while increasing the temperature.

[0070]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments. Synthesis Example 1 19.0 g (0.095 mol) of 4,4'-diaminodiphenyl ether and 1.2 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were placed in a 1-liter four-necked flask under a stream of dry nitrogen. (0.005 mol) was dissolved in 100 g of N-methyl-2-pyrrolidone. To this, 10.8 g (0.05 mol) of pyromellitic anhydride and 15.0 g (0.047 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride were added, and the mixture was added at room temperature for 6 hours. The reaction was performed to obtain a polyamic acid. Where N, N
-26 g of dimethylaminoethyl methacrylamide (0.
18 mol), 2.5 g of N-phenylglycine, 5 g of ethylene glycol dimethacrylate and 0.2 g of 3,3′-carbonylbis (7-diethylaminocoumarin) to obtain varnish A as a photosensitive heat-resistant resin precursor. .

Synthesis Example 2 N, N-diethylaminoethyl methacrylate 33 g (0.18 mol) was added to the polyamic acid obtained in Synthesis Example 1.
Diethylene glycol dimethacrylate (10 g), N-phenyldiethanolamine (1.25 g) and N-phenylglycine (1.25 g) were added to obtain a varnish B as a photosensitive heat-resistant resin precursor.

Synthesis Example 3 In a dry air stream, 10.9 g (0.05 mol) of pyromellitic anhydride was dissolved in 100 g of γ-butyrolactone in a 500 ml four-necked flask. To this, 13 g (0.1 mol) of 2-hydroxyethyl methacrylate and 7 g of pyridine were added and reacted at 50 ° C. for 1 hour. The solution was cooled on ice and dicyclohexylcarbodiimide 21 g
(0.1 mol) in 25 g of γ-butyrolactone was added dropwise over 15 minutes. Further, 10 g (0.05 mol) of 4,4′-diaminodiphenyl ether was added to γ-
A solution dissolved in 25 g of butyrolactone was added dropwise over 10 minutes. This solution was reacted under ice cooling for 3 hours, and then reacted at 50 ° C. for 1 hour. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 3 liters of water to produce a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and then dried at 50 ° C. in a vacuum drier.
Dry for 24 hours. This polyamic acid ester powder 1
5 g, mercaptobenzimidazole 0.75 g, trimethylolpropane triacrylate 1 g, ethylene glycol dimethacrylate 2 g, pt-butylcatechol 0.5 g, Michler's ketone 0.5 g, 3-methacryloxypropyldimethoxysilane, 1-phenyl-1 ,
Varnish C, a photosensitive heat-resistant resin precursor to which 2-propanedione-2- (o-benzoyl) oxime was added, was obtained.

Synthesis Example 4 Instead of 4,4′-diaminodiphenyl ether of Synthesis Example 1, 3,5-diaminobenzoic acid-2-hydroxyethyl methacrylate (BEM-S manufactured by Kawasaki Kaken)
Synthesis Example 1 using 25.5 g (0.095 mol)
3,3 ', 4,4'- instead of pyromellitic anhydride
29.0 g of biphenyltetracarboxylic dianhydride (0.
099 mol) to obtain a polyamic acid. To this solution, 1.25 g of N-phenyldiethanolamine, 1.25 g of N-phenylglycine, and 10 g of ethylene glycol dimethacrylate were added to obtain Varnish D, a photosensitive heat-resistant resin precursor.

Synthesis Example 5 13 g of glycidyl methacrylate was added to the polyamic acid obtained in Synthesis Example 1 and reacted at room temperature for 12 hours. 2.5 g of N-phenylglycine, 5 g of ethylene glycol dimethacrylate and 0.2 g of 3,3′-carbonylbis (7-diethylaminocoumarin) were added to this varnish,
Varnish E, a photosensitive heat-resistant resin precursor, was obtained.

