JP3422703B2 - Positive photosensitive resin composition and semiconductor device using the same - 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-working type which is excellent in adhesion to a substrate in a developing process and which can obtain sufficient adhesion even when cured without strict control of oxygen concentration in the curing process. 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 properties and mechanical properties has been used as a surface protective film and an interlayer insulating film for semiconductor devices. , Large size, thin package, small size, transition to surface mounting by solder reflow, etc., there is a demand for remarkable improvement in heat cycle resistance, heat shock resistance, etc. It's coming. On the other hand, a technique of imparting photosensitivity to the polyimide resin itself has recently been attracting attention, and examples thereof include a photosensitive polyimide resin represented by the following formula (X).

[0003]

[Chemical 9]

If this is used, a part of the pattern forming process can be simplified and the process can be shortened.
Since a solvent such as methyl-2-pyrrolidone is required, there is a problem in safety and handling. Therefore, recently, a positive type 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 characteristics, and fine workability, and has potential as a resin for not only wafer coating but also interlayer insulation. The developing mechanism of this positive photosensitive resin is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, but upon exposure, the diazoquinone compound undergoes a chemical change and becomes soluble in the alkaline aqueous solution.
By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion, it is possible to create a coating film pattern only in the unexposed portion.

When the photosensitive resin disclosed in Japanese Patent Publication No. 1-46862 is actually used, the problem is the adhesion to the substrate, especially the silicon wafer.
That is, when performing wet etching using a developing solution in the developing step, there is a problem that the coating film of the unexposed portion which should be originally left may peel off or float up. Further, after patterning, an oxazole ring is formed in a heat treatment (curing) step, but the adhesion after curing is insufficient, and there is also a problem that the coating film peels off from the substrate especially when a 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 disclosed in Japanese Patent Publication No. 1-46862, the adhesiveness at the time of development,
There is an improvement in adhesion after curing. However, it is important to control the oxygen atmosphere concentration during the curing process.
If it is not less than 0 ppm, sufficient adhesion cannot be obtained. In order to carry out the curing under the atmospheric condition of the oxygen concentration of 10 ppm or less, an oven and a diffusion furnace having excellent airtightness are required, and a considerably large amount of investment is required. For this reason, the semiconductor manufacturing side desires a surface coating material that can obtain sufficient adhesion even if it is cured by a simple oxygen concentration control.

[0007]

SUMMARY OF THE INVENTION The present invention is a positive film which is excellent in adhesion to a substrate in a developing process and which can obtain sufficient adhesion even if cured without strict control of oxygen concentration in a curing process. An object of the present invention is to provide a mold type photosensitive resin composition and a semiconductor device using the same.

[0008]

The present invention has the general formula (I)
And 100 parts by weight of the polyamide (A), 1 to 100 parts by weight of the photosensitive diazoquinone compound (B), and the general formula (II)
A positive photosensitive resin comprising 0.1 to 10 parts by weight of the organosilicon compound (C) represented by the formula (1) and 0.1 to 10 parts by weight of the organosilicon compound (D) represented by the general formula (III). It is a composition.

[0009]

[Chemical 10]

[0010]

[Chemical 11]

[0011]

[Chemical 12]

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

[0013]

[Chemical 13]

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

[0015]

[Chemical 14]

It is selected from the above. Also, Y in formula (I)
Is, for example,

[0017]

[Chemical 15]

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

[0019]

[Chemical 16]

It is selected from the above. In addition, E of 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,
The terminal carboxylic acid derivative having at least one alkenyl group or alkynyl group at the terminal amino group is reacted to perform terminal blocking, and examples of the carboxylic acid derivative include 5-norbornene-2,3-dicarboxylic acid anhydride and maleic anhydride. Etc., but 5-norbornene-2,3-dicarboxylic acid anhydride is particularly preferable. Furthermore, Z in formula (1) is, for example,

[0021]

[Chemical 17]

However, the present invention is not limited to these. Z in the formula (1) is used when higher adhesiveness is required, and the usage ratio b is up to 40.0 mol%. When it exceeds 40.0 mol%, the solubility of the resin is extremely lowered, and undeveloped residue (scum) occurs, and pattern processing cannot be performed. In addition, when using these X, Y, E, and Z, each may be one kind or a mixture of two or more kinds.

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
It is a substance known from No. 3, No. 3,669,658. For example, the following may be mentioned.

[0024]

[Chemical 18]

[0025]

[Chemical 19]

Among these, the following are particularly preferable.

[0027]

[Chemical 20]

The photosensitive diazoquinone compound (B) is blended in the polyamide (A) in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the polyamide. If the blending amount is less than 1 part by weight, the patterning property of the resin will be poor. If the amount exceeds 100 parts by weight, the tensile elongation of the film is remarkably reduced.

If desired, a dihydropyridine derivative may be added to the positive photosensitive resin composition of the present invention in order to enhance the photosensitivity. 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-dicarboethoxy-1,4-dihydropyridine, 4- (2 ′, 4′-Dinitrophenyl) -2,6
-Dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine and the like can be mentioned.

