JPH11258787A - Positive photosensitive resin composition and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance adhesion to a substrate in a developing process and adhesion in a curing process by using a specified polyamide and a photosensitive diazoquinone compound and a specified organic silicon compound. SOLUTION: This positive photosensitive resin composition comprises 100 pts.wt. of the polyamide represented by formula I, 1-100 pts.wt. of the photosensitive deazoquinone compound, 0.1-10 pts.wt. of the organic silicon compound represented by formula II, and 0.1-10 pts.wt. of the organic silicon compound represented by formula III, and in formulae I-III, each of X and R5 is a tetravalent aromatic group; Y is a divalent aromatic group; Z is represented by formula IV; each of R1 , R2 , R6 , and R10 is a divalent organic group; each of R3 , R4 , R7 , R8 , R11 , and R12 is a univalent organic group; E is an aliphatic or alicyclic or aromatic group having an alkenyl or alkynyl group; R9 is a divalent aromatic or divalent organic group; each of (a) and (b) is 60-100 mol.% and 0-40 mol.%, respectively; and each of (n) and (p) is 2-500 and 0-2, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type which has excellent adhesiveness to a substrate in a developing step, and provides sufficient adhesiveness even when cured without strictly controlling the oxygen concentration in the curing step. The present invention relates to a photosensitive resin composition and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used as a surface protective film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvements in heat cycle resistance and heat shock resistance due to the shift to surface mounting due to the increase in size, thinning and miniaturization of packages, and solder reflow. It has become. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention, and examples thereof include a photosensitive polyimide resin represented by the following formula (X).

[0003]

Embedded image

When this is used, a part of the pattern forming process can be simplified, which has the effect of shortening the process.
Since a solvent such as methyl-2-pyrrolidone is required, there is a problem in safety and handling. Therefore, recently, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been developed. For example, Japanese Patent Publication No. 1-46862 discloses a positive photosensitive resin composed of a polybenzoxazole precursor and a diazoquinone compound. It has high heat resistance, excellent electrical properties and fine workability, and has the potential not only as a wafer coat but also as an interlayer insulating resin. The mechanism of development of the positive photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the aqueous alkali solution, but the exposure causes the diazoquinone compound to undergo a chemical change and become soluble in the aqueous alkaline solution.
By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, it becomes possible to form a coating film pattern of only the unexposed portion.

When the photosensitive resin disclosed in Japanese Patent Publication No. 1-46862 is actually used, a particular problem is adhesion to a substrate, especially a silicon wafer.
That is, when performing wet etching using a developing solution in the developing step, there is a problem that a coating film of an unexposed portion which should be originally left is peeled off or floated. In addition, after pattern processing, an oxazole ring is formed in a heat treatment (curing) process, but the adhesion after curing is insufficient, and there is also a problem that the coating film is peeled off from the substrate particularly when high-temperature moisture absorption treatment is performed. .

Japanese Patent No. 2627632 discloses a silane-modified carboxylic acid derivative as an adhesion aid for a polyimide resin. When this is added to the photosensitive resin described in Japanese Patent Publication No. 1-46862, adhesion during development,
There is an improvement in adhesion after curing. However, it is important to control the oxygen concentration during the curing process.
Unless it is 0 ppm or less, sufficient adhesion cannot be obtained. In order to carry out curing under an atmosphere condition having an oxygen concentration of 10 ppm or less, an oven or a diffusion furnace having excellent airtightness is required, and a considerably large investment is required. For this reason, there is a demand from the semiconductor manufacturing side for a surface coating material that can provide sufficient adhesion even when curing is performed with simple oxygen concentration management.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a positive electrode which has excellent adhesion to a substrate in a developing step and which can obtain sufficient adhesion even when cured without strictly controlling the oxygen concentration in a curing step. It is an object of the present invention to provide a photosensitive resin composition and a semiconductor device using the same.

[0008]

The present invention provides a compound represented by the general formula (I):
And 100 to 100 parts by weight of a photosensitive diazoquinone compound (B) represented by the formula (II):
A positive photosensitive resin comprising 0.1 to 10 parts by weight of an organosilicon compound (C) represented by the formula (I) and 0.1 to 10 parts by weight of an organosilicon compound (D) represented by the formula (III): A composition.

