JPH11223940A - Photosensitive heat-resistant resin precursor composition - Google Patents

Abstract

(57) [Problem] To provide a photosensitive heat-resistant resin precursor composition capable of alkali development. (A) a diamine compound represented by the general formula (2) or (3) and a quinonediazide compound (b) with respect to a polymer having a structural unit represented by the general formula (1) as a main component. A photosensitive heat-resistant resin precursor composition comprising: Embedded image Embedded image Embedded image (R1 is a trivalent or tetravalent organic group having at least 2 to 30 carbon atoms. R2 and R6 are divalent organic groups having at least 2 to 30 carbon atoms.
R3 and R7 are divalent organic groups having 2 to 30 carbon atoms. R
4 is a monovalent organic group containing aromatics. R5 has 1 to 1 carbon atoms
Organic groups containing up to 0 or one or more of hydrogen. l and m are integers from 1 to 100,000, n is an integer of 1 or 2, and p and q are integers from 1 to 4. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive heat-resistant resin precursor composition useful as a surface protective film of a semiconductor, and more particularly to a photosensitive heat-resistant resin precursor composition which can be developed in a short time with an aqueous developer. About things.

[0002]

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

However, in the case of adding naphthoquinonediazide to polyamic acid, the desired pattern cannot be obtained in most cases because the solubility of carboxyl groups of polyamic acid is high due to the dissolution inhibiting effect of naphthoquinonediazide on alkali. There was a problem. In addition, in the case of adding a soluble polyimide resin having a hydroxyl group, although the problems just described have been reduced, the structure is limited in order to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. Points were problems. The polyamide resin having a hydroxyl group to which naphthoquinonediazide is added also has a limited structure in order to obtain solubility, therefore, the resin obtained after heat treatment is inferior in solvent resistance, and the heat-treated film is formed of fuming nitric acid. When used as an LSI protective film because it does not dissolve in concentrated sulfuric acid or the like, there is a problem that it is difficult to perform a defect inspection of a product.

Further, in order to maintain the mechanical properties of the film after the heat treatment, the molecular weight of the photosensitive heat-resistant resin precursor composition needs to be a certain level or more. However, when the molecular weight is increased as described above, there is a problem that the solubility is reduced and the developing speed is increased.

In view of the above drawbacks, the present invention provides a resin composition obtained by adding naphthoquinonediazide to a polyamic acid ester having a hydroxyl group, which is eliminated during heat treatment and has a group causing a polymerization reaction introduced at the terminal. It was found that it hardly dissolved in an alkali developer before exposure, but dissolved in an alkali developer in a short time after exposure, and that heat treatment eliminated the terminal groups and improved the molecular weight. Have also been found to be dramatically improved, leading to the present invention.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a photosensitive heat-resistant resin precursor composition which can be developed in a short time with an alkaline aqueous solution and is excellent in mechanical properties and heat resistance. It is intended to do so.

[0007]

The present invention provides (a) a polymer represented by the general formula (2) or (3) with respect to a polymer having a structural unit represented by the general formula (1) as a main component. A photosensitive heat-resistant resin precursor composition comprising a diamine compound and (b) a quinonediazide compound.

[0008]

Embedded image

Embedded image

Embedded image (R1 is a trivalent or tetravalent organic group having at least 2 to 30 carbon atoms. R2 and R6 are divalent organic groups having at least 2 to 30 carbon atoms.
R3 and R7 are divalent organic groups having 2 to 30 carbon atoms. R
4 is a monovalent organic group containing aromatics. R5 has 1 to 1 carbon atoms
Organic groups containing up to 0 or one or more of hydrogen. l and m are integers from 1 to 100,000, n is an integer of 1 or 2, and p and q are integers from 1 to 4. )

[0009]

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

In the above general formula (1), R 1 represents a structural component of an acid, and this component is preferably a trivalent or tetravalent group containing an aromatic ring and having 6 to 30 carbon atoms. Specifically, trimellitic acid, trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid,
Examples include, but are not limited to, diphenylsulfonetetracarboxylic acid, bis (phthalic acid) hexafluoropropane, and the like.

