JP2001242640A - Processing method for photosensitive resin composition and semiconductor device using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method which suppresses the damage of a photosensitive resin composition in etching. SOLUTION: In the processing method, a photosensitive resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone compound is applied, prebaked, exposed and developed to form a pattern, curing is carried out at a temperature higher than the prebaking temperature and lower than the final curing temperature, and after etching, the photosensitive resin composition is finally cured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a photosensitive resin composition which can reduce damage during etching.

[0002]

2. Description of the Related Art In recent years, ICs and LSIs have been used in the semiconductor industry.
For example, a photosensitive resin composition such as a photoresist or a photosensitive polyimide is widely used for an insulating film or a protective film in a package that requires the preparation or processing of an ultrafine circuit such as a superfine circuit. A feature of the photosensitive resin is that a resin pattern having excellent accuracy can be obtained with a relatively simple apparatus. In particular, a positive photoresist based on a novolak resin using a diazoquinone type as a photosensitizer does not swell during development, so it is possible to form a pattern with excellent resolution, and the developer is easy to work with an alkaline aqueous solution. It is widely used in the production of the above-mentioned semiconductor fine circuits and the like.

On the other hand, a photosensitive heat-resistant resin composition such as photosensitive polyimide used for an insulating film and a protective film of a semiconductor also has a positive photosensitive heat-resistant property having characteristics such as high resolution and no pollution of a developing solution. Resin compositions have been developed in the same manner as photoresists (for example, JP-A-63-96162, JP-B-1-46862, etc.), and have attracted attention as highly integrated semiconductor insulating and protective film resins. ing. Most positive photosensitive resins are obtained by adding a photosensitive agent such as the above-mentioned diazoquinone compound to an alkali-soluble polymer. In the unexposed area, these diazoquinone compounds and the like are insoluble in an alkaline aqueous solution, but undergo a chemical change upon exposure to become soluble in the alkaline aqueous solution. For this reason, utilizing the difference in solubility between the exposed and unexposed regions, the coating film of the resin composition to which the compound is added is exposed and then treated with an aqueous alkaline solution to form a coating film pattern of only the unexposed portions. Becomes possible.

[0004] JP-A-63-96162 and Japanese Patent Publication No.
The positive photosensitive heat-resistant resin composition described in Japanese Patent No. 466862 or the like is different from a photoresist made of a novolak resin and is permanently left on a semiconductor as an insulating film or a protective film. The photoresist made of novolak resin is exposed and developed, and is peeled off immediately after pattern formation. However, the photosensitive heat-resistant resin composition has about 300 to
A general curing process involves heat treatment at a temperature of 400 ° C. to convert the film into a film having excellent thermal stability. Thereafter, a photoresist is applied and patterned, and using this as a mask, the glass inorganic protective film is etched by reactive ion etching (RIE) or the like, and then the photoresist is peeled off.
It is a molding material such as epoxy resin, phenol resin, silicone resin, etc., and is molded by casting, transfer forming, and the like.

In the above process, there is no damage at the time of etching because the photosensitive resin composition is not directly exposed by RIE or the like, but in recent years, the photosensitive resin composition is used as a mask instead of applying a photoresist. (Japanese Patent Application No. 10-060800). In the case of this process, since the photosensitive resin composition remains permanently, the surface of the photosensitive resin composition becomes uneven due to damage at the time of etching, which is likely to be defective in appearance, and encapsulation of a sealing resin or the like. Occasionally, there was a problem that sealing could not be completed completely between the recesses, resulting in voids, which tended to cause cracks from the voids during reliability tests (such as during moisture absorption treatment).

[0006]

SUMMARY OF THE INVENTION The present invention provides a processing method for remarkably reducing damage during etching of a photosensitive resin composition.