Synthesis Example 6 Instead of 4,4′-diaminodiphenyl ether of Synthesis Example 1, 30.4 g (0.095 mol) of 2,2-bis (trifluoromethyl) benzidine was used, and N-methyl-2
-Dissolved using 150 g of pyrrolidone. Except for the above, it was prepared in the same manner as in Synthesis Example 1. Where 3,3 ', 4
29.4 g of 4'-biphenyltetracarboxylic dianhydride
(0.1 mol), and the mixture was reacted at room temperature for 6 hours to obtain a polyimide precursor. 30 g of nifedipine and 50 g of N-methyl-2-pyrrolidone were added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a photosensitive heat-resistant resin precursor varnish F.

Synthesis Example 7 2,2-bis (3-amino-4-hydroxybenzene) hexafluoropropane (BAHF) under a stream of dry nitrogen
18.3 g (0.05 mol) was dissolved in 100 ml of N, N-dimethylacetamide and cooled to -5 ° C. Here, 26.4 g (0.3 mol) of glycidyl methyl ether was added, and 21.1 g of trimellitic anhydride chloride was added.
(0.1 mol) dissolved in 50 g of acetone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. 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 2.5 g (0.01 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added, and the mixture was stirred at 20 ° C. for 6 hours. Continued. 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 drier at 60 ° C. for 2 hours.
Dried for 0 hours. This dried polyhydroxyamidamic acid (polyimide oxazole precursor) solid 1
0 g and 2 g of 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) as orthonaphthoquinonediazidesulfonic acid ester were converted to γ-
The resin was dissolved in 20 g of butyrolactone to obtain a varnish G as a photosensitive heat-resistant resin precursor.

Synthesis Example 8 Under a dry nitrogen stream, 36.6 g (0.1 mol) of BAHF was dissolved in 150 ml of N, N-dimethylacetamide and cooled to -5 ° C. 52.8 g (0.6 mol) of glycidyl methyl ether was added thereto, and 20.3 g (0.1 mol) of isophthalic dichloride was added to acetone 100
g 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 polyhydroxyamic 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 polyhydroxyamide (polybenzoxazole precursor) solid and 2 g of orthonaphthoquinonediazidosulfonic acid ester used in Synthesis Example 7 were dissolved in 20 g of γ-butyrolactone, and Varnish H, a photosensitive heat-resistant resin precursor, was dissolved. I got

Synthesis Example 9 2-amino-4-nitrophenol 30.8 g (0.2
Mol) in acetone 200 ml, propylene oxide 60
g (0.68 mol) and cooled to -15 ° C.
A solution of 22.4 g (0.11 mol) of isophthalic chloride dissolved in 200 ml of acetone was gradually added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

30 g of the dried precipitate and 5% palladium-
3 g of carbon were added to a 500 ml autoclave together with 400 ml of methyl cellosolve. Here, hydrogen is applied at a pressure of 8
The pressure was increased to kgf / cm ² , the temperature was increased to 60 ° C., and the stirring was continued until no more hydrogen was absorbed. After stirring for 10 minutes after the hydrogen was no longer absorbed, the heating was stopped, and when the temperature became 30 ° C. or lower, the pressure in the vessel was released to stop the reaction. After completion of the reaction, the solution was filtered, and the filtrate was poured into 1 liter of water to obtain a precipitate of the desired hydroxy group-containing diamine compound. 50 ℃
For 20 hours.

In a stream of dry nitrogen, 17.0 g (0.045 mol) of the above hydroxyl group-containing diamine compound was added.
1.24 g (0.005 mol) of -bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 50 g of NMP. Here, 12.4 g (0.04 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic anhydride
Was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. 0.98 g (0.01 mol) of maleic anhydride was added thereto,
After stirring for an hour, a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, at 50 ° C 3
Stirred for hours.

To 30 g of the obtained solution was added 2 g of orthonaphthoquinonediazide sulfonic acid ester used in Synthesis Example 7 to γ.
-Butyrolactone was dissolved in 20 g to obtain a varnish I of a photosensitive heat-resistant resin precursor.

