JP2003255533A - Positive photosensitive resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition showing excellent suitability to edge rinse. <P>SOLUTION: The positive photosensitive resin composition comprises 100 pts.wt. polyamide resin represented by formula (1), 1 to 100 pts.wt. photosensitive diazoquinone compound (B) and 0.001 to 10 pts.wt. fluorine-free surfactant (C). <P>COPYRIGHT: (C)2003,JPO

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 excellent in edge rinse property and a semiconductor device.

[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 device. There is a demand for significant improvement in heat cycle resistance, heat shock resistance, etc. due to the trend toward larger size, larger size, thinner semiconductor device, smaller size, and surface mounting by solder reflow, and higher performance resin is required. It's starting to happen. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has been attracting attention, and examples thereof include a photosensitive polyimide resin represented by the following formula (2).

[0003]

[Chemical 2]

If this is used, part of the pattern forming process can be simplified, and it has the effect of shortening the process and improving the yield, but since a solvent such as N-methyl-2-pyrrolidone is required during development, it is safe. There is a problem with the handling and handling. Therefore, recently, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has been developed, and a positive photosensitive resin composition composed of a polybenzoxazole precursor and a diazoquinone compound that is a photosensitive material has been disclosed (for example, , Patent Document 1.). It has high heat resistance, excellent electrical properties, and fine workability, and has potential as a resin composition for not only wafer coating but also interlayer insulation. The developing mechanism of this positive photosensitive resin composition is that the unexposed portion of the diazoquinone compound is insoluble in an alkaline aqueous solution, but the exposure causes the diazoquinone compound to undergo a chemical change,
It becomes soluble in 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 such a polyimide resin composition is used for a semiconductor, a removability of the polyimide resin composition on the peripheral portion (edge) of a silicon wafer is an item required from the side of manufacturing a semiconductor device. In a semiconductor manufacturing process, a silicon wafer is transferred by a dedicated arm, but if the polyimide resin composition remains around the silicon wafer at this time, a problem arises that the semiconductor manufacturing apparatus is contaminated. Therefore, in the semiconductor manufacturing process, a step (edge cutting) of removing the polyimide resin composition around the silicon wafer is generally performed. As a typical edge-cutting method, in the case of a polyimide resin composition, the resin composition is dispensed on a silicon wafer and spin-coated, but at the final stage, the peripheral portion is edge-rinsed and then dried on a hot plate. There is a way to do it. However, in this method, the polyimide resin composition often recedes from the surroundings to cause sink marks during drying on a hot plate, which causes an obstacle in the semiconductor manufacturing process. A positive photosensitive resin composition based on a polybenzoxazole precursor resin also has a problem in this edge rinse property and needs to be improved (see, for example, Patent Document 2).

[0006]

[Patent Document 1] Japanese Patent Publication No. 1-46862 (pages 1 to 8)

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a positive type photosensitive resin composition having excellent edge rinse property while maintaining good developing performance.

[0008]

[Means for Solving the Problems] 100 parts by weight of a polyamide resin (A) represented by the general formula (1), 1 to 100 parts by weight of a photosensitive diazoquinone compound (B), and a non-fluorine-containing surfactant (C) of 0.1. A positive photosensitive resin composition containing 001 to 10 parts by weight.

[0009]

[Chemical 3]

In a more preferred form, the non-fluorine-containing surfactant (C) has a siloxane structure, and the non-fluorine-containing surfactant (C) has a dimethylpolysiloxane-polyoxyalkylene copolymer structure. It is a positive photosensitive resin composition. A semiconductor device manufactured using the positive photosensitive resin composition, wherein the positive photosensitive resin composition has a film thickness of 0.1 to 30 μm after dehydration and ring closure.
The semiconductor device is obtained by applying it onto a semiconductor element so as to obtain, and pre-baking, exposing, developing, and heating.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION X in a polyamide resin containing a structure represented by the general formula (1) used in the present invention represents a divalent to tetravalent cyclic compound group, R ₁ is a hydroxyl group, OR ₃ And m is an integer of 0 to 2, which may be the same or different.
Y represents a divalent to hexavalent cyclic compound group, R ₂ is a hydroxyl group,
Carboxyl group, in _{O-R 3, COO-R} 3, n is 0-4
Of integers, which may be the same or different. Here, R ₃ is an organic group having 1 to 15 carbon atoms. However, when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. When R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.

