JP2000275842A - Positive photosensitive resin composition, production of pattern, and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive photosensitive resin compsn. having excellent sensitivity and resolution by incorporating a specified polyphenylene oxide and a compd. which produces an acid by light. SOLUTION: The resin compsn. contains a polyphenylene oxide having the recurring unit expressed by the formula and a compd. which produces an acid by light. In the formula, R1 is a halogen atom or 1-9C alkyl group, and when a plurality of R1 are present, each may be same as or different from others, and x is an integer 0 to 3. The mol.wt. of the polyphenylene oxide is preferably 4,000 to 100,000 weight average mol.wt. from the viewpoint of physical properties of the film, and more preferably 10,000 to 40,000. The compd. which produces the acid by the light has functions to produce the acid by irradiation of the light and to enhance the solubility of the irradiated region by the light with an alkali soln. As for the kinds of the compd., for example, photosensitive diazoquinone compds., aryl diazonium salts, diaryl iodonium salts, triaryl sulfonium salts or the like can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive photosensitive resin composition excellent in sensitivity, resolution and heat resistance, a method for producing a pattern using the same, and an electronic component.

[0002]

2. Description of the Related Art Conventionally, as a photoresist using a heat-resistant resin, a precursor thereof, and the like, and its use, for example,
A negative type photoresist obtained by introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (JP-A-49-11541, JP-A-49-15441).
No. -40922, No. 54-145794, No. 56-38038, etc., and those using a polybenzoxazole precursor in the same manner (Japanese Patent Laid-Open No. 2-60659, 1988 by the Society of Polymer Science, Japan). And the like, and a positive type photoresist obtained by introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (J. Macromol. Sci. Chem., A24, 10, 1407). , 1
987), a mixture of a soluble hydroxylimide or polyoxazole precursor and a naphthoquinonediazide compound (JP-B-64-60630, USP-439).
5482), and a mixture of a polyimide precursor and naphthoquinonediazide (JP-A-52-13315).

[0003] However, the negative type photoresist has a problem in resolution in terms of its function, and in some applications, the yield in production is lowered. Also,
Conventional positive photoresists have low sensitivity and resolution due to problems associated with the absorption wavelength of the photosensitizer and low light transmittance of the heat-resistant resin or its precursor, and are limited in the final structure because the polymer structure is limited. However, the physical properties of the resulting film were limited, making it unsuitable for multipurpose use.

[0004]

SUMMARY OF THE INVENTION The present invention provides a positive photosensitive resin composition having excellent sensitivity, resolution and heat resistance. The present invention also provides a method for producing a pattern which is excellent in sensitivity, resolution and heat resistance by using the above-mentioned composition, and in which a pattern having a good shape is obtained. The present invention also provides a highly reliable electronic component having a pattern having a good shape and characteristics.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):

Embedded image (Wherein, R ¹ represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of groups, each may be the same or different, and x is an integer of 0 to 3). The present invention relates to a positive photosensitive resin composition containing a polyphenylene oxide (A) having a repeating unit and a compound (B) that generates an acid by light.

In the present invention, the polyphenylene oxide (A) may be represented by the following general formula (1):

Embedded image (In the formula, R ¹ represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of them, they may be the same or different, and x is an integer of 0 to 3.) The present invention relates to a positive photosensitive resin composition having repetition.

In the present invention, the polyphenylene oxide (A) may further comprise a compound represented by the general formula (3):

Embedded image (In the formula, R ² each independently represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of them, they may be the same or different, and y is an integer of 0 to 4.) The present invention relates to a positive photosensitive resin composition having a repeating unit represented by the formula:

The present invention also relates to a positive photosensitive resin composition wherein the compound (B) which generates an acid by light is a photosensitive diazoquinone compound. The present invention also relates to a positive photosensitive resin composition in which the photosensitive diazoquinone compound is 2,3,4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone.

The present invention also relates to a method for producing a pattern, comprising a step of applying and drying the positive photosensitive resin composition on a support substrate, a step of exposing, and a step of developing using an alkaline aqueous solution. Furthermore, the present invention relates to an electronic component having a pattern obtained by the above-mentioned manufacturing method as a surface protective film or an interlayer insulating film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive resin composition of the present invention will be described in detail. The polyphenylene oxide (A) of the present invention has a repeating unit represented by the general formula (1) and has a phenolic hydroxyl group. By having the repeating unit, the photosensitive resin composition of the present invention is provided with good solubility in an aqueous alkali solution. There is no particular limitation on the bonding position of the phenolic hydroxyl group, but from the viewpoint of easiness of synthesis and the like, a repeating unit represented by the above general formula (2) is preferably bonded to the ortho bond to the ether bond.

