JP3514167B2 - Photosensitive heat-resistant resin precursor composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive heat-resistant polyimide resin composition, which is suitable for a surface protection film, an interlayer insulating film, etc. of a semiconductor device and which is exposed to ultraviolet light and dissolved in an alkaline aqueous solution.

[0002]

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

However, in the case where naphthoquinonediazide is added to ordinary polyamic acid, the solubility of the carboxyl group of polyamic acid is higher than the effect of naphthoquinonediazide on alkali dissolution, so that the desired pattern can be obtained in most cases. There was a problem that it did not exist. In addition, in the case of adding a soluble polyimide resin having a hydroxyl group, the problems as described above are lessened, but the structure is limited to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. The point was a problem. A polyamide resin having a hydroxyl group, to which naphthoquinonediazide is added, has a problem in that there is a limitation in the structure in order to obtain solubility, and thus the resin obtained after heat treatment has poor solvent resistance.

[0004] In consideration of the above drawbacks, the present invention is the addition of epoxy compounds that act as quinonediazide compound and a curing agent to the resin precursor having a hydroxyl group and a carboxyl group, after development film reduction is small and It was found that the pattern shape after heat treatment was good, and the present invention was achieved.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems and enables development in a short time with an environment-friendly alkaline aqueous solution and has a good pattern shape after heat treatment. It is intended to provide a resin precursor composition.

[0006]

[Means for Solving the Problems] (a) A polymer having a structural unit represented by the general formula (1) as a main component, (b) a quinonediazide compound, and (c) a curing agent having 2 to 4 epoxy groups. It is a photosensitive heat-resistant resin precursor composition characterized by containing.

[0007]

[Chemical 2]

(R1 is a divalent to octavalent organic group having at least two or more carbon atoms, R2 is a divalent to hexavalent organic group having at least two or more carbon atoms, R3 is hydrogen, or An organic group having 1 to 20 carbon atoms.
Is an integer from 10 to 100000, m is an integer from 0 to 2, and p and q are integers from 0 to 4. m + p + q is 1
Indicates the above integer. )

[0009]

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

The polymer containing the structural unit represented by the general formula (1) as a main component preferably has a hydroxyl group. In this case, due to the presence of the hydroxyl group, the solubility in an alkaline aqueous solution is better than that of a polyamic acid having no hydroxyl group. Particularly, among the hydroxyl groups, phenolic hydroxyl groups are preferable from the viewpoint of solubility in an alkaline aqueous solution.

In the above general formula (1), the residue containing R1 represents a structural component of an acid, and the acid component contains an aromatic ring and has 0 to 4 hydroxyl groups. Number 6 to 3
A divalent to octavalent group of 0 is preferable. Examples thereof include divalent acids such as phthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, hydroxyphthalic acid, hydroxydiaminodiphenyl ether dicarboxylic acid, and bis. (Carboxy-hydroxyphenyl) hexafluoropropane, dihydroxydiphenylsulfonedicarboxylic acid, dihydroxydiphenyldicarboxylic acid, and other trivalent acids trimellitic acid, trimesic acid, naphthalenetricarboxylic acid, biphenyltricarboxylic acid, hydroxytrimellitic acid, dihydroxybiphenyl Butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarbohydrate, which is a tetravalent acid such as tricarboxylic acid Acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, hydroxypyromellitic acid, dihydroxybenzophenonetetracarboxylic acid, trihydroxybenzophenonetetracarboxylic acid, tetrahydroxybenzophenonetetracarboxylic acid, etc. be able to.

Specifically, a structure represented by the following general formula (2) is preferred, and in this case, R4 and R6
Is preferably one containing an aromatic ring in view of the heat resistance of the polymer to be obtained, and among these, particularly preferable structures include trimellitic acid, trimesic acid, and naphthalenetricarboxylic acid residues. Further, R5 is preferably a trivalent to hexavalent organic group having a hydroxyl group and having 3 to 20 carbon atoms. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. Such examples include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane, bis (3-amino-4-).
Hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2, 4-diamino - phenol, 2,5-di-aminophenol, 1, Four
-Diamino-2,5-dihydroxybenzene residue and the like can be mentioned.