The polyamide resin containing the structure represented by the general formula (1) is blended, if necessary, with a compound selected from a diamine having a structure of X, bis (aminophenol), 2,4-diaminophenol and the like. A compound selected from a silicone diamine having a Z structure and a tetracarboxylic acid anhydride, a trimellitic acid anhydride, a dicarboxylic acid or a dicarboxylic acid dichloride, a dicarboxylic acid derivative, a hydroxydicarboxylic acid, a hydroxydicarboxylic acid derivative or the like having a Y structure; It is obtained by reacting. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like.

[0013] In the polyamide resin containing the structure represented by the general formula _{(1), O-R 3} , COO-R 3 as a substituent of O-R _3, Y as a substituent of X is a hydroxyl group, a carboxyl group For the purpose of adjusting the solubility in the aqueous alkaline solution of 1, is a group protected by an organic group having 1 to 15 carbon atoms, and if necessary, a hydroxyl group and a carboxyl group may be protected. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, tert-butoxycarbonyl group, phenyl group,
Examples thereof include a benzyl group, a tetrahydrofuranyl group and a tetrahydropyranyl group. About 30% of this polyamide resin
When heated at 0 to 400 ° C., dehydration ring closure occurs, and a heat resistant resin is obtained in the form of polyimide, polybenzoxazole, or a copolymer of both.

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

[Chemical 4] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 5] It is selected more preferably, and two or more kinds of these may be used.

Further, Y of the polyamide resin of the general formula (1) is
For example,

[Chemical 6] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 7] It is selected more preferably, and two or more kinds of these may be used.

In the present invention, from the viewpoint of storability, for example, a diamine having a structure of X or a compound selected from bis (aminophenol), 2,4-diaminophenol and the like, and a structure of Z to be blended if necessary. And a compound selected from tetracarboxylic acid anhydride having the structure of Y, tetracarboxylic acid anhydride having the structure of Y, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. After synthesizing the obtained polyamide resin containing the structure represented by the general formula (1), an aliphatic group or cyclic group having at least one alkenyl group or alkynyl group at the terminal amino group contained in the polyamide resin is synthesized. Capped as an amide with an acid anhydride containing a compound group Door is preferable. Examples of the group derived from an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

[0019]

[Chemical 8] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 9] It is selected more preferably, and two or more kinds of these may be used.

Further, Z of the polyamide resin of the general formula (1) which is optionally used is, for example,

[Chemical 10] However, the present invention is not limited to these, and two or more kinds may be used.

Z in the general formula (1) is used when particularly excellent adhesion is required for a substrate such as a silicon wafer, and the usage ratio b is up to 40 mol%. If it exceeds 40 mol%, the solubility of the resin is extremely lowered, the undeveloped residue (scum) is generated, and pattern processing cannot be performed, which is not preferable. In addition, these X, Y,
When Z is used, it may be one kind or a mixture of two or more kinds.

The photosensitive diazoquinone compound (B) used in the present invention is 1,2-benzoquinonediazide or 1,2-benzoquinonediazide.
A compound having a 2-naphthoquinonediazide structure,
U.S. Pat. Nos. 2,772,975 and 2,79
It is a substance known from 7,213 and 3,669,658. For example:

[0024]

[Chemical 11]

[0025]

[Chemical 12]

Of these, particularly preferred are phenol compounds and 1,2-naphthoquinone-2-diazide-5.
Sulfonic acid or 1,2-naphthoquinone-2-diazide-
It is an ester compound with 4-sulfonic acid. Examples of the phenol compound include, but are not limited to, the followings. These may be used alone or in combination.

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

The amount of the photosensitive diazoquinone compound (B) used in the present invention is 1 to 100 parts by weight based on 100 parts by weight of the polyamide resin represented by the general formula (1). If it is less than the lower limit, the patterning property will be poor, and if it exceeds the upper limit, the sensitivity will be significantly lowered.

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.

The present invention is characterized in that a non-fluorinated surfactant is added to a resin composition comprising a polyamide resin represented by the general formula (1) and a photosensitive diazoquinone compound. Non-fluorine-based surfactants are more biodegradable than fluorine-based surfactants and can be expected in environmental safety. However, it is generally said that the effect of lowering the surface tension is inferior. However, in the present invention, when a non-fluorine-containing surfactant is added to the photosensitive resin composition of the present invention, it has been found that in its leveling property and edge rinse property, performance equivalent to that of a conventional fluorine-based compound can be obtained. Is.