[0009]

Embedded image

[0010]

Embedded image

[0011]

Embedded image

The polyamide of the formula (I) is synthesized from a diamine having the structure of X, a dicarboxylic acid having the structure of Y and a carboxylic acid derivative having the structure of E. When the polyamide is heated at about 300 to 400 ° C. Dehydration ring closure,
It changes to a heat-resistant resin called polybenzoxazole.
X of the polyamide (1) of the present invention is, for example,

[0013]

Embedded image

However, the present invention is not limited to these. Among these, particularly preferred are:

[0015]

Embedded image

[0016] It is more selected. In the formula (I), Y
Is, for example,

[0017]

Embedded image

However, the present invention is not limited to these. Particularly preferred of these are:

[0019]

Embedded image

[0020] It is more selected. E of the formula ()
Is obtained by reacting a dicarboxylic acid derivative having a structure of Y with a diamine having a structure of X to synthesize a polyamide,
A carboxylic acid derivative having at least one terminal alkenyl group or at least one alkynyl group is reacted with a terminal amino group to perform terminal capping. Examples of the carboxylic acid derivative include 5-norbornene-2,3-dicarboxylic anhydride and maleic anhydride. And the like, but 5-norbornene-2,3-dicarboxylic anhydride is particularly preferred. Further, Z in the formula (1) is, for example,

[0021]

Embedded image

However, the present invention is not limited to these. Z in the formula (1) is used when even higher adhesion is required, but its use ratio b is up to 40.0 mol%. If it exceeds 40.0 mol%, the solubility of the resin is extremely reduced, and undeveloped portions (scum) are generated, so that pattern processing cannot be performed. In using these X, Y, E, and Z, one type or a mixture of two or more types may be used.

The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797, 21
No. 3,669,658. For example, the following are mentioned.

[0024]

Embedded image

[0025]

Embedded image

Among these, the following are particularly preferred.

[0027]

Embedded image

The compounding amount of the photosensitive diazoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide, and if the compounding amount is less than 1 part by weight, the patterning property of the resin becomes poor. On the contrary, if it exceeds 100 parts by weight, the tensile elongation of the film is remarkably reduced.

A dihydropyridine derivative can be added to the positive photosensitive resin composition of the present invention, if necessary, to enhance the photosensitive characteristics. Examples of the dihydropyridine derivative include 2,6-dimethyl-3,5-diacetyl-
4- (2'-nitrophenyl) -1,4-dihydropyridine, 4- (2'-nitrophenyl) -2,6-dimethyl-3,5-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-Dinitrophenyl) -2,6
-Dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine and the like.

The positive photosensitive resin composition of the present invention further comprises an organosilicon compound (C) represented by the general formula (II):
It is important to use together with the organosilicon compound (D) represented by the general formula (III). The silicon compound (C) represented by the general formula (II) is described in Japanese Patent No. 2627632,
It is a known substance described in JP-A-1-215869. The silicon compound (D) represented by the general formula (III) is disclosed in U.S. Pat. Nos. 3,755,354 and 44,607.
It is a known substance disclosed in the specification of Japanese Patent No. 39. In the present invention, by adding both of these organosilicon compounds to a resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone, such as is not found in conventional silane coupling agents, etc., excellent adhesion during development and It has been found that a positive-type photosensitive resin composition capable of obtaining sufficient adhesion can be obtained without strict control of the oxygen concentration during curing.

When the silicon compound (C) represented by the general formula (II) is independently added to a resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone, the adhesion at the time of development and the adhesion after curing are as follows. Can be improved. However, a curing oven that can reduce the oxygen concentration to 10 ppm or less at the time of curing is required. For example, in an oven in which the oxygen concentration can be reduced to only 1 to 3%, peeling occurs. In order to prevent peeling even when cured in an oven in which the oxygen concentration can be reduced to only the 1-3% level, it is necessary to add 20 parts by weight or more of the silicon compound (C) to 100 parts by weight of the polyamide. However, when the amount of addition is increased in such a manner, there is a problem that the storage stability at room temperature is extremely deteriorated and aggregates are generated. On the other hand, the silicon compound (D) represented by the general formula (III) alone has poor adhesion at the time of development and peels off. In order to obtain sufficient adhesion even after curing at an oxygen concentration of 1 to 3%, polyamide 10
It is necessary to add 10 parts by weight or more to 0 parts by weight,
When the amount of addition is increased in such a manner, there is a problem that the residual film ratio at the time of development is significantly reduced.

