JP2002341542A - Positive photosensitive resin composition, method for manufacturing pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition excellent in sensitivity, resolution and heat resistance and having a low dielectric constant and to provide a method for manufacturing a pattern by using the above composition so that a pattern excellent in sensitivity, resolution and heat resistance and having a preferable form can be obtained. SOLUTION: The positive photosensitive resin composition contains (A) polynaphthylene having the repeating unit expressed by general formula (1) and (B) a compound which produces an acid by light. In formula (1), R<1> represents a halogen atom or 1-9C alkyl group and when a plurality of R<1> are present, they may be same or different, R<2> represents a hydrogen atom or monovalent organic group which is decomposed and converted into a hydrogen atom by the effect of an acid, x is an integer from 0 to 5, y is an integer >=1 and the sum of x and y is a natural number >=6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive photosensitive resin composition having excellent 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). 664, etc.), and those obtained by introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (J. Macromol. Sci. Chem., A24, 10, 14
07,1987), a mixture of a soluble hydroxylimide or polyoxazole precursor and a naphthoquinonediazide compound (JP-B-64-60630, USP-4).
395482), a mixture of a polyimide precursor and naphthoquinonediazide (JP-A-52-1331).
No. 5, Japanese Patent No. 5).

[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 with the absorption wavelength of the photosensitizer and low light transmittance of the heat-resistant resin or its precursor, and ultimately because the polymer structure is limited, The physical properties of the obtained film were limited, and it was not suitable for multipurpose use.

Further, the above-mentioned photoresist has a problem that it has a high dielectric constant, so that it is difficult to apply the photoresist as an interlayer insulating film in a package which is further miniaturized and miniaturized in the future.

[0005]

SUMMARY OF THE INVENTION The present invention provides a positive photosensitive resin composition having excellent sensitivity, resolution and heat resistance and having a low dielectric constant. Further, the present invention, by using the composition, sensitivity, resolution and excellent heat resistance,
An object of the present invention is to provide a method for producing a pattern capable of obtaining a pattern having a good shape. The present invention also provides a highly reliable electronic component having a pattern having a good shape and characteristics.

[0006]

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 them, they may be the same or different, and R ² is decomposed by the action of a hydrogen atom or an acid to form a hydrogen atom Represents a monovalent organic group that can be converted to a compound, wherein x is an integer of 0 to 5, y is an integer of 1 or more, and the total of x and y is a natural number of 6 or less. The present invention relates to a positive photosensitive resin composition containing polynaphthylene (A) and a compound (B) that generates an acid by light.

The present invention also relates to the above polynaphthylene (A)
However, as the general formula (1), the general formula (2)

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 them, they may be the same or different, and R ² and R ³ are decomposed by the action of a hydrogen atom or an acid. Represents a monovalent organic group which can be converted to a hydrogen atom;
And y is an integer of 1 or more, and the sum of x and y is a natural number of 5 or less), a polynaphthylene (A) having a repeating unit represented by the following formula: The present invention relates to a positive photosensitive resin composition comprising

[0008] The present invention, the general formula (1) ^{R 2} in
There is a hydrocarbon group having 1 to 9 carbon atoms, with the detachment of the carboxyl groups in the heat curing process after the image formation, the positive-type photosensitive resin is a divalent substituent which can be converted into -R 2 ^H Composition. The present invention also provides the polynaphthylene (A),
Furthermore, the general formula (3)

Embedded image(Where R¹Is a halogen atom or an alkyl having 1 to 9 carbon atoms.
Represents a kill group, and when there are a plurality of
X is an integer from 0 to 4;², R ³Is water
One that can be decomposed and converted to a hydrogen atom by the action of a hydrogen atom or acid
Having a repeating unit represented by
The positive photosensitive resin set according to claim 1, 2 or 3, wherein
About adult.

According to the present invention, there is also provided a method for producing a pattern comprising the steps of applying the positive photosensitive resin composition according to any one of the above on a supporting substrate and drying, exposing, and developing using an aqueous alkaline solution. About the law. Furthermore, the present invention
The present invention relates to an electronic component having a pattern obtained by the above 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 polynaphthylene (A) of the present invention has a repeating unit represented by the general formula (1) and has a phenolic hydroxyl group in advance, or develops a phenolic hydroxyl group through exposure and a subsequent heating step. 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 substituent having a protected hydroxy group, but from the viewpoint of easiness of synthesis and the like, as shown in the repeating unit represented by the general formula (3), 2,
Those that bind to the 6-position are preferred.