[0011] Further, R1 is selected from the group consisting of isophthalic acid, terephthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid and diphenyl carboxylic acid.
Valent groups can also be copolymerized. When such a divalent group is used as the R1 component, the content is preferably 20 mol% or less of the whole. Outside this range, there is a problem that the solubility in an alkaline developer decreases during development, the resistance of the film after heat treatment to an organic solvent decreases, and the solubility in a strong acid such as fuming nitric acid decreases. Absent. In the present invention, the R1 component may be composed of only one kind, or may be composed of a plurality of combinations.

In the general formula (1), R2 represents a structural component of hydroxydiamine. Among them, preferred examples of R2 include 2,2-bis (m-amino-p-hydroxyphenyl) hexafluoropropane and 3,3′-
Dihydroxy-4,4'-diaminobiphenyl, 3,
3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenylsulfone, hydroxy-metaphenylenediamine, 2,2-bis (p-amino-m-hydroxyphenyl) Hexafluoropropane, 3,3'-diamino-
4,4'-dihydroxybiphenyl, 3-hydroxy-
1,5-diaminobenzene, 6-hydroxy-2,4-
Examples include, but are not limited to, diaminopyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-hydroxytriazine, and the like.

It is also possible to modify with another diamine component in the range of 1 to 50 mol%. Examples of these include aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, aromatic paraphenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxy) Phenyl) sulfone and the like. 50 such diamine components
If the copolymerization is at least mol%, the solubility in an alkali developing solution will decrease, so further copolymerization is not preferred. In the present invention, R2 may be composed of only one kind, or may be composed of a plurality of combinations.

Further, R6 in the general formula (2) can be selected from the same as R2.

R3 in the general formula (1) represents a diamine compound. In view of the heat resistance of the obtained polymer, a compound having an aromatic ring is preferable. Examples of these include phenylenediamine, diaminodiphenylether, diaminodiphenylsulfone, diaminodiphenylmethane, diaminobenzanilide, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoro Examples thereof include propane and bis (aminophenoxyphenyl) sulfone.

Further, as long as the properties of the film are not significantly changed, aliphatic diamine compounds such as cyclohexyldiamine and methylenebiscyclohexylamine,
1,3-bis (3-aminopropyl) tetramethyldisiloxane, α, ω- (3-aminopropyl) permethylpolysiloxane, 1,3-bis (4-aminophenyl)
Those containing a siloxane structure such as tetramethyldisiloxane can also be used. The amount of modification of such an aliphatic diamine compound is 1% of the entire diamine component.
~ 40 mol%, more preferably 30 mol%
It is as follows. In the present invention, only one kind of R3 can be used, or a plurality of R3s described above can be used.

Further, R7 in the general formula (3) can be selected from the same as R3.

In the above general formula (1), R4 is selected from phenols and oximes. R4 is desorbed during heat treatment of the photosensitive heat-resistant resin precursor composition of the present invention, thereby generating a new carboxyl group at the terminal of the polymer of the general formula (1). The reaction of the diamine of (2) or (3) increases the molecular weight of the photosensitive heat-resistant resin precursor composition, and improves mechanical properties, chemical resistance, and the like.

From such a viewpoint, R4 is preferably a compound having a hydroxyl group having relatively high acidity. Illustrative of such compounds are phenol, cresol,
Phenols such as chlorophenol, nitrophenol, methoxyphenol, hydroxyacetophenone, ethyl hydroxybenzoate, dichlorophenol, dinitrophenol, trinitrophenol, trichlorophenol, hydroxybenzophenone, hydroxynitropyridine, hydroxynitroquinoline, hydroxynaphthoquinone, hydroxypyrimidine A phenolic analog in which a hydroxyl group is bonded to a heterocyclic ring, such as hydroxybenzotriazole, hydroxysuccinimide, hydroxynorbonene ヂ carboximide, hydroxyphthalimide,
Isonitrosoacetophenone, isonitrosopropiophenone, benzaloxime, 1,3-diphenyl-1,
3-propanedione-2-oxime, 1-phenyl-3
Oximes such as -ethoxy-2-oxime.