[0007]

According to the present invention, a pattern is formed from a photosensitive resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone, and then a temperature higher than a prebake temperature, but lower than a final curing temperature. , Followed by etching and final curing.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention reduces damage during etching by performing curing (pre-etch baking) at a temperature higher than a pre-bake temperature and lower than a final curing temperature after pattern formation and before etching. I found a processing method. Although the details of this reason are not yet clear, since polybenzoxazole is a polymerizable resin, it exists as a precursor or close to the precursor of polybenzoxazole at the time of pattern formation. When heated to 400 ° C., the polymerization reaction ends, forming an oxazoline ring and a tough film is obtained. When this oxazoline ring is formed, the flexibility of polybenzoxazole is limited. When etching is performed in this state, the composition having higher fluidity than polybenzoxazole is etched first, and the resin surface becomes uneven. In order to reduce the unevenness, it has been found that a method in which a temperature at which an oxazole ring is not completely formed is preferable.

In this state, the difference in etching rate during etching is reduced and the unevenness is reduced without significantly limiting the flexibility of the resin composition itself. The temperature of the pre-etch bake is better when the temperature is close to the pre-bake temperature with respect to the reduction of the unevenness.However, since the residual solvent may volatilize during etching and contaminate the etcher, etc. However, there is a problem that it easily accumulates on the resin surface or the opening of the wafer. Good conditions are
Between 120 ° C and 250 ° C. More preferably, 1
It is between 50 ° C and 200 ° C. If the temperature is lower than 120 ° C., the temperature becomes equal to or lower than the temperature of the pre-baking after applying the resin, there is almost no thermal effect, and there is a problem that the etcher is contaminated significantly. There is a problem that the effect of the etch bake hardly appears and the surface irregularities become prominent during etching.

[0010] Further, the irregularities at the time of etching appear more remarkably as the film thickness to be etched becomes thicker. However, the film thickness range is not particularly limited since the above film thickness range changes depending on the etching method, gas composition, power, and the like.

After completion of the etching under the above conditions, final curing is required. The pre-etch bake is only a measure for improving etching, and does not provide stability for the resin itself. The final curing needs to be performed at a temperature at which the oxazole ring is formed, and requires a temperature of 250 ° C. or higher, and is preferably in the range of 300 ° C. to 400 ° C. If the final curing temperature is lower than 250 ° C., there is a problem that the cyclization reaction is insufficient, the material is brittle in mechanical properties, and other physical properties are significantly reduced.

The polybenzoxazole precursor used in the present invention is represented by the general formula (1). The polybenzoxazole precursor of the formula (1) comprises a bisphenol having the structure of X, a dicarboxylic acid having the structure of Y, a terminal treating agent having the structure of E, and a modifier having a structure of Z if necessary. This polybenzoxazole precursor has about 2
When heated at 50 to 400 ° C., the ring closes and changes to polybenzoxazole having high heat resistance.

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Examples of X in the formula (1) include, but are not particularly limited to, the following.

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[0014] Examples of Y in the formula (1) include, but are not particularly limited to, the following.

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Examples of E in the formula (1) include, but are not limited to, the following.

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Further, examples of Z in the formula (1) include, but are not limited to, the following.

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When using these X, Y, E, and Z, one type or a mixture of two or more types may be used.

The positive resin composition of the present invention is based on a polybenzoxazole precursor represented by the general formula (1) as a main component and a positive photosensitive agent.
The positive photosensitive agent used in the present invention is a diazoquinone compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazite structure. These are U.S. Pat.Nos. 2,772,972, 2,797,213, 3,669,658.
Known substances disclosed in the above publication.

Positive resists obtained by blending these quinonediazide compounds with novolak resins are currently being actively used for fabricating circuits on semiconductor chips. That is, since the quinonediazide compound has a dissolution inhibiting ability, the solubility of the novolak resin can be reduced, and a relief pattern with a high residual film can be provided. However, Tokufair
As disclosed in 1-46862, some quinonediazide compounds that are effective for novolak resins have no effect on polybenzoxazole precursors and have low dissolution inhibiting ability. If the dissolution inhibiting ability is low, the residual film ratio becomes low, and a good pattern shape cannot be obtained. Examples of the quinonediazide compound used in the present invention include the following, but are not particularly limited thereto.

