JP2003302761A - Positive photosensitive resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having high sensitivity and high resolution and ensuring a small reduction in film thickness of an unexposed region after development and to provide a semiconductor device manufactured by using the same. <P>SOLUTION: The positive photosensitive resin composition consists of a polyamide resin (A), a compound (B) which generates an acid under light, a compound (C) protected by an acid-labile group which is decomposed in the presence of an acid to increase solubility in an aqueous alkali solution, a compound (D) which further generates an acid in the presence of an acid and a solvent (E). A positive photosensitive resin composition is also provided which contains a phenol compound (F) in the above positive photosensitive resin composition. The semiconductor device is manufactured using this positive photosensitive resin composition. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition having high sensitivity and high resolution, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for a surface protective film and an interlayer insulating film of a semiconductor device. There is a demand for significant improvement in heat cycle resistance, heat shock resistance, etc. due to the trend toward larger size, larger size, thinner semiconductor device, smaller size, and surface mounting by solder reflow, and higher performance resin is required. It's starting to happen.

On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has been attracting attention, for example, the following formula (8)
And the negative photosensitive polyimide resin shown in.

[Chemical 7]

If this is used, part of the pattern forming process can be simplified, and it has the effect of shortening the process and improving the yield, but since a solvent such as N-methyl-2-pyrrolidone is required during development, it is safe. There is a problem with the handling and handling. Therefore, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has been developed. For example, JP-A-3-24765
5, JP-A-5-204156, JP-A-6-
258836, JP-A-10-186658 and JP-A-10-307394 disclose a positive photosensitive resin composition composed of a polyamic acid which is a precursor of a polyimide resin and a diazoquinone compound which is a photosensitive material. Has been done. The diazoquinone compounds used as these photosensitive materials undergo a chemical change upon exposure to light and become soluble in an alkaline aqueous solution. However, the rate of change is not only about 40%, but also its own absorption of light is large, so that when it is applied to a thick film, the light does not reach the bottom of the film sufficiently. Therefore, there is a problem that a large amount of exposure is required to open the exposed portion, resulting in low sensitivity.

Further, a positive type photosensitive resin composition represented by a resist for semiconductors using ultraviolet rays such as g rays and i rays as a light source uses a novolac resin as a base resin. Has a low hydroxyl group concentration per unit molecular weight, and therefore has a weak dissolution inhibiting ability exhibited by interacting with a diazoquinone compound, and has a large amount of film loss in the unexposed portion after development. Therefore, before the exposed area is sufficiently dissolved and removed in the developing solution, the unexposed area becomes less than or equal to the target film thickness. The dimensional stability of the part decreases. Further, in the case of a carboxyl group, it cannot interact with the diazoquinone compound, and because it has a much higher solubility in an aqueous alkaline solution than the phenolic hydroxyl group, the dissolution inhibiting ability of the unexposed portion is not formed. However, there is a problem that the desired film thickness cannot be obtained and the pattern formation itself becomes difficult. In the case of a carboxyl group blocked with an appropriate protective group, the unexposed area has sufficient resistance to an aqueous alkaline solution, but the solubility of the exposed area is poor, resulting in a decrease in sensitivity, and a resin residue (scum) is observed after development. There is a problem that is.

Therefore, a chemically amplified positive photosensitive resin composition incorporating a catalytic action by a photochemical reaction has been developed. This chemically amplified positive-type photosensitive resin composition is generally composed of a base resin in which a hydroxyl group or a carboxyl group is protected with an appropriate acid labile group, and a photoacid generator that generates an acid when irradiated with light. ing. The developing mechanism of this chemically amplified positive photosensitive resin composition is as follows. The base resin protected with an acid labile group in the unexposed area has resistance to an alkaline aqueous solution which is a developing solution. On the other hand, in the exposed part, the acid generated from the photo-acid generating material diffuses by the heat treatment after the exposure to act as a catalyst, removes the protective group in the base resin, regenerates the hydroxyl group or the carboxyl group, and is soluble in the alkaline aqueous solution. Become. By utilizing the difference in solubility between the exposed portion and the unexposed portion and dissolving and removing the exposed portion, it is possible to create a coating film pattern only in the unexposed portion. Furthermore, this catalytic acid is present even after the elimination reaction and causes many reactions, resulting in a high apparent quantum yield, which not only facilitates high sensitivity but also provides high dissolution contrast, which is expected to improve resolution. it can.