In the positive photosensitive resin composition of the present invention, the organosilicon compound (C) represented by the general formula (II) is further used.
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. Further, the silicon compound (D) represented by the general formula (III) is represented by US Pat. Nos. 3,755,354 and 44607.
It is a known substance disclosed in the specification of No. 39. In the present invention, by adding these both organosilicon compounds to a resin composition consisting of a polybenzoxazole precursor and a photosensitive diazoquinone, excellent adhesion at the time of development, which is not seen in conventional silane coupling agents and the like. It was found that a positive-type photosensitive resin composition having sufficient adhesion can be obtained without strict control of oxygen concentration during curing.

When the silicon compound (C) represented by the general formula (II) is added alone to the resin composition comprising the polybenzoxazole precursor and the photosensitive diazoquinone, the adhesiveness at the time of development and the adhesiveness after curing are Can be improved. However, a curing oven is required so that the oxygen concentration can be 10 ppm or less at the time of curing. For example, peeling occurs in an oven in which the oxygen concentration can be reduced only to the level of 1 to 3%. It is necessary to add 20 parts by weight or more of the silicon compound (C) to 100 parts by weight of polyamide in order to prevent the oxygen concentration from being peeled off even when cured in an oven that can reduce the oxygen concentration to only 1 to 3% level. However, there is a problem in that storage stability at room temperature is extremely deteriorated and aggregates are generated when the amount of such addition is increased. On the other hand, when the silicon compound (D) represented by the general formula (III) is used alone, the adhesion during development is poor and peeling occurs. Furthermore, even if curing is performed 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 this way, there is a problem that the residual film rate during 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 together, even if curing is carried out at an oxygen concentration level of 1 to 3%, It has been found that sufficient adhesion can be obtained after curing. Furthermore, since the total amount of both silicon compounds added may be 20 parts by weight or less with respect to 100 parts by weight of polyamide, there is no significant decrease in the residual film rate during development and deterioration of storage stability at room temperature. The cause of this improvement in adhesion due to the combined 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
Examples thereof include, but are not limited to,-(2-aminoethyl) -3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane.

Examples of the acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid. Dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic 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 acid dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid 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 (2,2
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. However, the present invention is not limited to these. In addition, when using 1
It may be one kind or a mixture of two or more kinds.

Of these, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and bis (3 , 4-dicarboxyphenyl) sulfone dianhydride. The compounding amount of the organosilicon compound represented by the general formula (II) in 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 parts by weight, sufficient adhesion to the substrate cannot be obtained, and if it exceeds 10 parts by weight, storage stability at room temperature deteriorates, which is not preferable.

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 and 3-aminopropyltriethoxysilane.

Examples of acid anhydrides include maleic anhydride, chloromaleic anhydride, cyanomaleic anhydride,
Examples thereof include citraconic acid and phthalic anhydride, and these can be used alone or in combination of two or more kinds. Of these, maleic anhydride is particularly preferable. The compounding amount of the organosilicon compound represented by the general formula (II) to the positive photosensitive resin composition is polyamide (A) 1
It is 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 to form a varnish for use.
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, 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 and the like can be mentioned, and they may be used alone or in combination.

In the method of using the positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support such as 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 prebaking at 60 to 130 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic rays. As the actinic rays, X rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. Next, the irradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, di-n. -Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine,
Aqueous solutions of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and aqueous solutions in which an appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol and a surfactant are added. Can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As a rinse liquid,
Use distilled water. Next, heat treatment is performed to form an oxazole ring and obtain a final pattern having high heat resistance. The positive photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films and the like.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 * Synthesis of Polyamide 443.2 g (0.9 mol) of dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid with 2 mol of 1-hydroxybenzotriazole and hexa Fluoro-2,2-bis (3-amino-4)
-Hydroxyphenyl) propane 366.3 g (1.0
Mol) and N were placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and N
-Methyl-2-pyrrolidone (3000 g) was added and dissolved. Then, 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 acid anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the reaction was terminated by further stirring for 12 hours. 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 thoroughly with water, and dried under vacuum to obtain the target polyamide (A-1). Obtained.

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

* Characteristic Evaluation This positive type photosensitive resin composition was applied on a silicon wafer by using a spin coater and then prebaked at 120 ° C. for 4 minutes to obtain a coating film having a film thickness of about 5 μm. . To this coating, g-line stepper exposure machine NSR-1505
Exposure was performed using G3A (manufactured by Nikon Corporation) through a reticle. 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. The residual film ratio (film thickness after development / film thickness before development) at this time was 87.6.
%, Which was a very high value. Further, no peeling was observed in the remaining pattern, and it was confirmed that the adhesiveness during development was excellent. Then, the positive type photosensitive resin composition was applied onto a silicon wafer in the same manner as above, prebaked, and then using a clean oven made by Koyo Lindbark, 30 minutes / 150 ° C., 30 minutes / 250 ° C., 30 minutes / Three
It was heated and cured in the order of 50 ° C. The oxygen atmosphere concentration at this time was 1 to 2%. The obtained coating film is 1mm square
It was cut into 00 pieces. The cellophane tape was attached to this, and it was tried to peel it off, but the number of peeled coating films (this is called "the number of peelings after curing") is 0, and the adhesion of the cured film to the silicon wafer is excellent. I was able to confirm that. Furthermore, this silicon wafer was heated at 125 ° C. for 2.3a.
Pressure cooker processing (PCT) for tm500 hours
After applying, cellophane tape was similarly attached, and peeled off and evaluated. The number of peeled coating films (referred to as "the number of peelings after high temperature and high humidity treatment") was 0. It was confirmed that the adhesion after the treatment was also excellent.