However, when the silicon compound (C) represented by the general formula (II) and the silicon compound (D) represented by the general formula (III) are used in combination, even when curing is performed at an oxygen concentration of 1 to 3%, It has been found that sufficient adhesion can be obtained after curing. Further, since the total amount of both silicon compounds added may be 20 parts by weight or less based on 100 parts by weight of the polyamide, there is no remarkable decrease in the residual film ratio at the time of development or storage stability at room temperature. The cause of the improvement in adhesion due to the use of both organosilicon compounds is unknown.

The organosilicon compound represented by the general formula (II) is obtained by reacting a silicon compound having an amino group with an acid dianhydride. Examples of the silicon compound having an amino group include 3-aminopropyltrimethoxysilane and N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and the like, but are not limited thereto.

Examples of the acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-
2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride,
Naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 7-
Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5
6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7
Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,
4,5,8-tetrachloronaphthalene-2,3,6,7
-Tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-
Diphenyltetracarboxylic dianhydride, 2,3,3 ',
4'-diphenyltetracarboxylic dianhydride, 3,
3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ", 4"- p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,
3-dicarboxyphenyl) -propane dianhydride, 2,
2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3
-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
Perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride , Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8
-Tetracarboxylic dianhydride, phenanthrene-1,
2,6,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine -2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic dianhydride, etc. And the like, but are not limited thereto. In addition, please use 1
It may be a kind or a mixture of two or more kinds.

Of these, particularly preferred are bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and bis (3 , 4-dicarboxyphenyl) sulfone dianhydride. The amount of the organosilicon compound represented by the general formula (II) to be added to the positive photosensitive resin composition is 0.1 to 10 with respect to 100 parts by weight of the polyamide (A).
Parts by weight. If the amount is less than 0.1 part by weight, sufficient adhesion to the substrate cannot be obtained, and if it exceeds 10 parts by weight, the storage stability at room temperature becomes poor.

The organosilicon compound represented by the general formula (III) can be obtained by reacting a silicon compound having an amino group with an acid anhydride. Examples of the silicon compound having an amino group include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) Examples thereof include, but are not limited to, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and the like.

Examples of the acid anhydride include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride,
Examples thereof include citraconic acid and phthalic anhydride, which can be used alone or in combination of two or more. Of these, maleic anhydride is particularly preferred. The compounding amount of the organosilicon compound represented by the general formula (II) in the positive photosensitive resin composition is polyamide (A) 1
0.1 to 10 parts by weight with respect to 00 parts by weight. If the amount is less than 0.1 part by weight, sufficient adhesion to the substrate cannot be obtained, and if it exceeds 10 parts by weight, the film loss during development is undesirably large.

If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of the present invention. In the present invention, these components are dissolved in a solvent and used in the form of a varnish.
Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3
-Butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc., and may be used alone or as a mixture.

In the method of using the positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after pre-baking at 60 to 130 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine,
An aqueous solution of an alkali such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as alcohol such as methanol or ethanol or a surfactant. Can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As the rinse liquid,
Use distilled water. Next, heat treatment is performed to form an oxazole ring, and a final pattern having high heat resistance is obtained. The positive photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as interlayer insulation for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like.

[0040]

The present invention will be described below in detail with reference to examples. << Example 1 >> * Synthesis of polyamide 443.2 g (0.9 mol) of a dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid with 2 mol of 1-hydroxybenzotriazole was added to hexa. Fluoro-2,2-bis (3-amino-4
-Hydroxyphenyl) propane 366.3 g (1.0
Mol) was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube.
3000 g of -methyl-2-pyrrolidone was added and dissolved. Thereafter, the reaction was carried out at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1, the precipitate was collected by filtration, washed sufficiently with water, and dried under vacuum to obtain the desired polyamide (A-1). Obtained.

* Preparation of Positive Photosensitive Resin Composition 100 g of the synthesized polyamide (A-1), 25 g of diazoquinone (B-1) having a structure of the following formula, and an organosilicon compound (C-1) having a structure of the following formula 5), 5 g of an organosilicon compound (D-1) having a structure of the following formula was dissolved in 250 g of N-methyl-2-pyrrolidone, and then 0.2 μm
To obtain a photosensitive resin composition.