The stability of the ester bond formed between the hydroxyl group having a relatively high acidity and the carboxyl group is relatively low, and exchange reaction with the amino group easily occurs at a temperature of about 50 ° C. to about 200 ° C. , An increase in molecular weight occurs.

In the general formula (1), R5 represents an organic group having 1 to 10 carbon atoms or hydrogen. Here, when R5 is a hydrogen atom, the dissolution rate in an alkali developing solution is increased. Further, when R5 is an organic group, the dissolution rate in an alkali developer decreases. R5 has 1 carbon atom
An organic group of 0 or more is not preferable because the solubility in an alkali developing solution is reduced and the exposed portion may not be dissolved. From the above, in the present invention, the dissolution rate in an alkali developer can be controlled by controlling the amounts of hydrogen atoms and organic groups in R5.

Preferred examples of R5 include a hydrogen atom, a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, an ethoxymethyl group and an ethoxyethyl group. Group,
Groups such as butoxymethyl group, 2-hydroxypropyl group, 2-hydroxypentyl group, 2-hydroxy-3-
It is an organic group having an alcoholic hydroxyl group such as a methoxypropyl group, a 2-hydroxy-3-ethoxypropyl group, and a 2-hydroxy-3-propyloxypropyl group.

In addition, a hydroxyphenyl group having a phenolic hydroxyl group, a hydroxynaphthyl group,
A group having 10 or more carbon atoms, such as a hexadecyl group or a lauryl group, can be modified to 20 mol% or less of the whole. In the present invention, R5 may be composed of one type or two or more types.

The photosensitive heat-resistant resin precursor composition of the present invention first forms an ester of a phenol or oxime with one carboxyl group of the corresponding tricarboxylic acid or tetracarboxylic acid, and then forms this compound with a hydroxydiamine component or The polymer of the general formula (1) can be obtained by reacting with a diamine component.

The heat-resistant resin precursor composition of the present invention can be prepared by adding the diamine component and the hydroxydiamine component in a ratio of 0.8 to 1.2 times mol per mol of the polymer thus obtained. Can be obtained. At this time, if the ratio of the hydroxy diamine component to the diamine component is less than 0.1, the number of hydroxyl groups in the polymer becomes too small, and the contrast between the exposed part and the unexposed part decreases. Therefore, a desirable ratio of diamine to hydroxydiamine is 0.1 to 20.

The molecular weight of the resulting heat-resistant resin precursor composition can be changed by changing the reaction temperature, reaction time and the like. The molecular weight at this time is 2
If it is less than 0000, the film becomes brittle, so that mechanical properties and pattern workability are remarkably reduced. In addition, the molecular weight is 50
If it exceeds 0000, the solubility of the polymer is significantly reduced. Therefore, the molecular weight is from 20,000 to 5,000
00 is desirable.

Next, in order to impart photosensitivity, a quinonediazide compound is added to obtain the photosensitive heat-resistant resin precursor composition of the present invention. As the quinonediazide compound to be added, a compound in which a sulfonyl acid of naphthoquinonediazide is ester-bonded to a phenolic hydroxyl group is preferable.

In addition, compounds such as ethylene glycol or glycerin having an alcoholic hydroxyl group and a sulfonyl acid of naphthoquinonediazide in an ester bond, aniline having an amino group, phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, etc. Compounds in which an amino group and a sulfonyl acid of naphthoquinonediazide are amide-bonded, hydroxy-diaminopyrimidine having a hydroxyl group and an amino group, hydroxydiaminobenzene, aminophenol, bis (hydroxy-
Compounds in which the amino group of a compound such as aminophenyl) hexafluoropropane and the sulfonyl acid of naphthoquinonediazide are amide-bonded, or those in which the hydroxyl group of these compounds and the sulfonyl acid of naphthoquinonediazide are ester-bonded, and both the amino group and the hydroxyl group For example, a compound in which a sulfonylic acid of naphthoquinonediazide and an amide bond and an ester bond are used can be used.

