JP2001215698A - Positive type photosensitive resin composition and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive resin composition excellent in adhesion to metal copper after curing, and a semiconductor device using the composition. SOLUTION: The positive type photosensitive resin composition comprises 100 pts.wt. polyamide (A), 1-100 pts.wt. photosensitive diazoquinone compound (B) and 0.05-20 pts.wt. organotitanium-based compound (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition capable of obtaining excellent adhesion after curing with a copper-based metal, 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 for a surface protective film and an interlayer insulating film of a semiconductor element. Demand for high dielectric constant, low dielectric constant, and improved adhesion with wiring metals such as copper and titanium by shifting to chip size package (CSP) and wafer level package (WLP) etc. Therefore, a high-performance polyimide resin has been required. In particular, copper wiring is rapidly being adopted as a centerpiece of high speed replacement for conventional aluminum wiring, and the current polyimide has a disadvantage that adhesion is very poor. On the other hand, in these applications, the process of imparting photosensitivity to the polyimide resin itself has recently been receiving attention because the process is long and complicated in the conventional non-photosensitive polyimide. For example, as a photosensitive polyimide resin, the following formula ( 4) and so on.

[0003]

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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 this positive photosensitive resin is such that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, and the exposure causes the diazoquinone compound to undergo a chemical change and become soluble in the alkaline aqueous solution. By utilizing the difference in solubility between the exposed part and the unexposed part, a coating film pattern can be formed only in the unexposed part.

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, wet etching using a developing solution is performed at the time of development. However, at the time of development, there is a problem that an unexposed portion of the coating film, which should be originally left, is completely peeled off or floated. In addition, such a photosensitive resin is subjected to heat treatment (curing) after pattern processing to form an oxazole ring, to form a permanent film having excellent heat resistance and mechanical properties, and to be used as a surface coating material or an interlayer insulating film of a semiconductor. . However, the adhesiveness after curing is also insufficient, and there is also a problem that the resin is peeled off from the substrate especially when a high-temperature moisture absorption treatment is performed.

Further, Japanese Patent No. 2627632 discloses a silane-modified carboxylic acid derivative as an adhesion aid for polyimide. When this is added to the photosensitive resin disclosed in Japanese Patent Publication No. 1-46862, the adhesiveness during development and the adhesiveness after curing are improved. But,
There is a problem that adhesion to copper as the wiring metal is weak. At present, when copper wiring is used, a metal for improving adhesion (titanium, chromium, etc.) is provided in advance on the top and bottom of copper, or a thin coating of adhesion improving primer is applied. Need to be kept.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive resin composition having excellent adhesion to copper metal after curing and a semiconductor device using the same.

[0008]

According to the present invention, there is provided a compound represented by the general formula (1):
100 parts by weight of a polyamide (A), 1 to 100 parts by weight of a photosensitive diazoquinone compound (B), and an organotitanium compound (C) represented by formulas (2) and (3).
It is a positive photosensitive resin composition comprising 0.05 to 20 parts by weight.

[0009]

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[0010]

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[0011]

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The polyamide of the formula (1) is composed of bisaminophenol having the structure of X and dicarboxylic acid having the structure of Y. When this polyamide is heated at about 300 to 400 ° C., the ring is closed, and the heat resistance of polybenzoxazole is obtained. Changes to resin.

X of the polyamide (1) of the present invention is, for example,

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

[0015]

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[0016] It is more selected. Also, Y of the formula (1)
Is, for example,

[0017]

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

[0019]

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[0020] It is more selected.

Further, Z in the formula (1) is, for example,

Embedded image Etc., but are not limited to these.

Z in the formula (1) is used in the case of a substrate requiring even higher adhesiveness, and its use ratio b can be used up to 40.0 mol%. 40.
If it exceeds 0 mol%, the solubility of the resin is extremely reduced, scum is generated, and pattern processing cannot be performed. When using X, Y, 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]

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[0025]

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Among these, the following are particularly preferred.