* Characteristic evaluation After coating this positive photosensitive resin composition on a silicon wafer using a spin coater, it was prebaked on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 5 μm. . A g-line stepper exposure machine NSR-1505 is applied to this coating film.
Exposure was performed through a reticle using G3A (manufactured by Nikon Corporation). Next, the exposed portion was dissolved and removed by immersion in a 1.4% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that the pattern was formed. At this time, the remaining film ratio (film thickness after development / film thickness before development) was 87.6.
% And a very high value. Further, in the remaining pattern, no peeling was observed, and it was confirmed that the adhesion at the time of development was excellent. Next, the positive photosensitive resin composition is applied on a silicon wafer in the same manner as above, and prebaked, and then using a clean oven manufactured by Koyo Lindvark for 30 minutes / 150 ° C., 30 minutes / 250 ° C., 30 minutes / 3
Heating and curing were performed in the order of 50 ° C. The oxygen atmosphere concentration at this time was 1-2%. 1 mm square
It was cut into 00 squares. The cellophane tape was stuck on this, and it was going to peel off, but the number of peeled coating films (this is called "the number of peeling after curing") is 0, and the adhesion of the cured film to the silicon wafer is excellent. That was confirmed. Further, the silicon wafer was heated at 125 ° C. and 2.3a.
Pressure cooker processing (PCT) for tm500 hours
After applying a cellophane tape and peeling it off, the number of peeled coating films (referred to as “the number of peelings after high-temperature and high-humidity treatment”) was 0, and It was confirmed that the adhesion after the treatment was also excellent.

The above-mentioned positive photosensitive resin was applied on a simulated element wafer having an Al circuit on the surface so as to have a final thickness of 5 μm, and then subjected to pattern processing and cured in the same manner as above.
After that, it is divided for each chip size, 16Pin DIP (Dual Inl
After mounting on a lead frame for ine package) using a conductive paste, sealing with an epoxy resin for semiconductor encapsulation (Sumitomo Bakelite Co., Ltd., EME-6300H)
16 Pin DIP was obtained. 85 ° C / 8
After treating for 168 hours under the condition of 5% humidity, it was immersed in a 260 ° C. solder bath for 10 seconds, and then subjected to a high-temperature, high-humidity pressure cooker treatment (125 ° C., 2.3 atm, 100% R).
H) was performed to check for open defects in the Al circuit.
The results are shown in Table 1, even for PCT 1000 hours.
There were no semiconductor defects.

Example 2 Evaluation was performed by changing the organosilicon compound C-1 in Example 1 to C-2. << Example 3 >> Organosilicon compound C-1 in Example 1
Was replaced with C-3 for evaluation. << Example 4 >> Organosilicon compound D-1 in Example 1
Was changed to D-2 for evaluation. << Example 5 >> The organosilicon compound D-1 in Example 1
Was replaced with D-3 for evaluation. Example 6 Organosilicon compound C-1 in Example 1
Was evaluated with an addition amount of 3 g and an organosilicon compound D-1 of 1 g. << Example 7 >> Organosilicon compound C-1 in Example 1
Was evaluated with the addition amount of 9 g and the organosilicon compound D-1 being 9 g. Example 8 The evaluation was performed by replacing the photosensitive diazoquinone compound B-1 in Example 1 with B-2. Example 9 A dicarboxylic acid obtained by reacting 1 mol of diphenylsulfone-4,4′-dicarboxylic acid instead of 1 mol of diphenylether-4,4′-dicarboxylic acid in the synthesis of polyamide in Example 1. A polyamide (A-2) was synthesized using the derivative, and the other evaluations were performed in the same manner as in Example 1.

Example 10 In the synthesis of the polyamide in Example 1, 0.8 mol of terephthalic acid and 0.2 mol of isophthalic acid were reacted instead of 1 mol of diphenyl ether-4,4'-dicarboxylic acid. A polyamide (A-3) was synthesized using the obtained dicarboxylic acid derivative, and the other evaluations were the same as in Example 1. << Example 11 >> In the synthesis of polyamide in Example 1, hexafluoro-2,2-bis (3-amino-4-
(Hydroxyphenyl) propane instead of 1 mole 3,
Polyamide (A-4) was synthesized using 1 mol of 3′-diamino-4,4′-dihydroxydiphenylsulfone, and the other evaluations were performed in the same manner as in Example 1. Example 12 In the synthesis of the polyamide in Example 1, hexafluoro-2,2-bis (3-amino-4-
(Hydroxyphenyl) propane 3 moles instead of 1 mole
Polyamide (A-5) was synthesized using 1 mol of '-diamino-4,4'-dihydroxydiphenyl ether,
Otherwise, the same evaluation as in Example 1 was performed. Example 13 In the synthesis of polyamide in Example 1, hexafluoro-2,2-bis (3-amino-4-
329.6 g (0.9) of hydroxyphenyl) propane
Mol), and 24.9 g (0.1 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added instead.
6) was synthesized, and the others were evaluated in the same manner as in Example 1. Example 14 Polyamide (A-7) was synthesized using 0.2 mol of maleic anhydride instead of 0.2 mol of 5-norbornene-2,3-dicarboxylic anhydride in the synthesis of polyamide in Example 1. Otherwise, the same evaluation as in Example 1 was performed. << Example 15 >> The photosensitive diazoquinone compound B-1 in Example 1 was replaced with B-3, and the addition amount was further reduced from 25 g to 15 g, and the addition amount of the organosilicon compound D-1 was changed to 0.5 g. An evaluation was performed. << Example 16 >> The photosensitive diazoquinone compound B-1 in Example 1 was changed to B-4, and the addition amount was further increased from 25 g to 32 g, and the addition amount of the organosilicon compound C-1 was increased to 0.5 g. An evaluation was performed. As shown in Table 1, the results of Examples 2 to 16 all showed good performance.