When the molecular weight of these quinonediazide compounds is 1000 or more, the quinonediazide compounds do not thermally decompose sufficiently in the subsequent heat treatment, and thus problems such as a decrease in heat resistance, mechanical properties and adhesion of the resulting film occur. there is a possibility. From such a viewpoint, the preferable molecular weight of the quinonediazide compound is 300 to 100.
0. More preferably, it is 350 to 800.

Examples of the solvent used in the present invention include N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like, which are common solvents for polyamic acid esters. Polar aprotic solvents, tetrahydrofuran, ethers such as dioxane, acetone,
Solvents such as ketones such as methyl ethyl ketone and diisobutyl ketone, esters such as propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene can be used alone or in combination.

Further, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide may be added.

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

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

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

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

First, a photosensitive heat-resistant precursor composition is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating thickness is different depending on the coating method, the solid concentration of the composition, the viscosity, and the like.
It is applied so as to have a thickness of 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 performed using an oven, a hot plate, infrared rays or the like at a temperature in the range of 50 to 150 degrees 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. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm), h-line (405 nm), and g of a mercury lamp are used.
Preferably, a line (436 nm) is used. However, visible light of 450 to 550 nm, ultraviolet light of 350 nm or less, electron beam, X-ray, and the like can also be used.

The formation of the polyimide pattern is achieved by removing the exposed portions using a developing solution after exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Even if alcohols such as isopropanol, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone are used alone or in combination of several kinds. Good. After development, it is rinsed with water. Here, a rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, acetic acid, carbon dioxide, oxalic acid and phosphoric acid to water.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 to 500 degrees. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 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 by the photosensitive heat-resistant precursor composition according to the present invention is used for a passivation film of a semiconductor, a protective film of a semiconductor element, an interlayer insulating film of a multilayer wiring for high-density mounting, and the like. Used.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

Measurement method of properties Measurement of molecular weight GPC (gel permulation) manufactured by Waters
Showa Denko Corporation's Shode
x KF-804F and cosmosil 5 made by Nakarai
Using GPC-100, pump flow rate 0.8 at 40 ° C
The measurement was performed using THF (tetrahydrofuran) as a solvent at ml / min. The molecular weight is based on a molecular weight of 500 to 66.
000 monodisperse polystyrene was used.

Measurement of melting point Differential thermal analyzer (DSC) DSC-5 manufactured by Shimadzu Corporation
Using 0, measurement was performed at a heating rate of 20 ° C./min up to 400 ° C.

Measurement of Film Thickness The thickness of the photosensitive heat-resistant resin precursor was measured at a refractive index of 1.64 using an optical film thickness measuring device Lambda Ace manufactured by Dainippon Screen Co., Ltd. The film thickness before development (T1) and the film thickness of the unexposed portion after development (T2) are T2 / T1 (remaining film ratio) <
When it was 0.6, it was considered that there was no contrast between the exposed part and the unexposed part.

Measurement of Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer manufactured by Tokimec.

Synthesis Example 1 Synthesis of p-nitrophenyl trimellitic anhydride 13.9 g (0.1 mol) of p-nitrophenol and 11.1 g (0.11 mol) of triethylamine were added to acetone 1
Was dissolved in 00 g. The solution was cooled to 5 ° C. or less, and 23.2 g (0.11 g) of trimellitic anhydride chloride was added thereto.
(Mol) in 50 g of acetone was added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction was carried out at 5 ° C to 10 ° C for 3 hours. After the completion of the reaction, the deposited precipitate was collected by filtration. The precipitate was placed in a beaker containing 1 liter of water and washed with stirring. After the completion of the washing, a white precipitate was collected by filtration. The collected white precipitate was recrystallized from acetic anhydride (mp 18
3 ° C).