The polyphenylene oxide (A) of the present invention
May have a repeating unit represented by the general formula (3) together with a repeating unit represented by the general formula (1). In this case, assuming that the number of repeating units represented by the general formula (1) is m and the number of repeating units represented by the general formula (3) is n, the copolymerization ratio (m / n) is 10 /
It is preferably 90 or more, more preferably 50/50 to 85/15, and particularly preferably 75/25. If the copolymerization ratio m / n is less than 10/90, the developability in an aqueous alkaline solution tends to decrease.

Although the molecular weight of the polyphenylene oxide (A) of the present invention is not particularly limited, the weight average molecular weight is preferably 4,000 to 100,000, more preferably 10,000 to 40,000, in view of physical properties of the film. In the present invention, the molecular weight can be measured by a gel permeation chromatography method and determined using a standard polystyrene calibration curve.

The method for producing the polyphenylene oxide (A) of the present invention is not particularly limited, and various methods can be used.
For example, a compound having two phenolic hydroxyl groups such as catechol or a derivative thereof is reacted with dihydropyran in the presence of a catalyst such as p-toluenesulfonic acid pyridine salt (PPTS) to protect one of the phenolic hydroxyl groups. Then, using the obtained compound and, if necessary, other phenols as a raw material, polymerization is carried out in the presence of a catalyst to synthesize polyphenylene oxide, and finally, the polyphenylene oxide can be obtained by removing a protecting group with hydrochloric acid or the like. . An example of this reaction is shown below.

[0014]

Embedded image (M and n indicate the number of repetitions, and the obtained copolymer is a random copolymer of each repeating unit)

In the present invention, the compound having two phenolic hydroxyl groups used as a raw material of polyphenylene oxide includes catechol, 3-methylcatechol, 3-ethylcatechol, 3-propylcatechol, 3-chlorocatechol, -Bromocatechol, 3
-Fluorocatechol, 3-iodocatechol, 4-methylcatechol, 4-ethylcatechol, 3,4-dimethylcatechol, resorcinol, 2-methylresorcinol and the like, and other phenols that can be used in combination therewith include phenol, o-cresol, m-
Cresol, o-ethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol,
2,6-xylenol, 3,5-xylenol, thymol, carvacrol and the like.

The compound (B) which generates an acid by light used in the present invention has a function of generating an acid by irradiation with light and increasing the solubility of the irradiated portion in an aqueous alkali solution. Examples thereof include a photosensitive diazoquinone compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt.
Although there is no particular limitation, a photosensitive diazoquinone compound is preferred because of its high sensitivity.

The photosensitive diazoquinone compound is a compound obtained by subjecting an o-quinonediazidosulfonyl chloride to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. And many types are already known. For example,

Embedded image (Where Q is a hydrogen atom,

Embedded image And at least one of each of the compounds

Embedded image ) And the like.

Among these, 2,3,4-tris [-2
-Diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (D4SB) undergoes a transfer reaction upon irradiation with i-rays or g-rays to become indene carboxylic acid, and the absorption decreases in the region of 300 nm or more. Are particularly preferred because they are known (Polymer, 36 (11), (1995) 2153).

The compounding amount of the compound (B) which generates an acid by light to the polyphenylene oxide (A) is preferably 1 to 100 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the polyphenylene oxide (A). More preferably, it is part by weight. If the amount is less than 1 part by weight, the patterning properties tend to be poor, and if it exceeds 100 parts by weight, the film formability tends to decrease.

The positive photosensitive resin composition of the present invention may contain, if necessary, an organosilicon compound for imparting adhesion.
An adhesion imparting agent such as a silane coupling agent and a leveling agent may be added. Examples of these include, for example, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris (acetylacetonate)
Aluminum and acetyl acetate aluminum diisopropylate are exemplified. can give. When an adhesion promoter is used, polyphenylene oxide (A) 1
0.1 to 20 parts by weight is preferable with respect to 00 parts by weight,
0.5 to 10 parts by weight is more preferable.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidinone, γ-butyrolactone, N, N
-Dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether,
There are 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 acetate, cyclohesanone, tetrahydrofuran and the like. May be used.