[0020]

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The positive photosensitive resin composition used in the present invention may optionally contain a dihydropyridine derivative for enhancing the photosensitive characteristics. Examples of the dihydropyridine derivative include 2,6-dimethyl-3,5-diacetyl-4- (2′-nitrophenyl) -1,4-dihydropyridine and 4- (2′-nitrophenyl) -2,6
-Dimethyl-3,5-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dihydrophenyl)
-2,6-dimethyl-3,5-dicarbomethoxy-1,
4-dihydropyridine and the like can be mentioned.

In the positive photosensitive resin composition used in the present invention, a dissolution accelerator can be blended in order to enhance the sensitivity characteristics and improve the solubility of the exposed portion. Examples of the dissolution promoter include the following phenol compounds, but are not particularly limited thereto.

[0023]

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[0024]

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The positive photosensitive resin composition used in the present invention contains an organosilicon compound represented by the general formulas (4), (5) and (6), and a positive photosensitive resin cured film and a silicon wafer. It is blended to improve the adhesiveness with the cured epoxy resin for semiconductor encapsulation. The organosilicon compounds may be used alone or in combination of two or more. On the other hand, if the amount is too small, the effect of improving the adhesiveness cannot be obtained, and if the amount is too large, the mechanical strength of the cured film of the positive photosensitive resin is lowered, and the effect of reducing the stress is not preferable.

[0026]

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The organosilicon compounds represented by the general formulas (4) and (5) are prepared by combining an acid (di) anhydride and a silane coupling agent having an amino group in an organic solvent at 20 to 100 ° C.
It is obtained by reacting for minutes to 10 hours.

Examples of the acid anhydride include maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, phthalic anhydride and the like. But are not particularly limited thereto.

Examples of the acid dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Anhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4 ′
-Benzophenonetetracarboxylic dianhydride, naphthalene-, 2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4, 5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6
7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3
5,6,7-hexahydronaphthalene-2,3,6,7
-Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3 , 3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic dianhydride Anhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3
3 "-p-terphenyltetracarboxylic dianhydride,
2,3,3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) -propane dianhydride, bis (2,
3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3
8,9-tetracarboxylic dianhydride, perylene-3,
4,9,10-tetracarboxylic dianhydride, perylene-
4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene -1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,1
0-tetracarboxylic dianhydride, pyrazine-2,3
5,6-tetracarboxylic dianhydride, pyrrolidine-2,
3,4,5-tetracarboxylic dianhydride, thiophene-
2,3,4,5-tetracarboxylic dianhydride, 4,4
'-Hexafluoroisopropylidene diphthalic dianhydride; and the like, but is not particularly limited thereto.

Examples of the silane coupling agent having an amino group include γ-aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane.
Aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-
Aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (Β-aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like,
It is not particularly limited to these.

The organosilicon compound represented by the general formula (6) is obtained by reacting a silane coupling agent having an epoxy group with a tetracarboxylic dianhydride at 20 to 100 ° C. for 30 minutes to 10 hours. Examples of the acid dianhydride include those similar to those in the case of the organosilicon compound of the general formula (4), but are not particularly limited thereto. Further, as the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane And the like, but not particularly limited thereto.

The organosilicon compounds represented by the above general formulas (4), (5) and (6) are obtained by reacting, and have excellent properties in a positive photosensitive resin composition containing the same. However, excellent properties can be exhibited by blending each raw material without reacting.

If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition used in the present invention. In addition, various solvents are used to form a varnish. As the solvent, N
-Methyl-2-pyrrolidone, γ-butyrolactone, N,
N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl- 1,3-
Examples include, but are not limited to, dibutylene glycol acetate, 1,3-dibutylene glycol-3-monomethyl ether, methyl puruvate, ethyl puruvate, methyl-3-methoxypropionate, and the like. Also,
The solvents may be used alone or as a mixture.