[0013]

[Chemical 3]

In the general formula (2), R4 and R6 are trivalent to tetravalent organic groups selected from 2 to 20 carbon atoms, and R5 is trivalent to 6 having a hydroxyl group selected from 3 to 20 carbon atoms.
Valent organic groups, R7 and R8 are hydrogen, or have 1 to 20 carbon atoms.
Up to organic groups, u and w are 1 or 2, and v is an integer from 1 to 4.

R7 and R8 are hydrogen or have 1 carbon atom.
To 20 organic groups are preferred. When the carbon number is 20 or more, the solubility in an alkali developing solution is lowered.

U and w represent 1 or 2, and v
Represents an integer from 1 to 4. When v is 5 or more, the characteristics of the resulting heat resistant resin film deteriorate.

Among the compounds of the general formula (2), examples of preferable compounds include those having the structures shown below, but are not limited thereto.

[0018]

[Chemical 4]

In the above general formula (1), the residue containing R2 represents the structural component of the diamine. Among these, preferred examples of R2 include those having an aromatic group and a hydroxyl group due to the heat resistance of the resulting polymer, and specific examples thereof include bis (amino-hydroxy-phenyl) hexafluoropropane, Compounds such as diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and the general formulas (3), (4),
The structure shown in (5) can be given.

[0020]

[Chemical 5]

In the general formula (3), R9 and R11 are trivalent to tetravalent organic groups selected from 2 to 20 carbon atoms, and R10 is
A divalent organic group having 2 to 30 carbon atoms, x and y each represent an integer of 1 or 2.

[0022]

[Chemical 6]

R12 and R14 in the general formula (4) have 2 carbon atoms.
R20 is a trivalent to hexavalent organic group selected from 3 to 20 carbon atoms, and z is 1
Indicates an integer from 1 to 4.

[0024]

[Chemical 7]

R15 in the general formula (5) has 2 to 20 carbon atoms.
R16 is a divalent organic group selected from the group consisting of 3 to 2 carbon atoms.
A trivalent to hexavalent organic group selected from 0, and a represents an integer of 1 to 4.

Among these, R9, R11 of the general formula (3),
R13 of the general formula (4) and R16 of the general formula (5) are preferably an organic group having an aromatic ring in view of the heat resistance of the obtained polymer. R10 of general formula (3) and R1 of general formula (4)
2, R14 and R15 in the general formula (5) are preferably organic groups having an aromatic ring in view of the heat resistance of the obtained polymer.

In the general formula (3), the residue containing R9 and R11 represents a trivalent to tetravalent organic group having a hydroxyl group, and one having an aromatic ring is preferred because of the heat resistance of the resulting polymer. preferable. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis ( (Hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

R10 in the general formula (3) has 2 to 30 carbon atoms.
Represents a divalent organic group. An aromatic divalent group is preferable to the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. Other than these, an aliphatic cyclohexyl group and the like can also be used.

In the general formula (4), R12 and R14 represent a divalent organic group having 2 to 30 carbon atoms. An aromatic divalent group is preferable to the heat resistance of the obtained polymer. Examples of such groups include a phenyl group, a biphenyl group,
Examples thereof include a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group, but in addition to these, an aliphatic cyclohexyl group can also be used.

The residue containing R13 in the general formula (4) represents a trivalent to tetravalent organic group having a hydroxyl group, and is preferably one having an aromatic ring in view of the heat resistance of the resulting polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis ( (Hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

In the general formula (5), R15 represents a divalent organic group having 2 to 30 carbon atoms. From the heat resistance of the obtained polymer, a divalent group having an aromatic group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group and a diphenylsulfone group. However, other than this, an aliphatic cyclohexyl group or the like can also be used.

The residue containing R16 in the general formula (5) represents a trivalent to tetravalent organic group having a hydroxyl group, and one having an aromatic ring is preferable from the heat resistance of the resulting polymer. Specifically, a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis ( (Hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. Further, aliphatic groups such as hydroxycyclohexyl group and dihydroxycyclohexyl group can also be used.