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight based on 100 parts by weight of the polyamide. If the compounding amount is less than 1 part by weight, the patterning property of the resin is poor. Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film is significantly 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, for example, 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-carbomethoxy-1,4-dihydropyridine and the like can be mentioned.

In the positive photosensitive resin composition of the present invention, it is important to further use the organic titanium compound (C) represented by the general formulas (2) and (3). In the present invention, when these organotitanium-based compounds are added to a resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone, sufficient adhesion to copper metal after curing, which cannot be seen with conventional silane coupling agents, etc. It was found that a positive photosensitive resin composition capable of obtaining the following was obtained.

The organic titanium compounds represented by the general formulas (2) and (3) include, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl) Pyrophosphite) titanate, tetraoctylbis (dioctylpyrophosphite) titanate, tetra (2,2-diallyloxymethyl-1)
-Butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltri (N-aminoethylaminoethyl) titanate and the like. It is not limited to. In use, one kind or a mixture of two or more kinds may be used.

The amount of the organic titanium compound represented by the general formulas (2) and (3) in the positive photosensitive resin composition is 0.05 to 20 parts by weight based on 100 parts by weight of the polyamide (A). is there. If the amount is less than 0.05 part by weight, sufficient adhesion to the substrate cannot be obtained, and if the amount exceeds 20 parts by weight, aggregation may occur, which is not preferable.

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 and the like 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, for example, a silicon wafer, ceramic, 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, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt or an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant thereto 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. Distilled water is used as the rinsing liquid. 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 comprises:
It is useful not only for semiconductors but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films, etc., but is particularly effective when used for semiconductors. When the positive photosensitive resin composition according to the present invention is used for a semiconductor device using a copper-based metal in particular, a highly reliable semiconductor device can be obtained. As a method for manufacturing a semiconductor device, a conventionally known method can be used.

[0035]

The present invention will be described below in detail with reference to examples. << Example 1 >> * Synthesis of polyamide 492.5 parts by weight (1 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 hex. Fluoro-2,2-bis (3-amino-4
-Hydroxyphenyl) propane (329.6 parts by weight, 0.9 mol) was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a material inlet, and a dry nitrogen gas inlet tube, and N-methyl-2 was added. -3000 parts by weight of pyrrolidone were added and dissolved. Thereafter, the reaction was carried out at 75 ° C. for 12 hours using an oil bath. Next, 5-norbornene-2,3-dissolved in 500 parts by weight of N-methyl-2-pyrrolidone
32.8 parts by weight (0.2 mol) of dicarboxylic anhydride 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 parts by weight of synthesized polyamide (A-1), 25 parts by weight of diazoquinone (B-1) having a structure of the following formula, and an organic titanium-based compound having a structure of the following formula After dissolving 1 part by weight of compound (C-1) in 250 parts by weight of γ-butyrolactone,
Filtration through a 0.2 μm filter gave a photosensitive resin composition.

* Characteristics Evaluation The positive photosensitive resin composition was applied on a silicon wafer by using a spin coater on a substrate on which titanium and copper were sputtered, and then dried on a hot plate at 120 ° C. for 4 minutes. A coating film having a thickness of about 5 μm was obtained. A g-line stepper exposure machine NSR-1505G3A (Nikon Corporation)
From 50 mJ / cm ² to 20 through a reticle
mJ / cm ² increase at a time and was exposed to 540mJ / cm ^2. Next, the exposed portion was dissolved and removed by immersion in a 2.38% 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. Separately, a positive-type photosensitive resin composition is similarly applied onto a silicon wafer on a substrate on which titanium and then copper have been sputtered, and prebaked. Then, using a Koyo Lindvark clean oven, 30 minutes / 150 ° C., 30 minutes / The resin was heated at 320 ° C. in order and further heated at a nitrogen concentration of about 100 ppm or less. The obtained coating film was cut into 100 squares of 1 mm square. The cellophane tape was attached and peeled off, and the coating film was about to be peeled off from the substrate. However, the number of peeled coating films (referred to as “the number of peelings after curing”) was 0, and the cured film on the silicon wafer was removed. It was also confirmed that the adhesiveness with copper was excellent.