Examples of semiconductor resists to which these techniques are applied include Japanese Patent No. 2847414, Japanese Patent No. 2848611, Japanese Patent Laid-Open No. 3-249654, Japanese Patent Laid-Open No. 9-230588, and the like.
The base resin used for these is mainly polyhydroxystyrene, and although high resolution can be obtained, it has poor heat resistance and is not suitable for use as a surface protective film for semiconductor elements or an interlayer insulating film.

A chemically amplified photosensitive resin composition using a polyimide or polyamide resin as a base resin for use as a surface protective film or an interlayer insulating film of a semiconductor device is, for example,
JP-A-3-763, JP-A-4-120171, JP-A-11-202489, and JP-A-2001-2001
It is disclosed in Japanese Patent No. 194791. However, even after curing with heat, the hydroxyl groups remain, resulting in a decrease in moisture resistance reliability, and a decrease in resolution due to lack of sufficient dissolution contrast. Due to the increase in the amount, there was a problem that a desired film thickness could not be obtained, side etching was large, and the profile was poor.

[0009]

DISCLOSURE OF THE INVENTION The present invention has a heat resistance suitable for use in surface protection films and interlayer insulating films of semiconductor elements,
Further, the present invention relates to a positive photosensitive resin composition which is excellent in profile property without deterioration in moisture resistance reliability, deterioration in resolution, increase in film loss in unexposed area even at high sensitivity.

[0010]

The present invention is based on the general formula (1)
A polyamide resin (A), a compound (B) that generates an acid by light, a compound (C) protected by an acid labile group that decomposes in the presence of an acid and has increased solubility in an alkaline aqueous solution, Compound (D) which further generates an acid in the presence of an acid
And a positive photosensitive resin composition containing a solvent (E).

[Chemical 8]

A more preferable form is the general formula (1)
X in the polyamide resin represented by is selected from the group of formula (2) and Y in the polyamide resin represented by general formula (1)
Is selected from the group of formula (3), and the terminal of the polyamide resin (A) represented by the general formula (1) is bound by an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. Is a positive photosensitive resin composition.

[Chemical 9]

[Chemical 10]

A compound (C) protected by an acid labile group which decomposes in the presence of an acid and has increased solubility in an aqueous alkaline solution.
Is a C2-C20 alkoxycarbonyl group, a C2-C20 alkoxycarbonylmethyl group, a C2-C2
A phenol compound protected by a substituent selected from an alkoxyalkyl group having 20 carbon atoms, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group, or an alkyl group having 2 to 20 carbon atoms. At least one selected from the ester compounds, the solvent (E) is a cyclic ketone having 3 to 10 carbon atoms, a cyclic lactone having 3 to 10 carbon atoms, dimethyl sulfoxide, propylene glycol monoalkyl ether, propylene glycol mono. The positive photosensitive resin composition is at least one selected from alkyl ether acetate, dipropylene glycol monoalkyl ether, methyl lactate, ethyl lactate, and butyl lactate.

Further, the above-mentioned positive type photosensitive resin composition is
A positive photosensitive resin composition containing a phenol compound (F). A more preferable form is a positive photosensitive resin composition containing 1 to 30 parts by weight of a phenol compound (F) with respect to 100 parts by weight of a polyamide resin (A), wherein the phenol compound (F) is selected from the following structures. Is.

[Chemical 11]

[Chemical 12]

[Chemical 13]

A semiconductor device manufactured by using the above-mentioned positive photosensitive resin composition, wherein the film thickness of the positive photosensitive resin composition after heat-dehydration ring closure is 0.1 to 30 μm. It is a semiconductor device obtained by applying on a semiconductor element, prebaking, exposing, heating after exposure, developing, and heating.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide resin represented by the general formula (1) includes a bis (aminophenol) having a structure of X, a silicone diamine having a structure of Z and a dicarboxylic acid or a dicarboxylic acid having a structure of Y, which are blended if necessary. It is obtained by reacting an acid dichloride and a dicarboxylic acid derivative, and then substituting a protective group which becomes an acid labile group with a phenolic hydroxyl group in a polyamide resin. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like.