It is also possible to use a diamine containing no hydroxyl group as R2 in the general formula (1). Examples of these are phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl).
Examples thereof include sulfone and compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom.
Examples of such compounds include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or aromatic compounds thereof. Examples thereof include compounds in which the group ring is substituted with an alkyl group or a halogen atom, such as aliphatic cyclohexyldiamine and methylenebiscyclohexylamine.

R3 in the general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the stability of the resulting photosensitive heat-resistant resin precursor solution, R3 is preferably an organic group, but hydrogen is preferable from the viewpoint of solubility in an aqueous alkali solution. In the present invention, hydrogen atoms and alkyl groups can be mixed. By controlling the amounts of hydrogen and organic groups of R3, the dissolution rate in the alkaline aqueous solution changes, and therefore, by this adjustment, a photosensitive heat-resistant resin precursor composition having an appropriate dissolution rate can be obtained. R3 may be all hydrogen atoms or all organic groups, but a more preferable range is that 10% to 90% of R3 are hydrogen atoms. If the carbon number of R3 exceeds 20, it will not dissolve in the alkaline aqueous solution.

Further, in order to improve the adhesiveness to the substrate, R1 and R2 may be copolymerized with an aliphatic group having a siloxane structure within a range that does not lower the heat resistance. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane and the like are contained in an amount of 1-10.
It is preferable that R3 such as a copolymerized by mol% contains at least one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

The photosensitive heat-resistant resin precursor composition of the present invention is
It may be composed only of the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. At that time, it is preferable that the structural unit represented by the general formula (1) is contained in an amount of 90 mol% or more. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment film.

The heat resistant resin precursor of the present invention is synthesized by a known method. For example, tetracarboxylic acid 2 at low temperature
Method of reacting an anhydride with a diamine compound (CES
rog et al., Journal Polymer Sci
ence magazine, Part A-3, 1373 (196)
5)), a method for obtaining a diester from tetracarboxylic acid dianhydride and alcohol, and then reacting the amine with an amine in the presence of a condensing agent (JP-A-61-272022), tetracarboxylic acid dianhydride and alcohol. To obtain a diester, and then the remaining dicarboxylic acid is converted to an acid chloride and reacted with an amine (JP-A-55-30207).

The quinonediazide compound added to the present invention is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bound to a phenolic hydroxyl group with an ester. Examples of such substances include, but are not limited to, those shown below.

[0039]

[Chemical 8]

When the molecular weight of the naphthoquinonediazide compound is 1000 or more, the naphthoquinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that problems such as deterioration in heat resistant mechanical properties and adhesiveness of the obtained film occur. there is a possibility. From this point of view, the preferred naphthoquinonediazide compound has a molecular weight of 3
It is from 00 to 1000. More preferably, it is 350 to 800.

The amount of the naphthoquinonediazide compound added in the present invention is 100% of the polymer represented by the general formula (1).
It is 5 to 100 parts by weight, more preferably 7 to 40 parts by weight with respect to parts by weight. If the addition amount is less than 5 parts by weight, the photosensitive performance is not sufficient, and if it is more than 100 parts by weight,
It is not preferable because the mechanical properties of the film after heat treatment deteriorate.

[0042] As the curing agent added to the present invention, it may be mentioned etc. epoxy compound. When such a compound is added, it reacts with the hydroxyl group and the carboxyl group of the polymer to form a crosslinked structure, so that the shape before development can be maintained.