Example 1 and Comparative Example 1 Varnish A was coated on an 8-inch silicon wafer by using a coater developer Mark-7 (manufactured by Tokyo Electron Limited) so that the film thickness after prebaking would be 10 μm. And spin coated. Then, using four hot plates of the same apparatus, the treatment was performed in this order at 60 ° C. for 1 minute, at 80 ° C. for 1 minute, at 90 ° C. for 1 minute, and at 100 ° C. for 1 minute (Example 1). For comparison, pre-baking was performed in the same order using two hot plates at 70 ° C. for 2 minutes and at 95 ° C. for 2 minutes (Comparative Example 1). Next, apply the coating
Using a line stepper NSR-1755i7 (manufactured by Nikon), the exposure amount is 400 m through a reticle whose pattern has been cut.
G-line exposure was performed at J / cm ² .

After baking at 80 ° C. for 1 minute on a hot plate, penetration development was performed using a mixed solvent of N-methyl-2-pyrrolidone (70 parts) and xylene (30 parts). For development, a Mark-7 developing device was used. Then
Rinse with isopropyl alcohol for 20 seconds and spin dry with a spinner. The obtained exposed and developed wafer was cured using an inert gas oven INH-21CD (manufactured by Koyo Lindberg). Cure condition is 14
The test was performed at 0 ° C. for 30 minutes and at 350 ° C. for 60 minutes. Table 1 summarizes the results of measuring the dimensions (unit: μm) of the obtained pattern at five points (A, B, C, D, and E in FIG. 1) in the wafer. It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when two hot plates were used.

Example 2, Comparative Example 2 Varnish B was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 70 ° C, 1 minute at 80 ° C, 1 minute at 90 ° C
For 1 minute at 100 ° C. (Example 2)
Except for 4 minutes at 90 ° C. for comparison (Comparative Example 2)
Exposure, development, and curing were performed in the same manner as in Example 1. Table 1 summarizes the results of measuring the dimensions of the obtained pattern. It was found that the variation in pattern dimensions was better when prebaking was performed using five hot plates than when one hot plate was used.

Example 3, Comparative Example 3 Varnish C was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 70 ° C, 1 minute at 80 ° C, 1 minute at 90 ° C
, And processed in this order (Example 3).
C. for 2 minutes (Comparative Example 3). Exposure, development and curing were carried out in the same manner as in Example 1 except that cyclopentanone was used as a developing solution and propylene glycol monomethyl ether acetate was used as a rinsing solution. Table 1 summarizes the results of measuring the dimensions of the obtained pattern. Variation in pattern dimensions It was found that performing pre-bake using four hot plates was superior to that using one hot plate.

Example 4, Comparative Example 4 Varnish D was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 70 ° C, 1 minute at 80 ° C, 1 minute at 90 ° C
And processed in this order (Example 4) and 90 for comparison.
C. for 2 minutes (Comparative Example 4).
Except for using (Toray), exposure, development,
Cure. Table 1 summarizes the results of measuring the dimensions of the obtained pattern. It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

Example 5, Comparative Example 5 Varnish E was spin-coated as in Example 1, and
1 minute at 0 ° C, 1 minute at 70 ° C, 1 minute at 80 ° C, 1 minute at 90 ° C
And processed in this order (Example 5), and 90 for comparison.
Exposure, development, and curing were performed in the same manner as in Example 1 except that the operation was performed at 2 ° C. for 2 minutes (Comparative Example 5). Table 1 summarizes the results of measuring the dimensions of the obtained pattern. It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

Example 6, Comparative Example 6 Varnish F was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 70 ° C, 1 minute at 80 ° C, 1 minute at 90 ° C
And processed in this order (Example 6) and 90 for comparison.
C. for 2 minutes (Comparative Example 6).
Exposure and development were carried out in the same manner as in Example 1 except that a mixture consisting of 25 parts of ethanol, 70 parts of water, and 5 parts of tetramethylammonium hydroxide was used as a developing solution, and water was used as a rinsing solution. , Cured. Table 1 summarizes the results of measuring the dimensions of the obtained pattern. It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

Example 7, Comparative Example 7 Varnish G was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 90 ° C, 1 minute at 100 ° C, 110 ° C
For one minute in this order (Example 7), and for 2 minutes at 110 ° C. for comparison (Comparative Example 7), baking before development was omitted, and tetramethylammonium hydroxide was used as a developer. Exposure, development and curing were carried out in the same manner as in Example 1 except that a 38% aqueous solution was used and water was used as a rinsing liquid. Table 1 summarizes the results of measuring the dimensions of the obtained pattern.
It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

