JP2005010764A - Negative photosensitive resin composition, semiconductor device and display element, as well as method for manufacturing semiconductor device and display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative photosensitive resin composition which is high sensitivity to permit aqueous alkaline solution development and does not foam despite of curing and a semiconductor device or display element using the same and a method for manufacturing the semiconductor device or the display element. <P>SOLUTION: The negative type photosensitive resin composition contains an alkali-soluble resin (A), a photo-acid initiator (B) and a compound having a methylol group (C), in which the alkali-soluble resin (A) is preferably a polyamide resin containing the structure expressed by a specific formula and the compound having the methylol group (C) is a compound having ≥2 methylol groups. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a negative photosensitive resin composition that can be developed with an aqueous alkali solution, has high sensitivity, and does not foam even when cured, a semiconductor device and a display element using the same, and a method for manufacturing the semiconductor device and the display element It is about.

  Conventionally, polyimide resin having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like has been used for the surface protection film and interlayer insulating film of the semiconductor element. Due to the thinning and miniaturization of semiconductor devices and the transition to surface mounting by solder reflow, there is a demand for significant improvements in characteristics such as heat cycle resistance and heat shock resistance, and higher performance resins are required. I came.

  On the other hand, there is a technique for imparting photosensitivity to the polyimide resin itself, for example, a photosensitive polyimide resin represented by the following formula (2).

  When this is used, a part of the pattern creation process can be simplified, and there is an effect of shortening the process and improving the yield, but it is necessary to spray a solvent such as N-methyl-2-pyrrolidone in the form of a spray during development. Therefore, there are problems in safety and handling. Therefore, a positive photosensitive resin composition that can be developed with an aqueous alkaline solution has been recently developed. For example, Patent Document 1 discloses a positive photosensitive resin composition composed of a polybenzoxazole precursor as a base resin and a diazoquinone compound as a photosensitive material. This has high heat resistance, excellent electrical properties, and fine processability, and has the potential not only for wafer coating but also for interlayer insulation. The development mechanism of this positive photosensitive resin composition is that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, but the diazoquinone compound undergoes a chemical change upon exposure to become soluble in the alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a coating film pattern of only the unexposed portion can be created.

  When these photosensitive resin compositions are used, the sensitivity of the photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long and the throughput decreases. Therefore, for example, if the molecular weight of the base resin is decreased in order to improve the sensitivity of the photosensitive resin composition, the dissolution rate of the exposed part increases and the sensitivity is improved at a glance, but at the same time, the film loss of the unexposed part increases. In addition, the required film thickness cannot be obtained or the pattern shape is lost. For these reasons, development of a photosensitive resin composition having high sensitivity while satisfying the above characteristics is strongly desired.

  In the flow of increasing sensitivity, Patent Document 2, Patent Document 3, and Patent Document 4 describe a chemically amplified photosensitive resin composition comprising a polyimide precursor or polybenzoxazole precursor into which a protecting group is introduced and a photoacid generator. Things are disclosed. In this system, the acid generated from the photoacid generator cuts the protecting group of the polyimide or polybenzoxazole precursor and becomes soluble in an aqueous alkali solution, thereby allowing patterning. However, it is difficult to obtain a stable photosensitive resin because a polymer reaction is required to introduce a protective group into the polyimide or polybenzoxazole precursor and it is difficult to control the introduction of the protective group. In addition, after the pattern is formed, heat treatment is performed and cyclization is performed.

Japanese Examined Patent Publication No. 1-46862 JP-A-10-186664 JP-A-11-202489 Special table 2002-526793

  The present invention provides a negative photosensitive resin composition that can be developed with an aqueous alkali solution, has high sensitivity, and does not foam even when cured, a semiconductor device and a display element using the same, and a method for producing the same. With the goal.

Such an object can be achieved by the present invention described in the following [1] to [7].
[1] A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a compound (C) having a methylol group.
[2] The negative photosensitive resin composition according to item [1], wherein the alkali-soluble resin (A) is a polyamide resin containing a structure represented by the general formula (1).

