JP2009108074A - Naphthoquinone diazide sulfonic acid ester, positive photosensitive resin composition using it, and semiconductor unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition capable of obtaining a pattern of high resolving power and high film remaining rate even in an increased film thickness, and high sensitivity. <P>SOLUTION: This positive photosensitive resin composition contains (A) 100 pts.wt. of an alkali soluble resin and (B) 1-50 pts.wt. of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and/or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of a phenol compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive material capable of obtaining a pattern with high resolution and a high residual film ratio and high sensitivity, a positive photosensitive resin composition using the photosensitive material, a semiconductor device, and a method for manufacturing the semiconductor device. It is.

  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 (4).

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 type 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, in an attempt to improve the sensitivity of the photosensitive resin composition, for example, when the molecular weight of the base resin is reduced, the film thickness of the unexposed area is increased during development, so that the required film thickness cannot be obtained, There arises a problem that the pattern shape collapses. For these reasons, development of a photosensitive resin composition having high sensitivity while satisfying the above characteristics is strongly desired. Further, the film thickness of the photosensitive resin composition after heat dehydration and ring closure has been about 5 to 7 μm in the past, but tends to increase to about 10 to 20 μm, and the photosensitive resin has high sensitivity even when it becomes thicker. Development of compositions is desired.

Japanese Examined Patent Publication No. 1-46862

  The present invention provides a photosensitive material capable of obtaining a pattern with high resolution and a high residual film ratio and high sensitivity, a positive photosensitive resin composition using the photosensitive material, a semiconductor device, and a method for manufacturing the semiconductor device The purpose is to do. It is another object of the present invention to provide a high-sensitivity positive photosensitive resin composition that does not cause the above-described problems even when the film thickness is increased.

  The present invention is a 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of the phenol compound represented by the formula (1). It is a characteristic naphthoquinone diazide sulfonic acid ester. Furthermore, the present invention relates to 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and / or 1,2-naphthoquinone-2-diazide of a phenol compound represented by the formula (1) and 100 parts by weight of an alkali-soluble resin. A positive photosensitive resin composition comprising 1 to 50 parts by weight of -4-sulfonic acid ester (B). More preferably, the alkali-soluble resin is a 1,2-naphthoquinone-2-diazide composed of 100 parts by weight of a polyamide resin (A) having a structure represented by the general formula (2) and a phenol compound represented by the formula (1). It is a positive photosensitive resin composition containing 1 to 50 parts by weight of -5-sulfonic acid ester and / or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester (B).

  In the positive photosensitive resin composition, the phenolic compound represented by the formula (1) is added in an amount of 1,2 to 100 parts by weight of the polyamide resin (A) having the structure represented by the general formula (2). -1 to 50 parts by weight of naphthoquinone-2-diazide-5-sulfonic acid ester and / or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester (B), 1 to 30 parts by weight of phenol compound (C) It is a positive photosensitive resin composition characterized by including.

As a more preferred embodiment, X in the polyamide resin containing the structure represented by the general formula (2) is selected from the group of the following structure, and Y in the polyamide resin of the general formula (2) is selected from the group of the following structure. The polyamide resin having the structure represented by the general formula (2) is end-capped with an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group, and the phenol compound (C) Are compounds of 2 to 5 nuclei having phenolic hydroxyl groups, and they have the same number or more of hydroxyl groups with respect to the benzene ring. It is not always necessary for one benzene ring to have one hydroxyl group, and one benzene ring may have two or more hydroxyl groups, and the number of hydroxyl groups in the phenol compound is the number of benzene rings. Must be equal to or greater than Further, halogen atoms, alkyl groups, alkoxy groups, alkyl ester groups, cycloalkyl groups, and cycloalkoxy groups may be substituted on the benzene ring of these phenol compounds. As a particularly preferred phenol compound, a compound represented by the general formula (3) is desirable.

  Moreover, it is a semiconductor device manufactured using the positive photosensitive resin composition described above, and the film thickness after heating and dehydrating and ring-closing the positive photosensitive resin composition is 0.1. It is a method for producing a semiconductor device, which is obtained by applying on a semiconductor element so as to have a thickness of ˜30 μm, and prebaking, exposing, developing and heating.

  According to the present invention, it is possible to form a high-sensitivity positive photosensitive resin that can form a pattern with high resolution and a high residual film ratio even when the film thickness is increased while maintaining the conventional characteristics. it can.