In the method of using the positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, a ceramic substrate, an aluminum substrate or the like.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after pre-baking at 60 to 130 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic radiation. 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. 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, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine,
An aqueous solution of an alkali such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as alcohol such as methanol or ethanol or a surfactant. Can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. As the rinse liquid,
Use distilled water or the like. Thereafter, a pre-etch bake is performed. The pre-bake is performed at a temperature equal to or higher than the pre-bake, preferably at 120 to 250 ° C. Dryers include oven furnaces, furnace furnaces, hot plates, etc.
There is no particular limitation as long as high-temperature heat treatment is possible. Next, reactive ion etching (RIE) using a positive resin as a mask
Etching the glass inorganic protective film and the like by, for example, and then performing heat treatment to form an oxazole ring, thereby obtaining a final pattern having high heat resistance. The heating temperature is preferably 250 ° C. or higher, more preferably 300 ° C. to 400 ° C. in the sense that an oxazole ring is formed.
Sufficient performance can be obtained by performing a long-time baking even at 0 ° C. or lower, but the production time becomes longer. The oxygen concentration is preferably 5% or less under a nitrogen purge, more preferably 1% or less, as described above. 1000pp according to the type of dryer
It is preferable that the oxygen concentration be as low as not more than m. In this case, since oxidation is difficult, curing can be performed at a higher temperature, and heat resistance of the photosensitive resin can be improved.

The photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like. A semiconductor device manufactured by using the method for processing a photosensitive resin composition of the present invention is a highly reliable semiconductor device. As a method of manufacturing a semiconductor device except for the present processing method, a conventionally known method can be used.

[0036]

The present invention will be described below in detail with reference to examples. << Example 1 >> * Synthesis of polyamide Dicarboxylic acid derivative 443. obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole.
2 g (0.9 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 36
6.3 g (1.0 mol) were put into a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 3000 g of N-methyl-2-pyrrolidone was added.
And dissolved. Then use an oil bath at 75 ° C
For 12 hours. Next, 5-norbornene-2,3- dissolved in 500 g of N-methyl-2-pyrrolidone.
32.8 g (0.2 mol) of dicarboxylic anhydride were added,
The reaction was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1, the precipitate was collected by filtration, washed sufficiently with water, and dried under vacuum to obtain the desired polyamide (A-1). Obtained.

* Preparation of positive photosensitive resin composition 100 g of synthesized polyamide (A-1), 25 g of diazoquinone (B1) having a structure of the following formula, 10 g of phenol compound (P1) having a structure of the following formula, (P2 ) 5
g, the organosilicic acid compound obtained by reacting γ-aminopropyltriethoxysilane with maleic anhydride
g, γ-aminopropyltriethoxysilane and 3,
1 g of an organosilicon compound obtained by reacting 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride with N
-Methyl-2-pyrrolidone, dissolved in 250 g,
The mixture was filtered through a 2 μm Teflon filter to obtain a photosensitive resin composition.

[0038]

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[0039]

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* Preparation of pattern After applying this positive photosensitive resin composition on a silicon wafer by using a spin coater, it was dried at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 5 μm. Was. G-line stepper exposure machine NSR-1505G3A
50 mJ / c through a reticle by Nikon Corporation
Increase from m ² by 10mJ / cm ² 540mJ / cm
Exposure was performed up to ² . Next, the exposed portion was dissolved and removed by immersion in a 1.40% aqueous solution of tetramethylammonium hydroxide for 60 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 230 mJ / cm ² .
(The sensitivity is 230 mJ / cm ² ). At this time, the residual film ratio (film thickness after development / film thickness before development × 100) showed a very high value of 93.1% (the resin in this state is referred to as EX1).
After the developed wafer prepared here is cured at 130 ° C. for 90 minutes, the etching apparatus OPM-EM1000 is used.
Using Tokyo Ohka Kogyo Co., Ltd., oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness after processing is about 3
μm. The resin surface was in a good condition without any particular abnormality.