In the method for producing a pattern using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, aluminum substrate or the like. Application methods include spin coating using a spinner, spray coating using a spray coater, dipping,
Printing, roll coating and the like. Next, preferably after pre-baking at 60 to 120 ° C. to dry the coating film,
Actinic radiation can be irradiated in a desired pattern.
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 nm to 500 nm are preferable. Next, a pattern can be obtained by developing and dissolving and removing the irradiated portion.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; Secondary amines such as n-propylamine, and tertiary amines such as triethylamine and methyldiethylamine;
Aqueous alkalis such as amines, alcoholamines such as dimethylethanolamine and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and water-soluble organic solvents and interfaces. An aqueous solution to which an appropriate amount of an activator has been added can be suitably used.

As a developing method, a method such as spraying, paddle, immersion, and ultrasonic wave can be used. Next, the pattern formed by development can be rinsed. Distilled water can be used as the rinsing liquid. Next, a heat treatment is performed to obtain a final pattern having high heat resistance.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and more specifically, for surface protection films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

An example of the manufacturing process of the semiconductor device of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . An interlayer insulating film 4 is formed on the semiconductor substrate by spin coating or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, the surface protective film is coated with the photosensitive polymer composition by a spin coating method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is drawn on a predetermined portion. A pattern is formed by developing with an aqueous solution, and heated to form a resin film. This resin film protects the conductor layer from external stress, α-rays, and the like, and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0030]

The present invention will be described below in detail with reference to examples. Example 1 [Synthesis of polyphenylene oxide having phenolic hydroxyl group] 4.96 g of 3-methylcatechol and 1.81 ml of dihydropyran were dissolved in 6.0 ml of toluene, and p was added while maintaining the reaction system at 0 to 5 ° C. 0.025 g of pyridine toluenesulfonate were added. After stirring for several minutes, 3.62 ml of dihydropyran dissolved in 2.0 ml of toluene was further added.
Was slowly added dropwise. Further, 0.025 g of pyridine p-toluenesulfonate was added, and the mixture was added at room temperature in a nitrogen atmosphere at room temperature.
Stirred for hours. The reaction solution was diluted with 60 ml of ether.
Washed with 2% aqueous sodium hydroxide. The ether layer was dried with sodium sulfate and the ether was distilled off. The remaining colorless oily substance was purified by column chromatography (silica gel, toluene) to obtain 2- (tetrahydropyran-2-yl) oxy-6-methylphenol.

Next, 1.0 ml of pyridine was added to 0.030 g of cuprous chloride, and the mixture was stirred under a nitrogen atmosphere to obtain a solution of a copper (II) -pyridine complex. This was followed by 2- (tetrahydropyran-2-yl) oxy-6-methylphenol and 2.
6.0 mmol of 6-xylenol in total (7 mole ratio)
5:25), sodium sulfate and 5.0 ml of toluene were added, and the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into methanol to obtain a brown precipitate. The obtained precipitate was filtered off, dissolved in tetrahydrofuran, and deprotected by adding a small amount of hydrochloric acid. Further, this was poured into an aqueous hydrochloric acid solution, and the precipitate was filtered and washed with water to obtain a polyphenylene oxide copolymer (A-1, a molar ratio m: n = 75: 25 in the general formula (1), and a weight average molecular weight of 23,000). ) Got.

[Preparation of positive photosensitive resin composition] 100 parts by weight of the synthesized polyphenylene oxide (A-1)
After dissolving 25 parts by weight of 2,3,4-tris (-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone (B-1) in 200 parts by weight of cyclohexane, a 0.2 μm Teflon filter is used. To obtain a photosensitive resin composition.

[Evaluation of Characteristics] The photosensitive varnish was applied on a silicon wafer using a spin coater, and then dried in an oven at 100 ° C. for 10 minutes to obtain a coating film having a thickness of about 2 μm. The coating film was irradiated with ultraviolet light from a high-pressure mercury lamp through a glass mask, and then subjected to paddle development in a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds to dissolve and remove the exposed portion and rinse with pure water.
As a result, it was confirmed that a 1 μm punch pattern was resolved on the silicon wafer. Separately, a photosensitive varnish is similarly applied on a silicon wafer, and the varnish is placed in an oven for 10 minutes.
0 ° C / 30 minutes, 200 ° C / 30 minutes, 350 ° C / 30
The resin was cured by heating in the order of minutes. The obtained coating film was peeled off, and the glass transition temperature (Tg) was determined by TMA measurement (tensile).