The epoxy compound added to the present invention is preferably divalent or higher in order to form a crosslinked structure with the polymer. However, when it becomes more than 4 values,
The polymer tends to gel. Therefore, the epoxy group is preferably divalent to tetravalent. Also, two or more
If an alkoxyl group is included, these additives will be added during addition.
The rucoxyl group and the carboxyl group and hydroxyl group of the polymer
It is not preferable because it may react and gel. In addition, examples of these basic structures include those obtained by reacting a compound having a hydroxyl group with epichlorohydrin. The types of compounds having a hydroxyl group include those having an aromatic ring such as bisphenol A type, bisphenol F type, novolac type, phenol novolac type, orthocresol novolac type, aminophenol type, biphenol type, naphthalene type, tetrabromobisphenol type, etc. The brominated form of Also,
Glycidyl amine type, glycidyl ether type, glycidyl ester type, silicon modified type, alicyclic type, alcohol ether type, aliphatic amine type and the like can be mentioned as those containing no aromatic ring, but are not limited thereto. . Specific epoxy compounds include 1,1,
2,2-tetra (p- hydroxyphenyl) ethanone integrators tiger glycidyl ether, glycerol triglycidyl ether, ortho secondary butyl phenyl glycidyl ether, 1,6-bis (2,3-epoxypropoxy)
Naphthalene, diglycerol polyglycidyl ether,
Examples thereof include polyethylene glycol diglycidyl ether, and the following can be given, but the present invention is not limited thereto .

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046] Also, the amount of the curing agent in the present invention 0.1
If the amount is less than 30 parts by weight, the effect will not be exhibited, and if it exceeds 30 parts by weight, problems may occur such as deterioration of the film after development and deterioration of heat resistance. From this perspective,
The addition amount of the curing agent is preferably 0.1 to 30 parts by weight. More preferably, it is 1 to 20 parts by weight.

If necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, ethanol, etc. may be added for the purpose of improving the coating property between the photosensitive heat-resistant precursor composition and the substrate. Alcohols, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. Further, inorganic particles such as silicon dioxide and titanium oxide, or polyimide powder can be added.

Further, in order to improve the adhesiveness to a base substrate such as a silicon wafer, 0.5 to 10 parts by weight of a silane coupling agent, a titanium chelating agent or the like is added to the varnish of the photosensitive heat-resistant resin precursor composition. Alternatively, the base substrate can be pretreated with such a chemical solution.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent, or an aluminum chelating agent is added in an amount of 0.5 to 10% by weight based on the polymer in the varnish. Add part.

When the substrate is treated, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. 5 to 20 parts by weight of the dissolved solution is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, then 50 to 300 degrees Celsius
The reaction between the substrate and the above coupling agent proceeds by applying the temperature up to.

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

The photosensitive heat resistant precursor composition is coated on a substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but the substrate is not limited to these. As the coating method, spin coating using a spinner,
There are methods such as spray coating and roll coating.
The coating thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but usually the coating thickness after drying is 0.1
To 150 μm.

Next, the substrate coated with the photosensitive heat-resistant precursor composition is dried to obtain a photosensitive heat-resistant precursor composition film. Drying is preferably carried out using an oven, a hot plate, infrared rays or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

Next, the photosensitive heat-resistant precursor composition film is exposed to actinic radiation through a mask having a desired pattern. The actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), g
It is preferred to use the line (436 nm).

The formation of the pattern of the heat resistant resin can be achieved by removing the exposed portion with a developing solution after the exposure. As the developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl Aqueous solutions of compounds showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred. Further, in some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolaclone, or dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination of several kinds. Good. After development, rinse with water. Also here, rinse 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.

After development, a temperature of 200 to 500 ° C. is applied to convert the film into a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and gradually increasing the temperature or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 degrees, 200 degrees, and 350 degrees for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

The heat-resistant resin film formed from the photosensitive heat-resistant precursor composition according to the present invention is used for a passivation film for semiconductors, a protective film for semiconductor elements, an interlayer insulating film for multi-layer wiring for high-density packaging, and the like. .

[0058]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Method for measuring characteristics Measurement of film thickness Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.
Was used with a refractive index of 1.64. Film heat treatment method A pattern of a photosensitive heat-resistant resin precursor film was formed on a 4-inch silicon wafer as shown in this example. Then, an inert oven CLH- manufactured by Koyo Lindbergh
21CD at 140 ° C. for 30 minutes, then to 350 ° C. over 1 hour, and at 350 ° C. for 1 hour, oxygen concentration 2
Heat treatment was performed at 0 ppm or less to obtain a cured film.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (1) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) under a dry nitrogen stream.
18.3 g (0.05 mol) and allyl glycidyl ether 34.2 g (0.3 mol) were dissolved in 100 g of gamma-butyrolactone (GBL), and cooled to -15 ° C.
22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added to the reaction solution at a temperature of 0.
It was added dropwise so as not to exceed ℃. After the dropping was completed, the reaction was carried out at 0 ° C. for 4 hours. The solution was concentrated with a rotary evaporator and poured into 1 l of toluene to obtain an acid anhydride (1). This is shown below. The material obtained did not show a clear melting point up to 350 ° C.