Synthesis Example 2 Synthesis of p-methylcarbonylphenyl trimellitic anhydride 13.6 g (0.1 mol) of 4-hydroxyacetophenone and 11.1 g (0.11 mol) of triethylamine were dissolved in 100 g of acetone. The solution was cooled to 5 ° C. or less, and 23.2 g of trimellitic anhydride chloride was added thereto.
(0.11 mol) in 50 g of acetone was added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction was carried out at 5 ° C to 10 ° C for 3 hours. After the completion of the reaction, the deposited precipitate was collected by filtration. The precipitate was placed in a beaker containing 1 liter of water and washed with stirring. After the completion of the washing, a white precipitate was collected by filtration. The collected white precipitate was recrystallized from acetic anhydride (mp 165 ° C).

Synthesis Example 3 Synthesis of trimellitic anhydride-methyl ester A solution obtained by dissolving 23.2 g (0.11 mol) of trimellitic anhydride chloride in 100 g of acetone was cooled to 5 ° C., and 9.60 g of methanol (0. 0.3 mol) and 11.1 g (0.11 mol) of triethylamine.
The reaction was performed at 0 ° C. for 3 hours. After completion of the reaction, the deposited precipitate was removed, the solvent of the filtrate was removed by an evaporator, and the filtrate was washed with water. The precipitate was recrystallized from acetic anhydride (mp 163).
° C).

Example 1 10.01 g of 4,4'-diaminodiphenyl ether
(0.05 mol) with gamma-butyrolactone (GBL) 5
0 g was dissolved. To this, 0.1 mol of the acid anhydride active ester synthesized in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 1 hour and subsequently reacted at 30 ° C. for 2 hours. Then, 2,2
-Bis (m-amino-p-hydroxyphenyl) hexafluoropropane 18.3 g (0.05 mol) was added,
The reaction was performed at 80 ° C. for 6 hours. The molecular weight of this polymer is expressed as G
As measured by PC, the number average molecular weight was 23,200. 10 g of this polymer and 2 g of a naphthoquinonediazide compound (one of four Qs is H) shown below are dissolved in 30 g of GBL, and the viscosity at 25 ° C. is 3.0 Pa.
The varnish A of the photosensitive heat-resistant resin precursor composition which was s was obtained.

[0051]

Embedded image Varnish A of a photosensitive polyimide precursor was applied on a 6-inch silicon wafer so that the film thickness after prebaking would be 7 μm, and then 100 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). For 3 minutes to obtain a photosensitive polyimide precursor film. Next, an exposure machine (Nikon i-line stepper-NSR)
-1755-i7A), the reticle on which the pattern was cut was set, and i-ray exposure was performed at an exposure amount of 500 mJ / cm ² (intensity of 365 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing apparatus of -636, a 1.5% aqueous solution of tetramethylammonium was sprayed for 10 seconds at 50 rotations. Thereafter, the substrate was left still for 90 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds.

The film thickness of the unexposed portion after the development was 6.8 μm, and the reduction of the film in the unexposed portion due to the development was very good at 0.2 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

Example 2 5.00 g of 4,4'-diaminodiphenyl ether
(0.025 mol) and 2,2-bis (m-amino-p-
9.15) Hydroxyphenyl) hexafluoropropane
g (0.025 mol) was dissolved in 50 g of GBL. Here, the active ester of the acid anhydride synthesized in Synthesis Example 2 0.1
The reaction mixture was stirred at room temperature for 1 hour, and then reacted at 30 ° C. for 2 hours. Subsequently, 19.46 g (0.045 mol) of bis (4-aminophenoxyphenyl) sulfone was added, and the mixture was reacted at 80 ° C. for 6 hours. When the molecular weight of this polymer was measured by GPC, the number average molecular weight was 24100
Met. 10 g of this polymer and 2 g of the naphthoquinonediazide compound used in Example 1 were dissolved in 30 g of GBL to obtain a varnish B of a photosensitive heat-resistant resin precursor composition having a viscosity at 25 ° C. of 2.8 Pa · s.