[0011]

Embedded image

Although the molecular weight of the polynaphthylene (A) of the present invention is not particularly limited, the weight average molecular weight is preferably from 2,000 to 100,000, more preferably from 4,000 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 polynaphthylene (A) of the present invention is not particularly limited, and various methods can be used. For example, poly (2,6-dihydroxynaphthylene) is polymerized from 2,6-dihydroxynaphthalene in the presence of a catalyst.
And a compound having at least one phenolic hydroxyl group in a repeating unit, such as poly (2,6-dihydroxynaphthylene), is used.
The desired polynaphthylene having an organic group that can be decomposed by the action of an acid and converted into a hydrogen atom by reacting with a precursor of an appropriate protecting group can be synthesized.

In the present invention, the compound having at least one phenolic hydroxyl group used as a raw material of polynaphthylene includes 2,3-dihydroxynaphthalene,
2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,
Examples thereof include 7-dihydroxynaphthalene and 2,8-dihydroxynaphthalene.

R ² in the structural unit represented by the general formula (1) is a hydrocarbon group having 1 to 9 carbon atoms, preferably an alkylene group which may have an unsaturated bond; With the elimination of carboxyl groups during the heat curing process after image formation,
As long as it can convert -R 2 ^H, it is not particularly limited.
Examples thereof include a chain alkylene group and a chain alkylene group having an unsaturated bond. These may have a side chain. The place crosslinking reaction upon heat curing to have an unsaturated bond in R ^2, and more preferable because heat resistance of the resin is increased. The position of the unsaturated bond is not particularly limited,
Those located at the α-position and β-position of the carboxyl group as described below are advantageous for decarboxylation in the heating step. Among these, preferred groups are a vinylene group and an arylene group.

[0016]

Embedded image (Where p is an integer of 0 to 7, q is an integer of 1 to 5, s is an integer of 0 to 5, t is an integer of 1 to 2, u is 0 to 3
And the right side is adjacent to the carboxyl group)

R ³ in the repeating unit represented by the above general formula (1) is a monovalent organic group which can be decomposed by the action of an acid and converted into a hydrogen atom. There is no particular limitation as long as it can be converted into an atom. For example, an alkyl group (preferable carbon number 1 to 9), an alkoxycarbonyl group (preferable carbon number 2 to 5), an alkoxyalkyl group (preferable carbon number 2 to 5), an alkylsilyl group (preferable carbon number 1 to 20) or an acetal Alternatively, a protective group for an alkali-soluble group, which is a group constituting a ketal, may be mentioned as a preferable example.

Examples of the group constituting the acetal or ketal include those having the following structures.

Embedded image (Wherein, R ′, R ″ and R ′ ″ are each independently an alkyl group having 5 or less carbon atoms, and X is a divalent alkylene group having 3 or more carbon atoms (preferably 20 or less) (side chain May be included).)

Specifically, alkyl groups such as t-butyl and isopropyl; alkoxycarbonyl such as t-butoxycarbonyl; alkoxyalkyl such as methoxymethyl and ethoxyethyl; methylsilyl and ethylsilyl. Typical examples thereof include, but are not limited to, an alkylsilyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an alkoxy-substituted tetrahydropyranyl group, and an alkoxy-substituted tetrahydrofuranyl group. Most preferred groups are t-butyl groups,
An isopropyl group and a tetrahydropyranyl group.

The substitution rate of the protecting group represented by R ³ with respect to a hydrogen atom is preferably 1% or more.
% Is more preferable. If the substitution rate is lower than this, there may be an adverse effect such as an increase in the film thickness of the unexposed portion.