[3] The negative photosensitive resin composition according to [1] or [2], wherein the compound (C) having a methylol group is a compound having two or more methylol groups.
[4] A semiconductor device manufactured using the negative photosensitive resin composition according to any one of [1] to [3].
[5] A display element manufactured using the negative photosensitive resin composition according to any one of [1] to [3].
[6] The negative photosensitive resin composition according to any one of [1] to [3] is applied onto a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm. A method for producing a semiconductor device, which is obtained by pre-baking, exposure, post-baking, development and heating.
[7] The negative photosensitive resin composition according to any one of [1] to [3] is applied onto a display element substrate so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm. , Pre-baking, exposure, post-baking, development, and heating to obtain a display element manufacturing method.

  The present invention provides a negative photosensitive resin composition that can be developed with an aqueous alkali solution and that does not foam even when cured, a semiconductor device and a display element using the same, and a method for manufacturing the semiconductor device and the display element can do.

  The alkali-soluble resin used in the present invention is a resin having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain, and has a structure represented by cresol-type novolac resin, polyhydroxystyrene, and general formula (1). Polyamide resins including the structure represented by the general formula (1) are preferable from the viewpoint of heat resistance after the final heating.

X in the polyamide resin containing the structure represented by the general formula (1) represents a divalent to tetravalent organic group, R ₁ is a hydroxyl group, O—R ₃ , m is an integer of 0 to 2, and these are It may be the same or different. Y represents a divalent to hexavalent organic group, R ₂ represents a hydroxyl group, a carboxyl group, O—R ₃ , or COO—R ₃ , and n represents an integer of 0 to 4, 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, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, etc., and a structure of Z blended as necessary. And a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. having the structure of Y. Is obtained. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

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, an alkaline aqueous solution of the carboxyl group Is a group protected with an organic group having 1 to 15 carbon atoms for the purpose of adjusting the solubility in the solvent, and a hydroxyl group and a carboxyl group may be protected as necessary. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

When this polyamide resin is heated at about 300 to 400 ° C., dehydration ring closure occurs, and a heat resistant resin is obtained in the form of polyimide, polybenzoxazole, or copolymerization of both.
X of the polyamide resin containing the structure represented by the general formula (1) of the present invention is, for example,

However, it is not limited to these.
Among these, as particularly preferred,

Two or more types may be used.
Moreover, Y of the polyamide resin containing the structure represented by the general formula (1) is, for example,

However, it is not limited to these.
Among these, particularly preferred are:

Two or more types may be used.
In the present invention, it is desirable to seal the end from the viewpoint of storage stability. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (1). Specifically, for example, a diamine having a structure of X or a compound selected from bis (aminophenol), 2,4-diaminophenol and the like, a silicone diamine having a structure of Z blended as necessary, and a structure of Y are included. In general formula (1) obtained by reacting a compound selected from tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. After synthesizing a polyamide resin having the structure shown, an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group as the terminal amino group contained in the polyamide resin Is preferably used to cap as an amide. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

However, it is not limited to these.
Among these, particularly preferred are:

Two or more types may be used. The method is not limited to this method, and the terminal acid contained in the polyamide resin is capped as an amide using an amine derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. You can also

  Furthermore, Z of the polyamide resin including the structure represented by the general formula (1) used as necessary is, for example,

However, the present invention is not limited to these, and two or more types may be used.
Z of the polyamide resin having the structure represented by the general formula (1) is used when particularly excellent adhesion to a substrate such as a silicon wafer is required, for example. Up to%. If it exceeds 40 mol%, the solubility of the resin is extremely lowered, developing residue (scum) is generated, and pattern processing becomes impossible.

The photoacid generator (B) in the present invention is a photograph. Sci. Eng. , 18, p387 (1974), CHEMTECH, Oct. p624 (1980), Polym. Mater. Sci. Eng. 72, p406 (1995), Macromol. Chem. Rapid Commun. 14, p203 (1993), J.M. Photopolym. Sci. Technol. , 6, p67 (1993), Macromolecules, 21, p2001 (1988), Chem. Mater. 3, p462 (1991), Proc. 2-nitrobenzyl esters described in SPIE, 1086, 2 (1989); Photopolym. Sci. Technol. , 2, p429 (1989), Proc. SPIE, 1262, p575 (1990) described N-iminosulfonates, Polym. Mat. Sci. Eng. , 61, 269 (1989), naphthoquinonediazide-4-sulfonic acid esters; Photopolym. Sci. Technol. 4, p389 (1991), Proc. And halogen compounds described in SPIE, 2195, p173 (1994). These may be used alone or in combination of two or more.
The compound (C) having a methylol group in the present invention is

However, it is not limited to these.
Among these, compounds having two or more methylol groups are particularly preferable.
In the present invention, the amount of the methylol compound (C) added to the alkali-soluble resin (A) is 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. .