A coating film having a thickness of 15 μm after pre-baking was obtained by the same coating as described above, and then developed without exposure (the resin in this state was NEX1) at 130 ° C. After curing for 90 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
Was used to perform oxygen plasma treatment at 1000 W for 2 minutes. This wafer was cured at 320 ° C. for 30 minutes to obtain a cured film after peeling from the wafer. The tensile properties of this cured film were evaluated using Tensilon. The tensile strength is
The tensile modulus was 12.5 kg / mm ² , the tensile modulus was 256 kg / mm ² , and the tensile elongation was 45%, which was a high value. No decrease in strength due to plasma damage was observed.

Example 2 After the developed wafers (EX1 and NEX1) prepared in Example 1 were cured at 200 ° C. for 60 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness of EX1 is about 3.2
At μm, the resin surface was good without any particular abnormality. NEX1
After curing was performed in the same manner as in Example 1, the tensile properties were evaluated. The tensile strength was 12.3 kg / mm ² , the tensile modulus was 263 kg / mm ² , and the tensile elongation was as high as 52%, and no decrease in strength due to plasma damage was observed.

Example 3 After the developed wafers (EX1 and NEX1) prepared in Example 1 were cured at 225 ° C. for 60 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness of EX1 is about 3.2
At μm, the resin surface was good without any particular abnormality. NEX1
After curing was performed in the same manner as in Example 1, the tensile properties were evaluated. Tensile strength, 12.5 kg / mm ^2, the tensile modulus 259 kg / mm ^2, tensile elongation showed 49% as high, strength reduction due to plasma damage was observed.

Example 4 After the developed wafers (EX1 and NEX1) prepared in Example 1 were cured at 250 ° C. for 30 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness of EX1 is about 3.3
At μm, the resin surface was good without any particular abnormality. NEX1
After curing was performed in the same manner as in Example 1, the tensile properties were evaluated. Tensile strength, 12.7 kg / mm ^2, the tensile elastic modulus 248kg / mm ^2, tensile elongation showed 45% as high, strength reduction due to plasma damage was observed.

Example 5 In the synthesis of the polyamide in Example 1, it was obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole. Diphenylsulfone-4,4'-
A polyamide (A-2) is synthesized using a dicarboxylic acid derivative obtained by reacting 1 mol of dicarboxylic acid with 2 mol of 1-hydroxy-1,2,3-benzotriazole,
Otherwise, the same evaluation as in Example 1 was performed.

Example 6 In the synthesis of the polyamide in Example 1, instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-diamino-4,4'- Polyamide (A-3) is synthesized using dihydroxydiphenyl sulfone,
Otherwise, the same evaluation as in Example 1 was performed.

Comparative Example 1 After the developed wafers (EX1 and NEX1) prepared in Example 1 were cured at 350 ° C. for 60 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness of EX1 is about 3.7
The resin surface had many holes of about 2 to 10 μm in μm. NEX1 was evaluated for tensile properties after curing in the same manner as in Example 1. Tensile strength is 10.9kg / mm
^{2. The} tensile modulus was 232 kg / mm ² , and the tensile elongation was as low as 18%, indicating a decrease in strength due to plasma damage.

Comparative Example 2 After the developed wafers (EX1 and NEX1) prepared in Example 5 were cured at 380 ° C. for 30 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. EX1 film thickness is about 3.8μm
The resin surface had many holes of about 2 to 10 μm. NEX1 was evaluated for tensile properties after curing in the same manner as in Example 1. Tensile strength is 10.4kg / mm
^{2. The} tensile modulus was 221 kg / mm ² , and the tensile elongation was as low as 15%, indicating a decrease in strength due to plasma damage.