Example 2 Evaluation was performed by changing the organic titanium compound C-1 in Example 1 to C-2. << Example 3 >> The organic titanium compound C- in Example 1
Evaluation was performed by replacing 1 with C-3. Example 4 The evaluation was performed by replacing the photosensitive diazoquinone compound B-1 in Example 1 with B-2. Example 5 In the synthesis of a polyamide in Example 1, instead of an aromatic dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid with 2 mol of 1-hydroxybenzotriazole,
Using a dicarboxylic acid derivative obtained by reacting 1 mol of diphenylsulfone-4,4'-dicarboxylic acid with 2 mol of hydroxybenzotriazole, polyamide (A-
2) was synthesized, and the others were evaluated in the same manner as in Example 1.

Example 6 In the synthesis of the polyamide in Example 1, 1 mol of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxybenzotriazole 2
And a dicarboxylic acid derivative obtained by reacting 0.8 mol of terephthalic acid, 0.2 mol of isophthalic acid and 2 mol of 1-hydroxybenzotriazole instead of the aromatic dicarboxylic acid derivative obtained by reacting Was used to synthesize a polyamide (A-3), and the others were evaluated in the same manner as in Example 1. Example 7 In the synthesis of polyamide in Example 1, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane. Was used to synthesize a polyamide (A-4), and the others were evaluated in the same manner as in Example 1. Example 8 In the synthesis of the polyamide in Example 1, 3,3′-diamino-4,4′-dihydroxydiphenyl ether was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane. Was used to synthesize a polyamide (A-5), and the other evaluations were performed in the same manner as in Example 1. Example 9 In the synthesis of polyamide in Example 1, 323.6 parts by weight of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added (0.3% by weight).
9 mol), and 24.9 parts by weight (0.1 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added instead. 6) was synthesized, and the others were evaluated in the same manner as in Example 1.

Comparative Example 1 An evaluation was performed by changing the organic titanium compound in Example 1 to the organic silicon compound D-1. << Comparative Example 2 >> An evaluation was performed by changing the organic titanium-based compound in Example 1 to the organic silicon compound D-2. << Comparative Example 3 >> Evaluation was made in Example 1 without adding an organic titanium-based compound.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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Table 1 shows the evaluation results of Examples 1 to 9 and Comparative Examples 1 to 3.

[Table 1]

[0049]

According to the present invention, it is possible to obtain a positive photosensitive resin composition capable of obtaining sufficient adhesion to a copper metal on a substrate after curing, and a highly reliable semiconductor device using the same. .

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA10 AA14 AA20 AB16 AC01 AD03 BE01 CB26 CB33 CB43 CB45 CC06 CC20 DA18 FA01 FA29 4J002 CL071 EQ016 EV216 EZ007 GP03

Claims (6)

[Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
A positive photosensitive resin composition comprising 1 to 100 parts by weight and 0.05 to 20 parts by weight of an organic titanium compound (C) represented by formulas (2) and (3). Embedded image Embedded image Embedded image 2. R ₅ in the organotitanium compound (C),
R _6, R ₇ The positive photosensitive resin composition according to claim 1 comprising been selected from the following. Embedded image Embedded image Embedded image 3. X in the polyamide of the general formula (1)
Is selected from the following: The positive photosensitive resin composition according to claim 1 or 2, wherein Embedded image 4. Y in the polyamide of the general formula (1)
Is selected from the following: The positive photosensitive resin composition according to claim 1 or 2, wherein Embedded image 5. The positive photosensitive resin composition according to claim 1, wherein the photosensitive diazoquinone compound (B) is selected from the following. Embedded image 6. A polybenzoxazole resin comprising 100 parts by weight of a polyamide (A) represented by the general formula (1), 1 to 100 parts by weight of a photosensitive diazoquinone compound (B), and an organic titanium represented by the general formula (2) Compound (C) 0.05
After applying a positive photosensitive resin composition of up to 20 parts by weight on a semiconductor element, prebaking, exposing, developing and patterning and heating and curing, the cured resin has a thickness of 0%. A semiconductor device having a thickness of 1 to 50 μm.