The protective group which becomes an acid labile group has 2 to 2 carbon atoms.
It is an alkoxycarbonyl group of 0, an alkyl-substituted silyl group having 1 to 10 carbon atoms, and examples thereof include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a trimethylsilyl group, and the like, and a tert-butoxycarbonyl group is preferable. In addition, in order to obtain a resin in which the amount of film loss in the unexposed area after development is small and the dissolution contrast between the exposed area and the unexposed area is large,
It is desirable to replace 80% with a protecting group which becomes an acid labile group. If it is less than 5%, the unexposed portion may not have sufficient dissolution inhibiting ability and the film reduction amount may be large.
If it exceeds, not only the solubility of the exposed area becomes extremely slow and the sensitivity is lowered, but also the residue (scum) of the resin may be easily generated after the development. About 30% of this polyamide resin
When heated at 0 to 400 ° C., dehydration ring closure occurs and a heat resistant resin in the form of polybenzoxazole is obtained.

X of the polyamide resin of the general formula (1) of the present invention is, for example,

[Chemical 14] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 15] It is selected more preferably, and two or more kinds may be used.

Further, Y of the polyamide resin of the general formula (1) is
For example,

[Chemical 16] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 17] It is selected more preferably, and two or more kinds may be used.

The positive photosensitive resin composition of the present invention is obtained by reacting a dicarboxylic acid or dicarboxylic acid dichloride or dicarboxylic acid derivative having a structure Y with a bis (aminophenol) having a structure X from the viewpoint of storage stability. After synthesizing the polyamide resin, it is important to cap the terminal amino group with an acid anhydride containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group.

Examples of the aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group include:

[Chemical 18] However, the present invention is not limited to these.

Of these, particularly preferred are:

[Chemical 19] It is selected more preferably, and two or more kinds may be used.

Further, Z of the polyamide resin of the general formula (1) optionally used is, for example,

[Chemical 20] However, the present invention is not limited to these, and two or more kinds may be used.

Z in the general formula (1) is used when particularly excellent adhesion is required to a substrate such as a silicon wafer, and the use ratio b is up to 40 mol%. If it exceeds 40 mol%, the solubility of the resin is extremely lowered, the undeveloped residue (scum) is generated, and pattern processing cannot be performed, which is not preferable. In addition, these X, Y,
When Z is used, it may be one kind or a mixture of two or more kinds. N in the general formula (1)
Is from 2 to 300, but if it exceeds 300, scum may occur after development, which is not preferable.

The compound (B) which generates an acid by light used in the positive photosensitive resin composition of the present invention is Photo.
ograph. Sci. Eng. , 18 , p387 (1
974), CHEMTECH, Oct. p624 (19
80), Polym. Mater. Sci. Eng. ，
72 , p406 (1995), Macromol. Ch
em. Rapid Commun. 14 , p203 (1
993), J. Photopolym. Sci. Tec
hnol. , 6 , p67 (1993), onium salts, Macromolecules, 21 , p2001.
(1988), Chem. Mater. 3 , p462
(1991), Proc. SPIE, 1086 , 2 (1
989) described 2-nitrobenzyl ester, J. P
photopolym. Sci. Technol. , 2 ,
p429 (1989), Proc. SPIE, 126
2 , N-iminosulfonates described in p575 (1990), Polym. Mat. Sci. Eng. , 61 ,
Naphthoquinonediazide-4-described in 269 (1989).
Sulfonates, J. Photopolym. S
ci. Technol. , 4 , p389 (1991),
Proc. SPIE, 2195 , p173 (1994)
The halogen compounds described above and the like can be mentioned. The amount of the compound (B) added is not particularly limited, but is 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A). If the addition amount of the compound (B) is less than the lower limit value, there is a possibility that the exposed portion cannot be removed because the amount of acid sufficient for decomposing the acid labile group is insufficient. May precipitate during storage.

The positive-type photosensitive resin composition of the present invention is further decomposed in the presence of an acid in order to further improve the dissolution contrast between the exposed area and the unexposed area, so that the solubility in an alkaline aqueous solution is increased. It is important to add the compound (C) protected by a stable group. As a result, in the unexposed area, the resistance to the alkaline aqueous solution is improved, and in the exposed area, the acid labile group is desorbed by the action of the catalytic acid generated from the photo-acid generator to regenerate the hydroxyl group or carboxylic acid,
Promotes dissolution promoting action. Examples of the compound (C) protected with an acid labile group include an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxycarbonylmethyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and a carbon number. 1-10 alkyl-substituted silyl group, a tetrahydropyranyl group, a phenol compound protected by a substituent selected from a tetrahydrofuranyl group, or an ester compound substituted by a C2-20 alkyl group, preferred Is a tert-butoxycarbonyl group, t
These are phenol compounds protected by ert-butoxycarbonylmethyl group, tetrahydropyranyl group, and ester compounds substituted by tert-butyl group. Specific examples include the followings, but the invention is not limited thereto.