On a 6-inch silicon wafer, a varnish B of a photosensitive polyimide precursor was prebaked to a thickness of 7 μm.
m, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
By pre-baking at 3 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained. Next, the reticle with the pattern cut was set in an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 500 mJ / cm.
² (intensity of 365 nm) was used for i-line exposure.

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing apparatus of -636, a 1.5% aqueous solution of tetramethylammonium was sprayed for 10 seconds at 50 rotations. Thereafter, the substrate was left still for 90 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds.

The film thickness of the unexposed portion after the development was 6.5 μm, and the reduction of the film in the unexposed portion due to the development was as very good as 0.5 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

Example 3 bis (4-aminophenoxyphenyl) sulfone
46 g (0.045 mol) and 1.24 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
005 mol) was dissolved in 50 g of GBL. To this, 0.1 mol of the acid anhydride active ester synthesized in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 1 hour and subsequently reacted at 30 ° C. for 2 hours. Subsequently, 18.3 g of 2,2-bis (m-amino-p-hydroxyphenyl) hexafluoropropane
(0.05 mol) and reacted at 80 ° C. for 8 hours.
When the molecular weight of this polymer was measured by GPC, the number average molecular weight was 21,000.

10 g of this polymer and 2 g of the naphthoquinonediazide compound used in Example 1 were dissolved in 30 g of GBL to obtain a varnish C of a photosensitive heat-resistant resin precursor composition having a viscosity at 25 ° C. of 2.5 Pa · s. Was.

On a 6-inch silicon wafer, a varnish C of a photosensitive polyimide precursor was pre-baked to a thickness of 7 μm.
m, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
By pre-baking at 3 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained. Next, the reticle with the pattern cut was set in an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 500 mJ / cm.
² (intensity of 365 nm) was used for i-line exposure.

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing apparatus of -636, a 1.5% aqueous solution of tetramethylammonium was sprayed for 10 seconds at 50 rotations. Then, it was left still for 120 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds.

The film thickness of the unexposed portion after the development was 6.9 μm, and the reduction of the film in the unexposed portion due to the development was very good at 0.1 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

Comparative Example 1 10.01 g of 4,4′-diaminodiphenyl ether
(0.05 mol) with gamma-butyrolactone (GBL) 5
0 g was dissolved. To this, 0.1 mol of the acid anhydride active ester synthesized in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 1 hour and subsequently reacted at 30 ° C. for 2 hours. Subsequently, 21.6 g of bis (4-aminophenoxyphenyl) sulfone was used.
(0.05 mol) and reacted at 80 ° C. for 8 hours.
When the molecular weight of this polymer was measured by GPC, the number average molecular weight was 17,500.

10 g of this polymer and 2 g of the naphthoquinonediazide compound used in Example 1 were dissolved in 30 g of GBL to obtain a varnish D of a photosensitive heat-resistant resin precursor composition having a viscosity of 2.1 Pa · s at 25 ° C. Was.

On a 6-inch silicon wafer, a varnish D of a photosensitive polyimide precursor was pre-baked to a thickness of 7 μm.
m, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
By pre-baking at 3 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained. Next, the reticle with the pattern cut was set in an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 500 mJ / cm.
² (intensity of 365 nm) was used for i-line exposure.

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a -636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rotations for 10 seconds. Thereafter, the plate was left still for 90 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and dried by shaking off at 3000 rotations for 10 seconds, but all were dissolved and no pattern could be obtained.