[0060]

[Chemical 11]

Synthesis Example 2 Synthesis of hydroxyl group-containing acid anhydride (2) 10.8 g (0.05 mol) of 3-hydroxy-4-aminobiphenyl (HAB) and 30 g of glycidyl methyl ether (0. 34 mol) to GBL300
g, and cooled to -15 ° C. GBL50 here
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 dropping was completed, the reaction was carried out at 0 ° C. for 4 hours. This solution was put into 5 l of acetone to obtain an acid anhydride (2). This is shown below. The material obtained did not show a clear melting point up to 350 ° C.

[0062]

[Chemical 12]

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

The solid collected by recrystallization was treated with ethanol 100.
ml and tetrahydrofuran 300 ml
% Palladium-carbon (2 g) was added and the mixture was vigorously stirred.
Hydrogen was introduced here by a balloon to carry out the reduction reaction at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloon did not deflate any more. After the reaction was completed, the palladium compound as a catalyst was removed by filtration and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (1). This is shown below. The obtained solid was used for the reaction as it was.

[0065]

[Chemical 13]

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine compound (2) 2-amino-4-nitrophenol 15.4 g (0.1
50 ml of acetone, 30 g of propylene oxide
It was dissolved in (0.34 mol) and cooled to -15 ° C. 20.4 g (0.11 g of 3-nitrobenzoic acid chloride)
(Mol) was dissolved in 60 ml of acetone and added dropwise. After completion of dropping, the reaction was allowed to proceed at −15 ° C. for 4 hours, then the temperature was returned to room temperature, and the generated precipitate was collected by filtration.

The precipitate was dispersed in 200 ml of methyl cellosolve, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon containing hydrogen gas was attached to this, and stirring was continued at room temperature until the hydrogen gas balloon did not shrink any further, and stirring was further performed for 2 hours with the hydrogen gas balloon attached. After completion of the reaction, the palladium compound was removed by filtration, and the furnace liquid was concentrated by a rotary evaporator until the amount became half. Ethanol was added to this and washing was performed to obtain a diamine compound (2). This is shown below.

[0068]

[Chemical 14]

Example 1 57.4 g (0.095 mol) of diamine compound (1) synthesized in Synthesis Example 3 was placed in a 1-liter four-necked flask under a stream of dry nitrogen, and 1,3-bis (3-aminopropyl). 1.24 g (0.005 mol) of tetramethyldisiloxane was added to GBL
It was dissolved in 350 g. 71.4 g (0.1 mol) of the acid anhydride (1) synthesized in Synthesis Example 1 was added thereto together with 40 g of GBL, reacted at 20 ° C. for 1 hour, and then at 50 ° C.
And reacted for 4 hours.

Obtained solution (of which 130 g of polymer)
13.0 g of the quinonediazide compound (a) shown below
And 6.5 g of epoxy compound (b) ("Epicoat" -828 manufactured by Yuka Shell Epoxy Co., Ltd.)
A varnish A of the photosensitive heat-resistant resin precursor composition was obtained by adding together with 0 g.

The film thickness after prebaking the varnish A of the photosensitive heat-resistant resin precursor was 10 on a 4-inch silicon wafer.
It is applied so as to have a thickness of μm, and then hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.) is used to obtain 100 ° C.
By prebaking for 3 minutes, a photosensitive heat-resistant resin precursor film was obtained. Then, a mask with a cut pattern was set in an exposure device (contact aligner PLA-501F manufactured by Canon Inc.), and the exposure amount was 300 mJ / cm ² (36
Exposure was performed at an intensity of 5 nm).