The compound (B) which generates an acid by light used in the present invention exhibits acidity upon irradiation with actinic rays such as ultraviolet rays, and also releases the protecting group R ³ in polynaphthylene as the component (A). Has an action. Specific examples of the compound of the component (B) include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, and aromatic sulfonic acid esters. , Nitrobenzyl ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, naphthoquinonediazide-5-sulfonic acid ester and the like. Such compounds can be used in combination of two or more, if necessary, or in combination with another sensitizer. Among them, aromatic N-oxyimidosulfonate is preferable because it has high sensitivity, and diaryliodonium salt can be expected to have a suitable dissolution inhibiting effect in unexposed areas.

The compounding amount of the compound (B) which generates an acid by light into the polynaphthylene (A) is as follows.
The amount is preferably from 0.1 to 100 parts by weight, more preferably from 0.1 to 20 parts by weight, per 100 parts by weight. If the amount is less than 0.1 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. When using an adhesion imparting agent, 100 parts by weight of polynaphthylene (A)
0.1 to 20 parts by weight is preferable, and 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,
Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl-
There are 1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohesanone, cyclopentanone, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol and the like, and these may be used alone or as a mixture.

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. 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,
A desired pattern shape can be irradiated with actinic radiation.
X-rays, electron beams, ultraviolet rays, visible light, and the like can be used as actinic rays, 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;
Alkaline amines such as amines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and water-soluble organic solvents and surfactants Can be suitably used.

As a developing method, a system such as spray, 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 cause a decarboxylation reaction, whereby a final pattern having a high heat resistance and a low dielectric constant can be obtained.

The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the photosensitive resin composition of the present invention can be used 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.

One 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 of the window 6A is made of oxygen,
The window 6B is selectively etched by dry etching using a gas such as carbon tetrafluoride. 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 resin composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to an alkaline aqueous solution. To form a pattern and heat to form a resin film. This resin film causes the conductor layer to
The semiconductor device is protected from α rays and the like, and the obtained 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.

[0033]

The present invention will be described below in detail with reference to examples. Example 1 [Synthesis of polynaphthylene] 6.93 g of benzylamine was added to 3.20 g of 2,6-dihydroxynaphthalene, precipitated in ethyl acetate, and kneaded with ferric chloride hexahydrate in an agate mortar. It was left in a nitrogen atmosphere for one day.
This was purified with hydrochloric acid water to obtain poly (2,6-dihydroxynaphthylene) (A-1, number average molecular weight 13,000).

[Preparation of Positive Photosensitive Resin Composition] 100 parts by weight of the synthesized polynaphthylene (A-1) and 30 parts by weight of a naphthoquinonediazide derivative (B-1) were dissolved in ethyl lactate. The mixture was filtered through a Teflon (registered trademark) filter to obtain a photosensitive resin composition (C-1). B-1

Embedded image

[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 3 minutes to obtain a coating film having a thickness of about 1.6 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 0.5% 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 6 μm punch pattern was resolved on the silicon wafer. Separately, a photosensitive varnish is similarly applied on a silicon wafer, and the coated
0 ° C / 30 minutes, 200 ° C / 30 minutes, 350 ° C / 30
The resin was cured in the order of minutes, the resin was cured, the film thickness was measured, and the residual film ratio was determined. The obtained coating film was peeled off, and a 10% weight loss temperature (Td) was determined by TGA measurement.

Example 2 1.50 g of A-1 was dissolved in ethyl lactate, 6.21 g of di-tert-butyl dicarbonate and 0.35 g of dimethylaminopyridine were added and stirred. The reaction solution was added dropwise to heated hexane, and the obtained precipitate was washed with a dilute aqueous acetic acid solution and water, and then poly {2,6-di (t-butyloxycarbonyloxy) naphthylene} (A-2, (Average molecular weight 29,000) was obtained.

The synthesized polynaphthylene derivative (A-2)
100 parts by weight and p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (B-2) 1
5 parts by weight of PEGMEA (propylene glycol-1-
After dissolving in 200 parts by weight of monomethyl ether-2-acetate), the solution was filtered through a 0.2 μm Teflon filter to obtain a photosensitive resin composition (C-2). Next, the characteristics were evaluated in the same manner as in Example 1 using this photosensitive varnish.