Comparative Example 1 Evaluation was made in Example 1 without adding the organosilicon compound C-1 or the organosilicon compound D-1. As a result, as shown in Table 1, the number of peelings after curing was 100, which was very poor. In the semiconductor reliability evaluation, a defect occurred. << Comparative Example 2 >> In Example 1, the organosilicon compound C-1 was used.
The evaluation was performed without the addition of. As a result, the number of peelings after curing was 66, and the number of peelings after high-temperature and high-humidity treatment was 100, which was very poor. In the semiconductor reliability evaluation, a defect occurred. << Comparative Example 3 >> In Example 1, the organosilicon compound D-1 was used.
The evaluation was performed without the addition of. As a result, the number of peelings after curing was very poor at 100. In the semiconductor reliability evaluation, a defect occurred. << Comparative Example 4 >> In Example 1, the organosilicon compound C-1 was used.
Was evaluated without adding the organosilicon compound D-1 to an amount of 15 g. As a result, the number of peelings after curing was 5 and the number of peelings after high-temperature and high-humidity treatment was 90, which was very poor.
In the semiconductor reliability evaluation, a defect occurred. << Comparative Example 5 >> In Example 1, the organosilicon compound D-1 was used.
Was evaluated without adding the organosilicon compound C-1 with the addition amount of 8 g. As a result, the number of peelings after the high-temperature and high-humidity treatment was very low at 37. In the semiconductor reliability evaluation, a defect occurred. << Comparative Example 6 >> In Example 1, the organosilicon compound D-1 was used.
Was evaluated without adding the organosilicon compound C-1 to an amount of 15 g. As a result, the residual film ratio after development was as very poor as 67.1%. Table 1 shows the evaluation results of Examples 1 to 16 and Comparative Examples 1 to 6 described above.

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

[Table 1]

[0054]

According to the present invention, a positive-type photosensitive composition having excellent adhesion to a substrate in a development step and sufficient adhesion even when cured without strict control of oxygen concentration in a curing step. Resin composition and a highly reliable semiconductor device using the same.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI // H01L 21/312 H01L 21/30 502R

Claims (7)

[Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (I) and a photosensitive diazoquinone compound (B)
From 1 to 100 parts by weight, 0.1 to 10 parts by weight of the organosilicon compound (C) represented by the general formula (II) and 0.1 to 10 parts by weight of the organosilicon compound (D) represented by the general formula (III) A positive-type photosensitive resin composition comprising: Embedded image Embedded image Embedded image 2. R in the organosilicon compound (C)
The positive photosensitive resin composition according to claim 1, wherein ₅ is selected from the following. Embedded image 3. R in the organosilicon compound (D)
The positive photosensitive resin composition according to claim 1, wherein ₉ has the following structure. Embedded image 4. X in the polyamide of the general formula (I)
Is selected from the following: The positive photosensitive resin composition according to claim 1, 2 or 3. Embedded image 5. Y in the polyamide of the general formula (I)
Is selected from the following: The positive photosensitive resin composition according to claim 1, 2 or 3. Embedded image 6. The positive photosensitive resin composition according to claim 1, wherein the photosensitive diazoquinone compound (B) is selected from the following. Embedded image 7. The semiconductor device according to claim 1, wherein the film thickness of the positive photosensitive resin composition after heat dehydration and ring closure is 0.1 to 20 μm. Apply,
A semiconductor device made by pre-baking, exposing, developing and heating.