The development is SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing apparatus of -636, a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed at 50 rpm for 10 seconds. Then, it was left still for 100 seconds at 0 rotation, rinsed with water for 10 seconds at 400 rotations, and shaken off for 10 seconds at 3000 rotations to dry.

The film thickness of the unexposed portion after development was 9.4 μm, and the film reduction due to development was as small as 0.6 μm, which was good. As a result of observing the pattern after development, the pattern of 5 μm required as a buffer coat for semiconductor was resolved, and the pattern shape was not a problem. afterwards,
Heat treatment was performed by a predetermined method to obtain a cured film. When the pattern cross-sectional shape of this film was observed by SEM (scanning electron microscope), the taper angle was very small and there was no problem in shape.

[0074]

[Chemical 15]

Example 2 BAHF1 was placed in a 1-liter 4-neck flask under a stream of dry nitrogen.
1.0 g (0.03 mol) and 4.0 g (0.02 mol) of 4,4'-diaminodiphenyl ether were added to acetone 30
g and propylene oxide 58 g (1.0 mol), and the mixture was cooled to -10 ° C. A solution prepared by dissolving 21.1 g (0.1 mol) of trimellitic anhydride chloride in 40 g of acetone was gradually added dropwise thereto so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropping, the reaction was carried out at -5 ° C or lower for 1 hour to obtain 4,4'-diaminodiphenyl ether 9.
0 g (0.045 mol) and 1.3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0.0
A solution in which 80 mol of N-methylpyrrolidone (NMP) was dissolved was added, and the mixture was reacted at 0 ° C for 1 hour and then at 30 ° C for 4 hours.

After completion of the reaction, the solution was poured into 10 l of water to form a polyhydroxyamide acid precipitate. The precipitate is collected by filtration, washed with water and dried in a vacuum oven at 50 ° C for 20
Allowed to dry for hours. Here, 10 g of the polymer, 2.5 g of the quinonediazide compound (a) of Example 1 and 1 g of the epoxy compound (b) were mixed and dissolved in 40 g of GBL to obtain a varnish B of a photosensitive heat-resistant resin precursor composition.

The coating of the varnish B on the wafer and the pre-baking were the same as in Example 1, and the exposure was 500 mJ.
/ Cm ² (strength of 405 nm) was performed in the same manner as in Example 1.

Development was carried out in the same manner as in Example 1 except that the standing time was set to 50 seconds before the rinse treatment. The film thickness of the unexposed portion after development was 9.0 μm, and the film reduction due to development was as small as 1.0 μm, which was good. As a result of observing the pattern after development, the pattern of 5 μm required as a buffer coat for semiconductor was resolved, and the pattern shape was not a problem. Then, heat treatment was performed by a predetermined method to obtain a cured film. The pattern cross-sectional shape of this film is
When observed by EM, the taper angle was very small as in Example 1, and there was no problem in shape.

Example 3 Under a dry nitrogen stream, 6.1 g (0.025 mol) of the diamine compound (2) synthesized in Synthesis Example 4 and 4.5 g of 4,4'-diaminodiphenyl ether were placed in a 1-liter four-necked flask.
(0.0225 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0.62 g (0.00
25 mol) was dissolved in 100 g of NMP. Here 3,
14.7 g (0.05 mol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride was added at room temperature together with 33 g of NMP, and the mixture was allowed to react at room temperature for 1 hour and then at 50 ° C for 4 hours. 3 g of the quinonediazide compound (a) and 1 g of the epoxy compound (b) of Example 1 were dissolved in a solution containing 30 g of this polymer to obtain a varnish C of a photosensitive heat-resistant resin precursor composition.

Application of varnish C on the wafer, pre-baking, and exposure were performed in the same manner as in Example 1.