  The 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of the phenol compound represented by the formula (1) used in the present invention is photosensitive. It functions as a material.

  Example using 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazido-4-sulfonic acid ester of a phenol compound different from the phenol compound represented by formula (1) Is disclosed in Japanese Patent Application Laid-Open No. 2000-275833. When this compound is used, the effect of improving the sensitivity of the photosensitive resin composition is recognized, but the effect of improving the sensitivity is not effective for the recent demand for increasing the film thickness of the photosensitive resin composition for wafer coating. This is sufficient and further sensitivity is required. Accordingly, as a result of studying various photosensitive materials, the present inventors have found that the phenol compound represented by the formula (1) is a 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2. -It has been found that diazide-4-sulfonic acid ester is very effective in improving the sensitivity even with a thick film.

  As the 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of the phenol compound represented by the formula (1) used in the present invention, Esterification of 1 mol of the phenolic compound of (1) and 2.0 to 4.0 mol of 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid Reacted esters are preferred. If the ratio of esterification is less than 2.0 mol, the effect of improving the sensitivity is small, which is not preferable.

  Furthermore, in the present invention, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and / or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of the phenol compound represented by the formula (1) By combining with an alkali-soluble resin, it is possible to obtain a positive photosensitive resin composition that can obtain a pattern with a high resolution and a high residual film ratio and a high sensitivity.

  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 novolak resin, polyhydroxystyrene, and general formula (2). The polyamide resin containing is mentioned, However, The polyamide resin containing the structure shown by General formula (2) from the heat resistant point after the last heating is preferable.

X in the polyamide resin containing the structure represented by the general formula (2) represents a divalent to tetravalent cyclic compound group, R ₁ is a hydroxyl group, O—R ₃ , and m is an integer of 0 to 2, May be the same or different. Y represents a divalent to hexavalent cyclic compound group, R ₂ is a hydroxyl group, a carboxyl group, O—R ₃ , COO—R ₃ , n is an integer of 0 to 4, and these 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 (2) is, for example, a compound selected from a diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the 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 a dicarboxylic acid, an active ester 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 _{(2), 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 (2) 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 including the structure represented by the general formula (2) 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, from the viewpoint of storage stability, for example, a diamine or bis (aminophenol) having a X structure, a compound selected from 2,4-diaminophenol, etc., a silicone having a Z structure that is blended as necessary. Obtained by reacting a diamine with a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative having the structure of Y After synthesizing a polyamide resin having the structure represented by the general formula (2), 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 formed. It is preferable to cap as amide with acid anhydride containing . Examples of the group derived from an acid anhydride 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.

  Furthermore, Z of the polyamide resin including the structure represented by the general formula (2) 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 (2) 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.
Moreover, the compounding quantity of the photosensitive material (B) used by this invention to alkali-soluble resin (A) is 1-50 weight part with respect to 100 weight part of alkali-soluble resin. If the blending amount is less than the lower limit value, the patterning property of the resin becomes poor, and conversely if it exceeds the upper limit value, the sensitivity is greatly lowered.

  If necessary, a dihydropyridine derivative can be added to the positive photosensitive resin composition of the present invention in order to enhance the photosensitive properties. 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, etc. Can do.

  It has also been found that the positive photosensitive resin composition of the present invention can contain a phenol compound (C), and that a new effect is exhibited by using the phenol compound (C). 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of the phenol compound represented by the formula (1) is commonly used, for example. The molecular size is larger than that of the following naphthoquinone diazide sulfonate ester.

  Therefore, the solubility of the developer can be controlled over a wide range, but the solubility of the photosensitive material that has been exposed to light and chemically changed in the exposed area is slightly worse than that of a low-molecular photosensitive material. In some cases, a development residue (scum) may occur at the pattern corner. At this time, if a low molecular weight phenol compound is added, the entire solubility in the developer can be increased, scum is eliminated, and as a result, resolution is improved and sensitivity is further improved.

  The phenol compound (C) is a compound of 2 to 5 nuclei having a phenolic hydroxyl group, and they have the same number or more of hydroxyl groups with respect to the benzene ring. It is not always necessary for one benzene ring to have one hydroxyl group, and one benzene ring may have two or more hydroxyl groups, and the number of hydroxyl groups in the phenol compound is the number of benzene rings. Must be equal to or greater than Further, halogen atoms, alkyl groups, alkoxy groups, alkyl ester groups, cycloalkyl groups, and cycloalkoxy groups may be substituted on the benzene ring of these phenol compounds. Among them, particularly preferred phenol compounds are shown below.