Comparative Example 2 2,2-bis (m-amino-p-hydroxyphenyl)
A polymer was polymerized in the same manner as in Example 1 except that the amount of hexafluoropropane was changed to 36.6 g (0.1 mol). When the molecular weight of this polymer was measured by GPC, the number average molecular weight was 7,300. 10 g of this polymer and 2 g of the naphthoquinonediazide compound used in Example 1 were dissolved in 30 g of GBL, and a varnish E as a photosensitive heat-resistant resin precursor having a viscosity of 0.1 Pa · s at 25 ° C.
I got

A varnish E of a photosensitive polyimide precursor was coated on a 6-inch silicon wafer to a thickness of 7 μm after prebaking.
m, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
By pre-baking at 3 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained. Next, the reticle with the pattern cut was set in an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 500 mJ / cm.
² (intensity of 365 nm) was used for i-line exposure.

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a -636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rotations for 10 seconds. Thereafter, the substrate was left still for 90 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds. As a result, although a pattern was formed, the film thickness after development was as thin as 1.5 μm.

Comparative Example 3 10.01 g of 4,4′-diaminodiphenyl ether
(0.05 mol)) with gamma-butyrolactone (GBL)
Dissolved in 50 g. To this, 0.1 mol of the acid anhydride active ester synthesized in Synthesis Example 3 was added, and the mixture was stirred at room temperature for 1 hour and subsequently reacted at 30 ° C. for 2 hours. Then, 2,2
-Bis (m-amino-p-hydroxyphenyl) hexafluoropropane 18.3 g (0.05 mol) was added,
The reaction was performed at 80 ° C. for 8 hours. The molecular weight of this polymer is expressed as G
As measured by PC, the number average molecular weight was 4000.

10 g of this polymer and 2 g of the naphthoquinonediazide compound used in Example 1 were dissolved in 30 g of GBL to obtain a varnish F of a photosensitive heat-resistant resin precursor composition.

A varnish F of a photosensitive polyimide precursor was coated on a 6-inch silicon wafer to a thickness of 7 μm after prebaking.
m, and then using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
By pre-baking at 3 ° C. for 3 minutes, a photosensitive polyimide precursor film was obtained. Next, the reticle with the pattern cut was set in an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 500 mJ / cm.
² (intensity of 365 nm) was used for i-line exposure.

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a -636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rotations for 10 seconds. Thereafter, the plate was left still for 90 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and dried by shaking off at 3000 rotations for 10 seconds, but all were dissolved and no pattern could be obtained.

[0074]

According to the present invention, a photosensitive heat-resistant resin precursor composition which can be developed in an alkaline aqueous solution in a short time and has excellent mechanical properties and heat resistance can be obtained.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 501 G03F 7/004 501 7/039 501 7/039 501

Claims (3)

[Claims] (1) a diamine compound represented by the general formula (2) or (3) and (b) a quinonediazide with respect to a polymer having a structural unit represented by the general formula (1) as a main component. A photosensitive heat-resistant resin precursor composition comprising a compound. Embedded image Embedded image Embedded image (R1 is a trivalent or tetravalent organic group having at least 2 to 30 carbon atoms. R2 and R6 are divalent organic groups having at least 2 to 30 carbon atoms.
R3 and R7 are divalent organic groups having 2 to 30 carbon atoms. R
4 is a monovalent organic group containing aromatics. R5 has 1 to 1 carbon atoms
Organic groups containing up to 0 or one or more of hydrogen. l and m are integers from 1 to 100,000, n is an integer of 1 or 2, and p and q are integers from 1 to 4. ) 2. (a) α mol of the compound represented by the general formula (1), β mol of the hydroxydiamine represented by the general formula (2), and γ mol of the diamine compound represented by the general formula (3) 2. The photosensitive material according to claim 1, wherein the ratio of α, β, and γ is 0.8 ≦ (β + γ) /α≦1.2 0.1 ≦ β / γ ≦ 20. Heat-resistant resin precursor composition. 3. The photosensitive heat-resistant resin composition according to claim 1, wherein 1 to 40 mol% of the diamine component is a siloxane-containing diamine.