[0028]

[Chemical 21]

[0029]

[Chemical formula 22]

[0030]

[Chemical formula 23]

The amount of the compound (C) added is not particularly limited, but is 5 to 50 per 100 parts by weight of the polyamide resin (A).
Parts by weight. If the addition amount of the compound (C) is less than the lower limit value, sufficient dissolution contrast may not be obtained, and if it exceeds the upper limit value, the ratio of shrinkage during heat treatment for obtaining a heat resistant resin may be decreased. There is a possibility that the film thickness becomes large and the desired film thickness cannot be obtained, or the profile inside is deteriorated due to the tension inside the film.

The positive type photosensitive resin composition of the present invention generally has poor solubility and therefore cannot be added in a large amount, so as to supplement the amount of the catalytic acid from the photo-acid generator, the presence of an acid It is important to add the compound (D) which further generates an acid. Compound (D) which further generates an acid in the presence of an acid
As Chemistry Letters, p5
51 (1995), Polym. Preprints,
The acid propagation material described in Japan, 46 , 3, p527 (1997) can be mentioned. The amount of the compound (D) added is not particularly limited, but is 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A). If the addition amount of the compound (D) is less than the lower limit value, the amount of acid sufficient to decompose the acid labile group may be insufficient, and the exposed portion may not come off. May be precipitated.

The positive photosensitive resin composition of the present invention is used by dissolving these components in the solvent (E) to form a varnish. As the solvent (E), it is important to select a solvent containing no nitrogen in order to prevent deactivation of the acid generated from the photo-acid generator. As a specific example, for example,
Cyclic ketone having 3 to 10 carbon atoms, cyclic lactone having 3 to 10 carbon atoms, dimethyl sulfoxide, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, 3-methyl-3 -Methoxybutanol, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monoalkyl ether, trialkylbenzene, methyl pyruvate, ethyl pyruvate, methyl-3.
-Methoxypropionate and the like, preferred examples are γ-butyrolactone, ε-caprolactone,
Cyclopentanone, dimethyl sulfoxide, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methyl-3-methoxybutanol, mesitylene, methyl lactate, ethyl lactate, butyl lactate, These may be used alone or in combination.

The positive photosensitive resin composition of the present invention has a phenol compound (F) for increasing the diffusivity of the catalytic acid generated from the photo-acid generating material for the purpose of increasing the dissolution contrast between exposed and unexposed areas. ) May be added to the positive photosensitive resin composition. This is because the diffusion of the catalytic acid passes through the hydrophilic hydroxyl group in the system (Jpn.J.Appl.Ph.
ys. , Vol. 35, Pt. 1, No. 12B, p6
501 (1996)) behavior, and by adding an appropriate phenol compound (F), the elimination reaction of the protecting group is promoted. Further, since these phenol compounds (F) are soluble in an alkaline aqueous solution, the solubility of the exposed area is increased and the sensitivity is also increased. The addition amount of the phenol compound (F) is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A) represented by the general formula (1). If it is less than the lower limit, the effect of diffusing the catalytic acid may not be recognized, and if it exceeds the upper limit, the residual film rate may be significantly reduced during development, or precipitation during freeze storage may be impractical. is there.

Examples of the phenol compound (F) include, but are not limited to, the followings.

[Chemical formula 24]

[0036]

[Chemical 25]

[0037]

[Chemical formula 26]

Additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of the present invention, if necessary.

In the method of using the positive photosensitive resin composition of the present invention, first, the resin composition is applied to an appropriate support such as a silicon wafer, a ceramic substrate or an aluminum substrate. In the case of a semiconductor device, the coating amount is such that the final film thickness after curing is 0.1 to 30 μm. Film thickness is 0.1
If it is less than μm, it becomes difficult to sufficiently exert the function as a protective surface film of a semiconductor element, and if it exceeds 30 μm,
It becomes difficult to obtain a fine processing pattern. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, after prebaking at 60 to 130 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic rays.
As the actinic rays, X rays, electron rays, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. After exposure, using an oven or hot plate, 60
Heat treatment is performed at ˜130 ° C. By this post-exposure heating, the acid generated from the photo-acid generator diffuses and the protective group is eliminated by a catalytic reaction.

Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developing solution. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, 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 in which an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol and a surfactant are added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used.