This methylol compound reacts with the alkali-soluble resin by being post-baked using the acid generated from the photoacid generator (B) as a catalyst in the exposed area. The reaction is directly added to the hydroxyl group or benzene ring of the alkali-soluble resin. The alkali-soluble resin that has reacted with the methylol compound is reduced in solubility, and the exposed portion becomes insoluble in the aqueous alkaline developer, enabling negative pattern processing.
If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition in the present invention.

  In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents 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-methoxypropio 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, the composition is first applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is less than the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern, Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. 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 post-bake process is performed. The temperature at which the post-bake treatment is performed is 60 to 150 ° C., and the time can be between 10 seconds and 30 minutes. For heating, a hot plate, a simple oven, a diffusion furnace, or the like can be used.

  A relief pattern is obtained by dissolving and removing the unirradiated portion with a developer. Developers 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, 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 to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  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 oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

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 plates, solder resist films, liquid crystal alignment films and interlayer insulation films in display elements. is there.
A known method can be used as a method for manufacturing other semiconductor devices or display elements.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
* Synthesis of polyamide resin 360.4 g of dicarboxylic acid derivative obtained by reacting 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole (0. 9 mol) and 366.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 4 equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube It put into the separable flask of one neck, 3000 g of N-methyl-2-pyrrolidone was added and it was made to melt | dissolve. Thereafter, the mixture was reacted 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 100 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After the reaction mixture was filtered, the reaction mixture was put into a solution of water / methanol = 3/1 (volume ratio) to obtain a precipitate. The precipitate was dissolved in 1000 ml of tetrahydrofuran, and then poured into a 0.1% aqueous hydrochloric acid solution to obtain a precipitate. It was collected by filtration, washed thoroughly with water, dried under vacuum, represented by the general formula (1), X is the following formula X-1, Y is a mixture of the following formulas Y-1 and Y-2, a = The objective polyamide resin (PA-1) consisting of 100 and b = 0 was obtained.

* Preparation of Positive Photosensitive Resin Composition 100 g of synthesized polyamide resin (PA-1), 15 g of photoacid generator (S-1) having the following structure, and 38 g of methylol compound (M-1) having the following structure were mixed with propylene glycol monomethyl After dissolving in ether acetate, it was filtered through a 0.2 μm fluororesin filter to obtain a photosensitive resin composition.

* Characteristic evaluation This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then dried on a hot plate at 90 ° C. for 2 minutes to obtain a coating film having a thickness of about 5 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn) is used. Te, where it was exposed from the exposure dose 100mJ / cm ² 20mJ / cm ² increased by one and it was possible pattern created from 220 mJ / cm ² (sensitivity 220mJ / cm ^2). Next, it heated at 125 degreeC for 5 minute (s) using the hotplate. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 30 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that an 8 μm pattern was formed. Furthermore, when curing was performed in a nitrogen atmosphere at 150 ° C./30 minutes and 350 ° C./60 minutes in a clean oven, no foaming was observed in the coating film.

Example 2
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that M-2 was changed to 45 g instead of the methylol compound (C) M-1 in Example 1, and the same as in Example 1. Was evaluated.

Example 3
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that S-2 was changed to 20 g instead of the photoacid generator (S-1) in Example 1, and Example 1 and Similar evaluations were made.