Development was carried out in the same manner as in Example 1 except that the standing time was set to 80 seconds before the rinse treatment. The film thickness of the unexposed portion after development was 9.2 μm, and the film reduction due to development was as small as 0.8 μm, which was favorable. As a result of observing the pattern after development with an optical microscope, a line of 10 μm was resolved, and the pattern shape was not a problem. Then, heat treatment was performed by a predetermined method to obtain a cured film. When the pattern cross-sectional shape of this film was observed by SEM, it was a very sharp shape as in Example 1, and there was no problem.

Example 4 Under a dry nitrogen stream, 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether was dissolved in 200 g of NMP in a 1-liter four-necked flask, and BTDA 16.1 was added thereto.
g (0.05 mol), PMDA 10.5 g (0.048
Mol) was added and reacted at room temperature for 1 hour and then at 50 ° C. for 3 hours to obtain a polyamic acid. 11.7 g of the quinonediazide compound (a) and 11.7 g of the epoxy compound (b) of Example 1 were added to this polyamic acid solution (of which 46.6 g was the polymer), and the varnish of the photosensitive heat-resistant resin precursor composition was added. I got D.

The coating of the varnish D on the wafer and the pre-baking were performed in the same manner as in Example 1. Next, exposure machine (Nikon g-line stepper-NSR-1505-g6E)
Set the reticle with the cut pattern to the
Exposure was performed at 00 mJ / cm ² (intensity of 436 nm).

For development, the same apparatus as in Example 1 was used, 0.5% tetramethylammonium aqueous solution was used as the developing solution, and the standing time was set to 60 seconds before the rinse treatment.
The same procedure as in Example 1 was performed. The film thickness of the unexposed portion after development was 8.8 μm, and the film reduction due to development was 1.2 μm, which was small and favorable. As a result of observing the pattern after development, a pattern of 10 μm was resolved and the pattern shape was not a problem. Then, heat treatment was performed by a predetermined method to obtain a cured film. The pattern cross sectional shape of this film is SE
When observed with M, the shape was very sharp as in Example 1, and there was no problem.

Comparative Example 1 A varnish E of a photosensitive heat-resistant resin precursor composition was obtained in the same manner as in Example 1 except that the epoxy compound was not added.

The coating of the varnish E on the wafer, pre-baking, and exposure were carried out in the same manner as in Example 1. The development was performed in the same manner as in Example 1 except that the standing time was set to 50 seconds before the rinse treatment. The unexposed film thickness after development is 8.1.
μm, and the reduction of the film due to development was larger than that in Example 1. As a result of observing the pattern after development, the resolution was about 15 μm. Further, when the pattern shape after the heat treatment was observed by SEM, it was found that the pattern edge had a slight taper .

[0087]

According to the present invention, it is possible to obtain a photosensitive heat-resistant resin precursor composition having a small film loss after alkali development and having a very good pattern shape after heat curing.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01L 21/312 C08L 79/08 A 23/29 C09D 179/04 Z 23/31 179/08 Z // C08L 79/08 C08L 79 / 08 C09D 179/04 63:00 Z 179/08 H01L 21/30 502R (C08L 79/08 23/30 D 63:00) (56) Reference JP-A-3-20743 (JP, A) JP-A 6-258836 (JP, A) JP-A-6-348016 (JP, A) JP-A-7-219228 (JP, A) JP-A-10-7796 (JP, A) JP-A-10-10717 (JP, A) A) JP 63-13032 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/037 501 C08K 5/28 C09D 5/00 G03F 7/022 H01L 21/027 H01L 21/312 H01L 23/29 H01L 23/31 C08L 79/08 C09D 179/04 C09D 179/08 C08L 79/08 C08L 63:00

Claims (2)

(57) [Claims] 1. A polymer containing (a) a polymer having a structural unit represented by the general formula (1) as a main component, (b) a quinonediazide compound, and (c) a curing agent having 2 to 4 epoxy groups. A photosensitive heat-resistant resin precursor composition comprising: [Chemical 1] 2. The photosensitive heat-resistant resin precursor composition according to claim 1, wherein (b) is added to 100 parts by weight of the polymer (a).
5 to 100 parts by weight of quinonediazide compound, (c) cured
A photosensitive heat-resistant resin precursor composition comprising 0.1 to 30 parts by weight of an agent .