Example 3 The acid generator in Example 2 was replaced with diphenyliodonium-
Evaluation was performed in the same manner as in Example 2 except that 9,10-dimethoxyanthracene-2-sulfonate (B-3) was used. Example 4 Evaluation was performed in the same manner as in Example 2 except that the acid generator in Example 2 was changed to naphthylimidyl triflate (B-4).

Example 5 Evaluation was performed in the same manner as in Example 2 except that di-t-butyl dicarbonate and dimethylaminopyridine were changed to 3,4-dihydro-2H-pyran and pyridine p-toluenesulfonate. did.

Example 6 The acid generator in Example 5 was replaced with diphenyliodonium-
The evaluation was performed in the same manner as in Example 5 except that 9,10-dimethoxyanthracene-2-sulfonate (B-3) was used.

Example 7 Evaluation was performed in the same manner as in Example 5 except that the acid generator in Example 5 was changed to naphthylimidyl triflate (B-3).

Comparative Example 1-2 Example 1 was repeated except that the evaluation polymer was changed to A-3 and A-4, respectively, and the dissolution inhibitor was changed to a photosensitive diazoquinone compound (B-5) having the following structure. It was evaluated similarly.

[0043]

Embedded image Comparative Example 1 (A-3) Z ₁ = (CF ₃ ) ₂ C, Z ₂
= H Comparative Example 2 (A-4) Z ₁ = CH ₂ , Z ₂ = C
H ₃

[0044]

Embedded image

Comparative Example 3 The polymer evaluated in Example 2 was poly (t-butyloxycarbonyloxystyrene, weight average molecular weight 22.0
The evaluation was performed in the same manner as in Example 2 except that the value was changed to 00).

Table 1 shows the evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3.

[0047]

[Table 1]

[0048]

The positive photosensitive resin composition of the present invention is excellent in sensitivity, resolution and heat resistance and can form a film having a low dielectric constant. Further, according to the method for producing a pattern of the present invention, by using the composition, a pattern having a good shape excellent in sensitivity and resolution and having both heat resistance and low dielectric constant 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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuyuki Sasada 4-19-10-309 Shimomaruko, Ota-ku, Tokyo (72) Inventor Masahiko Hiro 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in Research Institute (reference) 2H025 AA00 AA01 AA02 AA03 AA10 AB17 AC01 AC04 AC05 AC06 AD03 BE00 BG00 FA01 FA03 FA17 4J002 CE001 EB116 EH146 EQ016 EV246 EV246 GP296 GP03

Claims (6)

[Claims] 1. A compound of the 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 them, they may be the same or different, and R ² is decomposed by the action of a hydrogen atom or an acid to form a hydrogen atom Represents a monovalent organic group that can be converted to a compound, wherein x is an integer of 0 to 5, y is an integer of 1 or more, and the total of x and y is a natural number of 6 or less. A positive photosensitive resin composition containing polynaphthylene (A) and a compound (B) that generates an acid by light. 2. Polynaphthylene (A) is represented by the following 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 R ² and R ³ are decomposed by the action of a hydrogen atom or an acid. Represents a monovalent organic group which can be converted to a hydrogen atom, x is an integer of 0 to 4, y is an integer of 1 or more, x and y
(A natural number of 5 or less)), and a poly (naphthylene) (A) having a repeating unit and a compound (B) which generates an acid by light. 3. In the general formula (1), R ² is a hydrocarbon group having 1 to 9 carbon atoms, which is converted to —R ² H with the elimination of a carboxyl group during the heat curing process after image formation. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is a divalent substituent. 4. The polynaphthylene (A) further comprises a compound represented by the general formula (3): (Wherein, R ¹ represents a halogen atom or an alkyl group having 1 to 9 carbon atoms, and when there are a plurality of, may each be the same or different, x is an integer of 0 to 4, R ² and R ³ represents a hydrogen atom or a monovalent organic group which can be converted into a hydrogen atom by being decomposed by the action of an acid.) The positive-type photosensitive resin according to claim 1, 2 or 3, wherein Composition. 5. A pattern comprising a step of applying and drying the positive photosensitive resin composition according to claim 1 on a support substrate, a step of exposing, and a step of developing with an aqueous alkali solution. Manufacturing method. 6. An electronic component having a pattern obtained by the method according to claim 5 as a surface protective film or an interlayer insulating film.