  Specific examples of the phenol compound represented by the general formula (3) include, but are not limited to, the following compounds.

The addition amount of a phenol compound (C) is 1-30 weight part with respect to 100 weight part of polyamide resins shown by General formula (2). When the addition amount of the phenol compound exceeds the upper limit, the remaining film ratio is remarkably lowered during development or precipitation occurs during freezing storage, and when it is less than the lower limit, the sensitivity during development is lowered.
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 relief pattern is obtained by dissolving and removing the irradiated 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 not only used for semiconductors, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, interlayer insulation films for elements in display elements, etc. Is also useful. As other semiconductor device manufacturing methods, known methods can be used.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
* Synthesis of naphthoquinonediazide sulfonic acid ester 31.6 g (0.05 mol) of the phenol compound of the formula (1) shown below and 1,4-naphthoquinone-2-diazide-4-sulfonic acid chloride 48.4 g (0. 18 mol: 3.6 mol per mol of phenol compound) and 400 ml of acetone were put into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. While maintaining the internal temperature at 20 ° C. or lower, 22.3 g (0.22 mol) of triethylamine was added dropwise. Then, after stirring for 5 hours, 5.4 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was put into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain the intended photosensitive material (1,2-naphthoquinone-based on 1 mol of phenol compound). 2-diazide-4-sulfonic acid 3.6 molar reactant) (Q-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 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was put into 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 general formula (2) And X is a mixture of the following formulas X-1 and Y is a mixture of the following formulas Y-1 and Y-2, and the target polyamide resin (PA-1) having a = 100 and b = 0 was obtained.

* Preparation of Positive Photosensitive Resin Composition 100 g of the synthesized polyamide resin (PA-1) and 15 g of the above (Q-1) were dissolved in 200 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter. A functional resin composition was obtained.

* 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 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 16 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), Nikon Corporation i-line stepper NSR-4425i Used to irradiate with varying exposure. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 620 mJ / cm ² . (Sensitivity is 620 mJ / cm ² ). The residual film ratio (film thickness after development / film thickness before development × 100) at this time was 88.1%, and the resolution was as high as 8 μm. Next, it was cured in a clean oven at 150 ° C./30 minutes and 320 ° C./30 minutes under an oxygen concentration of 1000 ppm or less. The film thickness after curing was 10.8 μm.

Example 2
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the addition amount of the photosensitive material (Q-1) in Example 1 was changed to 10 g, and the same evaluation as in Example 1 was performed. .

Example 3
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the addition amount of the photosensitive material (Q-1) in Example 1 was changed to 20 g, and the same evaluation as in Example 1 was performed. .

Example 4
* Synthesis of naphthoquinone diazide sulfonic acid ester 31.6 g (0.05 mol) of the phenol compound of the formula (1) and 53.7 g of 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride (0.20 mol: phenol) 4 moles per mole of compound) and 400 ml of acetone were placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and the flask internal temperature was 20 ° C. or lower. 24.3 g (0.24 mol) of triethylamine was added dropwise. Thereafter, after stirring for 5 hours, 6.0 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was put into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain the intended photosensitive material (1,2-naphthoquinone-based on 1 mol of phenol compound). 2-diazide-4-sulfonic acid 4 mol reactant (Q-2) was obtained. Next, a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the photosensitive material (Q-1) in Example 1 was changed to (Q-2), and the same evaluation as in Example 1 was performed. Went.

Example 5
* Synthesis of naphthoquinone diazide sulfonic acid ester 31.6 g (0.05 mol) of the phenol compound of the formula (1) and 40.3 g of 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride (0.15 mol: phenol) 3 moles per mole of compound) and 400 ml of acetone were placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube, and the flask internal temperature was 20 ° C. or lower. While maintaining the temperature, 18.2 g (0.18 mol) of triethylamine was added dropwise. Thereafter, after stirring for 5 hours, 4.5 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was put into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain the intended photosensitive material (1,2-naphthoquinone-based on 1 mol of phenol compound). 2-diazide-4-sulfonic acid 3 mol reactant (Q-3) was obtained. Next, a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the photosensitive material (Q-1) in Example 1 was changed to (Q-3), and the same evaluation as in Example 1 was performed. Went.