Example 2 The 2,3,4-tris (-2-diazo-
1 (2H) -naphthalenone-4-sulfonyloxy]
Evaluation was performed in the same manner as in Example 1 except that benzophenone was changed to a photosensitive diazoquinone compound (B-2) having the following structure.

[0035]

Embedded image

Example 3 The 2,3,4-tris (-2-diazo-
1 (2H) -naphthalenone-4-sulfonyloxy]
Evaluation was performed in the same manner as in Example 1 except that benzophenone was changed to a photosensitive diazoquinone compound (B-3) having the following structure.

[0037]

Embedded image

Comparative Example 1 The 2,3,4-tris (-2-diazo-
1 (2H) -naphthalenone-4-sulfonyloxy]
Evaluation was performed in the same manner as in Example 1 without adding benzophenone.

Comparative Example 2 Photosensitive diazoquinone compound (B-2) in Example 2
Was evaluated in the same manner as in Example 1 except that no was added.

Comparative Example 3 Photosensitive diazoquinone compound (B-3) in Example 3
Was evaluated in the same manner as in Example 1 except that no was added.

Comparative Example 4 [Synthesis of polyphenylene oxide] Cuprous chloride 0.03
To 0 g, 1.0 ml of pyridine was added and stirred under a nitrogen atmosphere to obtain a solution of a copper (II) -pyridine complex. To this 2.
6 mmol of 6-xylenol, sodium sulfate and 5.0 ml of toluene were added and reacted at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into methanol to obtain a polyphenylene oxide copolymer (A-2, m / n = 0/100 in the general formula (1)). And it evaluated similarly to Example 1 except having replaced (A-1) with (A-2) in Example 1.

Table 1 shows the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 4.

[0043]

[Table 1]

[0044]

The positive photosensitive resin composition of the present invention is excellent in sensitivity, resolution and heat resistance. Further, according to the method for producing a pattern of the present invention, by using the composition, a pattern having excellent sensitivity, resolution and heat resistance and having a good shape can be obtained. Further, the electronic component of the present invention has high reliability by having a pattern having a good shape and characteristics.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film layer 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film layer

Continued on the front page (72) Inventor Kazumasa Takeshi 370-1 Kubota, Yonezawa-shi, Yamagata Corp. Corp. Mukubota B Building 202 (72) Inventor Kenichi Okuyama 139-2 Toyama, Yonezawa-shi, Yamagata ABS Corp 206 F-term (reference) 2H025 AA02 AA10 AB16 AB17 AD03 BE00 CB19 CB45 DA01 DA02 DA40 EA04 FA17

Claims (7)

[Claims] 1. A compound of the general formula (1) (In the formula, R ¹ represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of them, they may be the same or different, and x is an integer of 0 to 3.) A positive photosensitive resin composition containing a polyphenylene oxide (A) having a repeating unit and a compound (B) that generates an acid by light. 2. Polyphenylene oxide (A) is represented by the following general formula (1): (Wherein, R ¹ represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of groups, each may be the same or different, and x is an integer of 0 to 3). The positive photosensitive resin composition according to claim 1, which has a repeating unit. 3. The polyphenylene oxide (A) further comprises a compound represented by the general formula (3): (In the formula, R ² each independently represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of them, they may be the same or different, and y is an integer of 0 to 4.) The positive photosensitive resin composition according to claim 1, which has a repeating unit represented by the formula: 4. The compound (B) which generates an acid by light,
4. The positive photosensitive resin composition according to claim 1, which is a photosensitive diazoquinone compound. 5. The method according to claim 1, wherein the photosensitive diazoquinone compound is 2,3,3.
The positive photosensitive resin composition according to claim 4, which is 4-tris [-2-diazo-1 (2H) -naphthalenone-4-sulfonyloxy] benzophenone. 6. Production of a pattern comprising a step of applying and drying the photosensitive polymer composition according to claim 1 on a support substrate, a step of exposing, and a step of developing using an alkaline aqueous solution. Law. 7. An electronic component having a pattern obtained by the method according to claim 6 as a surface protective film or an interlayer insulating film.