Example 8, Comparative Example 8 Varnish H was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 90 ° C, 1 minute at 100 ° C, 110 ° C
For 1 minute in this order (Example 8), and for 2 minutes at 110 ° C. for comparison (Comparative Example 8), baking before development was omitted, and tetramethylammonium hydroxide was used as a developer. Exposure, development and curing were carried out in the same manner as in Example 1 except that a 38% aqueous solution was used and water was used as a rinsing liquid. Table 1 summarizes the results of measuring the dimensions of the obtained pattern.
It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

Example 9, Comparative Example 9 Varnish I was spin-coated in the same manner as in Example 1, and
1 minute at 0 ° C, 1 minute at 90 ° C, 1 minute at 100 ° C, 110 ° C
For 1 minute in this order (Example 9), and for 2 minutes at 110 ° C. for comparison (Comparative Example 9), baking before development was omitted, and tetramethyl ammonium hydroxide was used as a developer. Exposure, development and curing were carried out in the same manner as in Example 1 except that a 38% aqueous solution was used and water was used as a rinsing liquid. Table 1 summarizes the results of measuring the dimensions of the obtained pattern.
It was found that the variation in pattern size was better when prebaking was performed using four hot plates than when one hot plate was used.

[0092]

[Table 1]

[0093]

According to the present invention, it is possible to provide a method of heat-treating a heat-resistant resin composition suitable for obtaining a pattern having excellent in-plane uniformity in dimensions from a polyimide precursor or a polybenzoxazole precursor. I can do it.

[0094]

[Brief description of reference numerals]

 1 Orientation flat

[Brief description of the drawings]

FIG. 1 is a measurement position of a pattern dimension in a wafer.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D075 BB21Z CA18 DC22 EB39 EB47 4J043 PA02 PA04 PA19 PC135 PC145 PC146 QB15 QB23 QB25 QB26 QB31 QB34 RA35 RA52 RA57 SA42 SA43 SA44 SA52 SA53 SA54 SA62 SA63 SA71 SA72 SB01 TA02 SB03 TA03 TA14 TA26 TA31 TA32. YB29 YB31 YB32 ZB22

Claims (6)

[Claims] 1. A heat treatment method for a heat-resistant resin precursor composition, comprising heating a heat-resistant resin precursor composition solution formed on a substrate with four or more different hot plates. 2. The heat treatment method for a heat-resistant resin precursor composition according to claim 1, wherein the temperatures of the hot plates are different from each other, and the hot plate is sequentially treated from a low-temperature hot plate to a high-temperature hot plate. 3. The heat-resistant resin precursor composition solution according to claim 1, comprising a photosensitive heat-resistant resin precursor composition having a structural unit represented by the general formula (1) as a main component. A heat treatment method for a heat-resistant resin precursor composition. 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, R ³ is hydrogen, an alkali metal Ion, ammonium ion, or carbon number 1-3
Represents an organic group of 0. n represents an integer from 0 to 2;
When R is 2, R ³ may be the same or different. p,
q represents an integer from 0 to 4, and n + q> 0. m
Represents an integer of 3 to 100,000. ) 4. A photosensitive heat-resistant resin precursor composition comprising a structural unit represented by the general formula (1) as a main component and comprising an ethylenically unsaturated double bond and an amino group. A heat treatment method for a heat-resistant resin precursor composition, comprising a compound represented by the formula (2). Embedded image (R ⁴ , R ⁵ , and R ⁶ are organic groups having 1 to 30 carbon atoms, at least one of which contains an ethylenically unsaturated double bond.) 5. The method for heat-treating a heat-resistant resin precursor composition according to claim 4, wherein the photosensitive heat-resistant resin precursor composition contains a photoinitiator and / or a photosensitizer. 6. A photosensitive heat-resistant resin precursor composition comprising a structural unit represented by the general formula (1) according to claim 3 as a main component, comprising a quinonediazide compound. A heat treatment method for a heat-resistant resin precursor composition, which is a product.