The above-mentioned positive type photosensitive resin was applied on a simulated element wafer having an Al circuit on the surface so that the final thickness was 5 μm, and then pattern processing was performed and curing was performed in the same manner as above.
Then, divide by chip size, 16Pin DIP (Dual Inl
ine Package) lead frame using conductive paste, and then encapsulated with epoxy resin for semiconductor encapsulation (Sumitomo Bakelite Co., Ltd., EME-6300H),
I got 16 Pin DIP. These packages are 85 ℃ / 8
After processing for 168 hours under the condition of 5% humidity, immerse in a solder bath at 260 ° C for 10 seconds, and then pressure cooker treatment at high temperature and high humidity (125 ° C, 2.3 atm, 100% R).
H) was applied to check the open failure of the Al circuit.
As shown in Table 1, the results are shown in PCT 1000 hours,
There were no semiconductor defects.

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

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

Comparative Example 1 Evaluation was carried out 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 addition, a defect occurred in the semiconductor reliability evaluation. << Comparative Example 2 >> Organosilicon compound C-1 in Example 1
Was evaluated without adding. As a result, the number of peelings after curing was 66, and the number of peelings after the high temperature and high humidity treatment was 100, which were very poor. In addition, a defect occurred in the semiconductor reliability evaluation. << Comparative Example 3 >> Organosilicon compound D-1 in Example 1
Was evaluated without adding. As a result, the number of peelings after curing was 100, which was very bad. In addition, a defect occurred in the semiconductor reliability evaluation. << Comparative Example 4 >> Organosilicon compound C-1 in Example 1
Was added to 15 g, and evaluation was performed without adding the organosilicon compound D-1. As a result, the number of peelings after curing was 5, and the number of peelings after the high temperature and high humidity treatment was 90, which were very poor.
In addition, a defect occurred in the semiconductor reliability evaluation. << Comparative Example 5 >> Organosilicon compound D-1 in Example 1
The amount of was added to 8 g, and the evaluation was performed without adding the organosilicon compound C-1. As a result, the number of peeling after the high temperature and high humidity treatment was 37, which was very bad. In addition, a defect occurred in the semiconductor reliability evaluation. << Comparative Example 6 >> Organosilicon compound D-1 in Example 1
The amount of was added to 15 g, and the evaluation was performed without adding the organosilicon compound C-1. As a result, the residual film rate after development was 67.1%, which was extremely poor. The evaluation results of Examples 1 to 16 and Comparative Examples 1 to 6 are shown in Table 1.

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Table 1]

[0054]

According to the present invention, a positive-type photosensitive material which has excellent adhesion to a substrate in the developing step, and has sufficient adhesion even when cured without strict control of oxygen concentration in the curing step. A resin composition and a highly reliable semiconductor device using the same can be obtained.

Continuation of the front page (56) Reference JP-A-5-197153 (JP, A) JP-A-7-128846 (JP, A) JP-A-6-95368 (JP, A) JP-A-9-302221 (JP , A) JP-A-9-146274 (JP, A) JP-A-9-222729 (JP, A) JP-A-6-348016 (JP, A) JP-A-10-10727 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/18

Claims (7)

(57) [Claims] 1. A photosensitive diazoquinone compound (B) and 100 parts by weight of a polyamide (A) represented by the general formula (I).
From 1 to 100 parts by weight and 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 photosensitive resin composition comprising: [Chemical 1] [Chemical 2] [Chemical 3] 2. R in the organosilicon compound (C)
The positive photosensitive resin composition according to claim 1, wherein ₅ is selected from the following. [Chemical 4] 3. R in the organosilicon compound (D)
_9. The positive photosensitive resin composition according to claim 1, wherein ₉ has the following structure. [Chemical 5] 4. X in the polyamide of general formula (I)
The positive photosensitive resin composition according to claim 1, 2 or 3, selected from the following. [Chemical 6] 5. Y in the polyamide of general formula (I)
The positive photosensitive resin composition according to claim 1, 2 or 3, selected from the following. [Chemical 7] 6. The positive photosensitive resin composition according to claim 1, 2, 3, 4 or 5, wherein the photosensitive diazoquinone compound (B) is selected from the following. [Chemical 8] 7. The positive photosensitive resin composition according to claim 1, 2, 3, 4, 5 or 6 is applied onto a semiconductor device so that the film thickness after heat dehydration ring closure is 0.1 to 20 μm. Apply
A semiconductor device formed by pre-baking, exposing, developing and heating.