The amount of the non-fluorinated surfactant (C) compounded in the polyamide resin (A) represented by the general formula (1) is 0.001 to 100 parts by weight of the polyamide resin (A).
When the amount is 10 parts by weight and the amount is less than the lower limit value, the effect due to the compounding is not exerted, and when the edge rinse is performed, a receding phenomenon is easily caused, which causes a poor appearance. On the other hand, when the amount exceeds the upper limit, there occurs a problem that foam breakage becomes worse when the polyamide resin and the photosensitive diazoquinone compound are dissolved in a solvent.

Examples of the non-fluorine type surfactant (C) in the present invention include organopolysiloxane type surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene. There are nonionic surfactants such as nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate, and surfactants composed of acrylic or methacrylic polymer. Among these, organopolysiloxane-based surfactants are particularly preferable. In the present invention, a non-fluorine-containing surfactant is dissolved in a solvent together with a polyamide resin and a photosensitive diazoquinone to form a varnish for use.

In the positive photosensitive resin composition of the present invention, a phenol compound may be used in combination for the purpose of improving the sensitivity, if necessary. The amount of phenolic compound is
The amount is preferably 1 to 30 parts by weight based on 100 parts by weight of the polyamide resin represented by the general formula (1). Examples of the phenol compound include the followings, but are not limited thereto.

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

If necessary, the positive photosensitive resin composition of the present invention may contain an additive such as a silane coupling agent.

In the present invention, these components are dissolved in a solvent to form a varnish for use. As the solvent, N-
Methyl-2-pyrrolidone, γ-butyrolactone, N, N
-Dimethylacetamide, dimethylsulfoxide, 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, and may be used alone or in combination.

In the method of using the positive photosensitive resin composition of the present invention, first, the resin composition is applied to a suitable support such as a silicon wafer, a ceramic substrate or an aluminum substrate. In the case of a semiconductor device, the coating amount is such that the final film thickness after curing is 0.1 to 30 μm. Film thickness is 0.1
If it is less than μm, it becomes difficult to sufficiently exert the function as a protective surface film of a semiconductor element, and if it exceeds 30 μm,
It becomes difficult to obtain a fine processing pattern. 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, a relief pattern is obtained by dissolving and removing the irradiated portion with a developing solution. 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, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or 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. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an imide ring and an oxazole ring, and a final pattern having high heat resistance is obtained. Known methods can be used for other methods of manufacturing the semiconductor device. 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.

[0048]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Synthesis of Polyamide Resin Diphenyl ether-4,4′-dicarboxylic acid Dicarboxylic acid derivative (active ester) obtained by reacting 1 mol with 1-hydroxy-1,2,3-benzotriazole 2 mol 443.2 g (0.9 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1.0 mol) were used as a thermometer,
The mixture was placed in a 4-neck separable flask equipped with a stirrer, a raw material charging port, and a dry nitrogen gas introducing tube, and 3000 g of N-methyl-2-pyrrolidone was added and dissolved. Then, the reaction was carried out at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g of 5-norbornene-2,3-dicarboxylic acid anhydride dissolved in 500 g of N-methyl-2-pyrrolidone (0.
2 mol) was added, and the reaction was completed by further stirring for 12 hours. After filtering the reaction mixture, the reaction mixture was added to a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the desired polyamide resin ( A-1) was obtained.

Preparation of Positive Photosensitive Resin Composition 100 parts by weight of synthesized polyamide resin (A-1), photosensitive diazoquinone compound (B-1) having a structure of the following formula
25 parts by weight, a surfactant having a structure of the following formula (C-
1) 0.06 parts by weight was dissolved in 180 parts by weight of γ-butyrolactone and then filtered through a 0.2 μm fluororesin filter to obtain a photosensitive resin composition.

<Characteristic Evaluation> This positive type photosensitive resin composition was applied onto a silicon wafer using a spin coater, γ-butyrolactone edge rinse was performed, and the film was dried at 120 ° C. for 4 minutes to obtain a film. A coating film having a thickness of about 5 μm was obtained. When the edge rinsed portion was observed from above with an optical microscope, there was no receding phenomenon in the edge portion and it was good (the width of the receding portion was 0 mm). The coating film was passed through a reticle by an i-line stepper exposure machine NSR-4425i (manufactured by Nikon Corp.) to 300 mJ / cm ^2.
The exposed portion was dissolved and removed by immersing it in a 2.38% tetramethyl hydroxide aqueous solution for 60 seconds, and then rinsed with pure water for 30 seconds to form a pattern. The appearance after development was also observed by an optical microscope and found to be extremely good with no voids or surface roughness.