Example 6
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 (2). 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 7
In the synthesis of the polyamide resin in Example 6, 1 mol of 3,3′-diamino-4,4′-dihydroxyphenylsulfone was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane. Using this, a polyamide resin (PA-3) represented by the formula (2), wherein X is the following formula X-2, 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 8
A thermometer containing 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 13.0 g (0.110 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. The reaction was represented by the general formula (2), where X is the following formula X-1 and Y is the following formula Y-3. And a polyamide resin (PA-4) 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 9
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 poured into water / methanol = 5/1 (volume ratio) to obtain a precipitate, which was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (2) A target polyamide resin (PA-5) consisting of a = 100 and b = 0 in which X is a mixture of the following formulas X-1 and X-3 and Y is the following formula Y-5. 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 10
* Synthesis of naphthoquinonediazide sulfonic acid ester 31.6 g (0.05 mol) of the phenol compound of the formula (1) used in Example 1 and 48.4 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride ( 0.18 mol: 3.6 mol per mol of phenol compound) and 4000 ml of acetone were put into a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. Then, 22.3 g (0.22 mol) of triethylamine was added dropwise while keeping the temperature inside the flask at 20 ° C. or lower. Then, after stirring for 5 hours, 5.4 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was poured into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain a photosensitive material (1,2-naphthoquinone relative to 1 mol of phenol compound). 2-diazide-5-sulfonic acid 3.6 mol reactant) (Q-4). A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the photosensitive material (Q-1) in Example 1 was changed to (Q-4), and the same evaluation as in Example 1 was performed. .

Example 11
As in Example 1, 100 g of polyamide resin (PA-1), 15 g of the above (Q-1), and 15 g of the following phenol compound (P-1) were dissolved in 200 g of γ-butyrolactone, and then made of 0.2 μm fluororesin. Filtration through a filter gave a positive photosensitive resin composition. Further, the same evaluation as in Example 1 was performed.

Example 12
In the same manner as in Example 6, after dissolving 100 g of polyamide resin (PA-2), 15 g of (Q-1) and 15 g of the following phenol compound (P-1) in 200 g of γ-butyrolactone, 0.2 μm of fluororesin Filtration through a filter gave a positive photosensitive resin composition. Further, the same evaluation as in Example 1 was performed.

Example 13
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that the phenol compound (P-1) in Example 11 was replaced with the following (P-2), and evaluation similar to that in Example 1 was obtained. Went.

<< Comparative Example 1 >>
* Synthesis of naphthoquinonediazide sulfonic acid ester 28.8 g (0.05 mol) of the phenol compound of the following formula (5) and 1,4-naphthoquinone-2-diazide-4-sulfonic acid chloride 48.4 g (0.18 mol) : 3.6 moles per mole of phenol compound) and 400 ml of acetone were placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. Was kept dropwise at 20 ° C. or lower, and 22.3 g (0.22 mol) of triethylamine was added dropwise. Then, after stirring for 5 hours, 5.4 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was put into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain the intended photosensitive material (1,2-naphthoquinone-based on 1 mol of phenol compound). 2-Diazide-4-sulfonic acid 3.6 mol reactant) (Q-5) was obtained. Next, a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 1 was changed to (Q-5), and the same evaluation as in Example 1 was performed. went.

<< Comparative Example 2 >>
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 6 was changed to (Q-5), and the same evaluation as in Example 1 was performed. .

<< Comparative Example 3 >>
* Synthesis of naphthoquinone diazide sulfonic acid ester 28.8 g (0.05 mol) of the phenol compound of the formula (5) used in Comparative Example 1 and 1,4-naphthoquinone-2-diazide-5-sulfonic acid chloride 48.4 g ( 0.18 mol: 3.6 mol per mol of phenol compound) 400 ml of acetone was put into a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. Then, 22.3 g (0.22 mol) of triethylamine was added dropwise while keeping the temperature inside the flask at 20 ° C. or lower. Then, after stirring for 5 hours, 5.4 g of acetic acid was added and neutralized, and then the precipitate was removed by filtration. The obtained solution was put into pure water, and the precipitate was collected by filtration, washed with pure water, and then vacuum-dried at room temperature to obtain the intended photosensitive material (1,2-naphthoquinone-based on 1 mol of phenol compound). 2-Diazide-5-sulfonic acid 3.6 mol reactant) (Q-6) was obtained. Next, a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 1 was changed to (Q-6), and the same evaluation as in Example 1 was performed. went.