Comparative Example 3 After the developed wafers (EX1 and NEX1) prepared in Example 1 were cured at 320 ° C. for 30 minutes, an etching apparatus OPM-EM1000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. Then, oxygen plasma treatment was performed at 1000 W for 2 minutes. The film thickness of EX1 is about 3.5
In μm, the resin surface had a few holes of about 1-3 μm. NEX1 was evaluated for tensile properties after curing in the same manner as in Example 1. Tensile strength is 11.3kg / mm
^{2. The} tensile elasticity was 242 kg / mm ² and the tensile elongation was 32%, indicating a slight decrease in strength due to plasma damage.

Table 1 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3.

[Table 1]

[0051]

According to the present invention, it is possible to reduce the damage of the resin at the time of etching the photosensitive resin composition on the semiconductor.

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[Procedure amendment]

[Submission date] March 10, 2000 (200.3.1.1)
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

Table 1 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3.

[Table 1]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/5455 C08K 5/5455 C08L 79/04 C08L 79/04 B G03F 7/004 501 G03F 7/004 501 7/037 501 7/037 501 H01L 21/027 H01L 21/30 502R 571 F-term (reference) 2H025 AA09 AA18 AB15 AB17 AD03 BE01 CB26 CB33 CB45 CC20 FA29 FA39 2H096 AA26 AA27 BA10 EA02 GA08 HA01 HA11 HA30 4J002 CM031 4J043 PA02 PA04 PA09 PA19 PB22 QB21 RA05 SA06 SA71 SB03 TA12 TB01 UA041 UA042 UA122 UA131 UA132 UB021 UB051 UB121 UB122 UB152 UB301 UB302 VA011 VA012 VA051 WA06 XA19 XA36 XB07 YA06 ZA11 ZA12A046

Claims (8)

[Claims] 1. A photosensitive resin composition comprising a polybenzoxazole precursor and a photosensitive diazoquinone compound is applied,
After prebaking, exposing, developing and forming a pattern, curing at a temperature higher than the prebaking temperature, but lower than the final curing temperature (hereinafter referred to as "preetch baking")
And thereafter, etching, and finally curing the photosensitive resin composition. 2. The method for processing a photosensitive resin composition according to claim 1, wherein the temperature of the pre-etch bake is from 120 ° C. to 250 ° C. 3. The method for processing a photosensitive resin composition according to claim 1, wherein the temperature at the time of the final curing is 250 ° C. or higher. 4. The method for processing a photosensitive resin composition according to claim 1, wherein the polybenzoxazole precursor is selected from the general formula (1). Embedded image 5. The polybenzoxazole precursor comprises 100 parts by weight of a polyamide represented by the general formula (1) and 1 to 100 parts by weight of a photosensitive diazoquinone compound (B). Processing method of the photosensitive resin composition. 6. The polybenzoxazole precursor comprises 100 parts by weight of a polyamide represented by the general formula (1), 1 to 100 parts by weight of a photosensitive diazoquinone compound (B), and the general formulas (2) and / or (3). The phenolic compound (C) represented by the formula (1), comprising 1 to 50 parts by weight.
A method for processing the photosensitive resin composition according to the above. Embedded image Embedded image 7. The polybenzoxazole precursor is composed of 100 parts by weight of a polyamide represented by the general formula (1), 1 to 100 parts by weight of a photosensitive diazoquinone compound (B), and general formulas (2) and / or (3). 1 to 50 parts by weight of a phenolic compound (C) represented by the formula and one or more kinds of organosilicon compounds selected from the group consisting of the organosilicon compounds represented by the general formulas (4), (5) and (6) ( D) 0.1-20
4. The method for processing a photosensitive resin composition according to claim 1, which comprises parts by weight. Embedded image Embedded image Embedded image 8. A semiconductor device manufactured by using the method for processing a photosensitive resin composition according to claim 1.