Example 2 The evaluation was carried out by changing the compounding amount of the non-fluorine type surfactant in Example 1 to 0.15 part by weight. Example 3 The evaluation was performed by changing the compounding amount of the non-fluorine-containing surfactant in Example 1 to 0.015 parts by weight. << Example 4 >> The same evaluations as in Example 1 were performed except that the non-fluorinated surfactant (C-1) in Example 1 was replaced with (C-2) having the following structure. <Example 5> The same evaluation as in Example 1 was carried out except that the non-fluorinated surfactant (C-1) in Example 1 was replaced with (C-3) having the following structure. Example 6 The same evaluations as in Example 1 were carried out except that the non-fluorinated surfactant (C-1) in Example 1 was replaced with (C-4) having the following structure. << Example 7 >> The photosensitive diazoquinone compound (B-1) in the photosensitive resin composition of Example 1 was replaced with a compound (B-
The same evaluation as in Example 1 was carried out except that 2) was used.

Example 8 In the synthesis of the polyamide resin in Example 1, hexafluoro-2,2-bis (3
A polyamide resin (A-2) was synthesized by using 3,3′-diamino-4,4′-dihydroxy instead of -amino-4-hydroxyphenyl) propane. Further, the same evaluation as in Example 1 was carried out except that the amount of the photosensitive diazoquinone compound (B-1) added was 30 parts by weight. Example 9 In the synthesis of the polyamide in Example 1, 3,3′-diamino-4,4′-dihydroxybiphenyl was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane. Polyamide resin (A-3) was synthesized using the same, and other evaluations were made in the same manner as in Example 1. Example 10 In the synthesis of the polyamide in Example 1, hexafluoro-2,2-bis (3-amino-4-)
Hydroxyphenyl) propane 366.3 g (1.0 mol) was reduced by 340.6 g (0.93 mol) and replaced by 1,3-bis (3-aminopropyl) -1,1,3,3.
17.4-g (0.07) of 3, -tetramethyldisiloxane
Mol) to synthesize a polyamide resin (A-4),
Others were evaluated in the same manner as in Example 1. << Example 11 >> The phenolic compound (D-1) having the following structure was added to the photosensitive resin composition of Example 1 in the amounts shown in Table 1, and the same evaluation as in Example 1 was performed. << Example 12 >> The phenol compound (D-2) having the following structure was added to the photosensitive resin composition in Example 1 in the amounts shown in Table 1, and the same evaluation as in Example 1 was performed.

Comparative Example 1 Evaluation was carried out in Example 1 without adding a non-fluorinated surfactant. << Comparative Example 2 >> 0.0005 parts by weight of the non-fluorine-based surfactant in Example 1 was blended and evaluated. << Comparative Example 3 >> 20 parts by weight of the non-fluorine-based surfactant in Example 1 was blended and evaluated. The evaluation results of Examples 1 to 11 and Comparative Examples 1 to 3 are shown in Tables 1 and 2.

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

According to the present invention, it is possible to obtain a positive type photosensitive resin composition which is excellent in edge rinse property and has a good appearance after development.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA03 AA04 AB16 AC01 AD03                       BE01 CB24 CB25 CB32 CC04                       FA17                 4J001 DA01 DB02 DC15 EB28 EB34                       EB44 EB55 EB57 EB58 EB60                       EC38 EC44 EC54 EC56 EC66                       EC67 EC68 EC70 EE26E                       EE35D EE38A EE38D EE42D                       EE65A EE72D EE83D EE83E                       FA01 FB06 FC03 FC06 GA13                       HA10 JA20 JC08

Claims (5)

[Claims] 1. A polyamide resin (A) represented by the general formula (1) (100 parts by weight) and a photosensitive diazoquinone compound (B).
1 to 100 parts by weight and a non-fluorine-based surfactant (C) 0.
A positive photosensitive resin composition comprising 001 to 10 parts by weight. [Chemical 1] 2. The positive photosensitive resin composition according to claim 1, wherein the non-fluorinated surfactant (C) has a siloxane structure. 3. The positive photosensitive resin composition according to claim 1, wherein the non-fluorine-based surfactant (C) has a dimethylpolysiloxane-polyoxyalkylene copolymer structure. 4. A semiconductor device manufactured using the positive photosensitive resin composition according to claim 1. Description: 5. The positive photosensitive resin composition according to claim 1, which has a film thickness of 0.1 to 0.1 after heat dehydration ring closure.
A semiconductor device, which is obtained by coating on a semiconductor element to a thickness of 30 μm, prebaking, exposing, developing, and heating.