<< Comparative Example 4 >>
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 11 was changed to (Q-5), and the same evaluation as in Example 1 was performed. .

<< Comparative Example 5 >>
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 12 was changed to (Q-5), and the same evaluation as in Example 1 was performed. .

<< Comparative Example 6 >>
A positive photosensitive resin composition was obtained in the same manner as in Example 1 except that (Q-1) in Example 13 was changed to (Q-5), and the same evaluation as in Example 1 was performed. .

  The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 3 are shown in Table 1, and the evaluation results of Examples 11 to 13 and Comparative Examples 4 to 6 are shown in Table 2.

Example 14
The positive photosensitive resin composition used in Example 1 was applied on a silicon wafer using a spin coater and then dried at 90 ° C. for 30 minutes in a box oven to obtain a coating film having a thickness of about 50 μm. . A mask aligner PLA-600F made by Canon Inc. was used through this mask through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn). The exposure amount was 3000 mJ. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 150 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that a 40 μm pattern was formed. The residual film ratio at this time (film thickness after development / film thickness before development × 100) was 80.4%. Next, it was cured in a clean oven at 150 ° C./30 minutes and 320 ° C./30 minutes under an oxygen concentration of 1000 ppm or less. The film thickness after curing was 28.8 μm.

<< Comparative Example 7 >>
The positive photosensitive resin composition used in Comparative Example 1 was applied on a silicon wafer using a spin coater, and then dried in a box oven at 90 ° C. for 30 minutes to obtain a coating film having a thickness of about 50 μm. . A mask aligner PLA-600F made by Canon Inc. was used through this mask through a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn). The exposure amount was 3000 mJ. Next, 170 seconds were required for pattern opening with a 2.38% tetramethylammonium hydroxide aqueous solution. Similarly, it was rinsed with pure water for 30 seconds. As a result, it was confirmed that a 60 μm pattern was formed. The residual film ratio (film thickness after development / film thickness before development × 100) at this time was 72.1%. Next, it was cured in a clean oven at 150 ° C./30 minutes and 320 ° C./30 minutes under an oxygen concentration of 1000 ppm or less. The film thickness after curing was as low as 25.2 μm.

Claims (11)

A naphtho, which is a 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or a 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of a phenol compound represented by the formula (1) Quinonediazide sulfonic acid ester.

Naphthoquinone diazide sulfonic acid ester is 1 mol of phenol compound represented by the formula (1) and 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride or 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride The naphthoquinone diazide sulfonic acid ester according to claim 1, which is an ester with 2.0 to 4.0 mol. 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and / or 1,2-naphthoquinone-2-diazide-4 of the phenol compound represented by the formula (1), 100 parts by weight of the alkali-soluble resin (A) -A positive photosensitive resin composition comprising 1 to 50 parts by weight of a sulfonic acid ester (B). The positive photosensitive resin composition according to claim 3, wherein the alkali-soluble resin (A) is a polyamide resin having a structure represented by the general formula (2).

1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and / or 1 of 100 parts by weight of a polyamide resin (A) having a structure represented by the general formula (2), a phenol compound represented by the formula (1) , 2-naphthoquinone-2-diazide-4-sulfonic acid ester (B) 1 to 50 parts by weight and a phenolic compound (C) 1 to 30 parts by weight. The positive photosensitive resin composition according to claim 5, wherein the phenol compound (C) is represented by the general formula (3).

The positive photosensitive resin composition according to claim 5 or 6, wherein X in the polyamide resin containing the structure represented by the general formula (2) is selected from the group of the following structures.

The positive photosensitive resin composition according to any one of claims 5 to 7, wherein Y in the polyamide resin including the structure represented by the general formula (2) is selected from the group of the following structures.

The polyamide resin having the structure represented by the general formula (2) is end-capped with an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. The positive photosensitive resin composition according to any one of the above. A semiconductor device manufactured using the positive photosensitive resin composition according to claim 3. The positive photosensitive resin composition according to any one of claims 3 to 9 is applied on a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm, and prebaking, exposure, development, A method for manufacturing a semiconductor device, which is obtained by heating.