Example 4
In the synthesis of the polyamide resin in Example 1, in place of 0.9 mol of terephthalic acid and 0.1 mol of isophthalic acid, 1 mol of diphenyl ether-4,4′-dicarboxylic acid was used and represented by the general formula (1), A polyamide resin (PA-2) in which X is the following formula X-1 and Y is the following formula Y-3 and a = 100 and b = 0 was synthesized. Otherwise, a positive photosensitive resin composition was obtained in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

Example 5
A thermometer containing 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 8.60 g (0.116 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) of pyridine. Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise to this reaction solution together with 30 g of N-methyl-2-pyrrolidone, and then 22.7 g (0.110 mol) of dicyclohexylcarbodiimide. Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature.
Thereafter, 27.1 g of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. (0.055 mol) and 44.8 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with 70 g of N-methyl-2-pyrrolidone are added at room temperature. Stir for 2 hours. Thereafter, the reaction was performed in the same manner as in Example 1 except that the reaction was performed at 75 ° C. for 12 hours using an oil bath, and the reaction was represented by the general formula (1). And a polyamide resin (PA-3) composed of Y-4. Otherwise, a positive photosensitive resin composition was obtained in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

Example 6
After dissolving 22.0 g (0.06 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane in 100 g of N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone Add 25.3 g (0.12 mol) of trimellitic acid chloride dissolved in 80 g while cooling to 5 ° C. or lower. Further, 11.4 g (0.144 mol) of pyridine is added and stirred at 20 ° C. or lower for 3 hours. Next, after adding 12.0 g (0.06 mol) of 4,4′-diaminodiphenyl ether, the mixture is reacted at room temperature for 5 hours. Next, the internal temperature is raised to 85 ° C. and stirred for 3 hours. After completion of the reaction, the filtered filtrate was added to water / methanol = 5/1 (volume ratio) to obtain a precipitate. The precipitate was dissolved in 1000 ml of tetrahydrofuran, and then poured into a 0.1% aqueous hydrochloric acid solution to obtain a precipitate. It is collected by filtration, thoroughly washed with water, and then dried under vacuum. The mixture is represented by the formula (1), X is represented by the following formulas X-1 and X-2, and Y is represented by the following formula Y-5. The objective polyamide resin (PA-4) which consists of a = 100 and b = 0 was obtained. Otherwise, a positive photosensitive resin composition was obtained in the same manner as in Example 1, and the same evaluation as in Example 1 was performed.

<< Comparative Example 1 >>
It is dissolved in 58.8 g of the polyamide (PA-1) obtained in Example 1, 7.6 g (0.075 mol) of triethylamine, and 320 mL of N-methyl-2-pyrrolidone (NMP). A solution prepared by dissolving 82.2 g (0.377 mol mol) of di-t-butyl dicarbonate in 150 g of NMP was added dropwise over 15 minutes, and then the temperature was raised to 65 ° C. in an oil bath and stirred as it was for 3 hours. After completion of the reaction, it was poured into 8 L of water to obtain a precipitate. The precipitate was dissolved in 1000 ml of tetrahydrofuran, and then poured into a 0.1% aqueous hydrochloric acid solution to obtain a precipitate. It is collected by filtration, washed thoroughly with water, dried under vacuum, represented by the general formula (1), X is the following formula X-1, Y is a mixture of the following formulas Y-1 and Y-2, A polyamide (PA-5) comprising a = 100 and b = 0 and having a hydroxyl group protected with a t-butoxycarbonyl group was obtained. The other evaluations were the same as in Example 1.

  The evaluation results of Examples 1 to 6 and Comparative Example 1 are shown in Table 1.

Claims (7)

A negative photosensitive resin composition comprising an alkali-soluble resin (A), a photoacid generator (B), and a compound (C) having a methylol group. The negative photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide resin having a structure represented by the general formula (1).

The negative photosensitive resin composition according to claim 1 or 2, wherein the compound (C) having a methylol group is a compound having two or more methylol groups. A semiconductor device manufactured using the negative photosensitive resin composition according to claim 1. A display element manufactured using the negative photosensitive resin composition according to claim 1. The negative photosensitive resin composition according to any one of claims 1 to 3 is applied on a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 µm, and is pre-baked, exposed, and post-baked. A method for producing a semiconductor device, which is obtained by developing and heating. The negative photosensitive resin composition according to any one of claims 1 to 3 is applied onto a display element substrate so that the film thickness after heat-dehydration and ring closure is 0.1 to 30 μm, and prebaking, exposure, A method for producing a display element, which is obtained by post-baking, developing and heating.