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 to obtain a final pattern having high heat resistance. The positive 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 publicly known method can be used as the method for manufacturing the semiconductor device other than the above.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples. <Example 1><Synthesis of polyamide resin> 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 1-hydroxy-1,2,3-
Dicarboxylic acid derivative (active ester) obtained by reacting with 2 mol of benzotriazole (352.4 g, 0.8)
8 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1
Mol) and were placed in a 4-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and γ
-Butyrolactone 3000 g was added and dissolved. Then, the reaction was carried out at 75 ° C. for 12 hours using an oil bath.

Next, 5-norbornene-2,3-dicarboxylic acid anhydride 3 dissolved in 500 g of γ-butyrolactone was used.
2.8 g (0.2 mol) was added, and the reaction was terminated by further stirring for 12 hours. After filtering the reaction mixture, the reaction mixture was poured 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.

49.6 g of the dried polyamide resin was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 250 g of γ-butyrolactone was added and dissolved. Then dicarbonate di-te
13.1 g (0.06 mol) of rt-butyl was added dropwise together with 25 g of γ-butyrolactone. Then pyridine 4.7
g (0.06 mol) was added dropwise together with 10 g of γ-butyrolactone, and the mixture was reacted at room temperature for 5 hours. After filtering the reaction mixture, the reaction mixture was mixed with water / methanol = 3/1 (volume ratio).
Into the solution of (1), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and represented by the general formula (1), where X is the following formula X-
1, Y is a mixture of the following formulas Y-1 and Y-2, and a = 10
A target polyamide resin (A-1) was synthesized in which 0, b = 0, n = 42, and 30% of all hydroxyl groups were protected by tert-butoxycarbonyl groups.

<Preparation of Positive Photosensitive Resin Composition> 10 g of synthesized polyamide resin (A-1), N-hydroxynaphthalimide trifluoromethanesulfonate 0.5
g, 1 g of a phenol compound protected by an acid labile group having the structure of the following formula (C-1), 0.5 g of ACPRESS 11M (manufactured by Nippon Chemix) as the compound (D), and the structure of the following formula (F-1) After dissolving 0.6 g of a phenol compound having γ in 25 g of γ-butyrolactone, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

<Characteristic Evaluation> This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then prebaked at 90 ° C. for 3 minutes on a hot plate,
A coating film having a film thickness of about 6.9 μm was obtained. Mask (Test Chart No. 1: Width 0.8) manufactured by Toppan Printing Co., Ltd.
An i-line stepper (manufactured by Nikon Corp.)
4425i) was used to irradiate while changing the exposure dose.
After that, baking was performed on a hot plate at 110 ° C. for 5 minutes after exposure. Next, the exposed portion was dissolved and removed by immersing it in a 2.38% tetramethylammonium hydroxide aqueous solution for 25 seconds twice, and then rinsed with pure water for 10 seconds. As a result, it was confirmed that the pattern was formed from the portion irradiated with the exposure amount of 150 mJ / cm ² .
(Sensitivity is 150 mJ / cm ² ). The amount of film reduction was 0.2 μm, which is a low value from the initial thickness of the film, and the resolution was 3 μm, which was a very high value, compared with the above-mentioned test mask. In addition, in order to see the profile of the pattern, its cross section is scanned with a scanning electron microscope (JX Co., Ltd., JXA).
The cross-sectional shape was evaluated by observing at -840A), and it was confirmed that a good shape was shown.

<Example 2> The phenol compound (C-1) protected with an acid labile group in Example 1 was converted into (C-
In 2), a positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the phenol compound (F-1) was replaced with (F-2) and the addition amount was changed as shown in Table 1. It was produced and evaluated in the same manner as in Example 1. <Example 3> In the synthesis of the polyamide resin in Example 1, the dropping amount of di-tert-butyl dicarbonate was set to 13.
Changed from 1 g to 10.9 g (0.05 mol) and represented by the general formula (1), X is the following formula X-1 and Y is the following formula Y-1.
And a mixture of Y-2, a = 100, b = 0, n = 4
2 and 25% of all hydroxyl groups are protected with tert-butoxycarbonyl groups (A-
2) was synthesized. 10 g of this polyamide resin (A-2)
0.5 g of N-hydroxynaphthalimide trifluoromethanesulfonate, 1.2 g of a phenol compound protected by an acid labile group having a structure of the following formula (C-2),
As a compound (D), 0.8 g of ACPRESS 11M (manufactured by Nippon Chemix) was dissolved in 25 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to remove the phenol compound (F), and thus positive type photosensitivity. A resin composition was obtained. Others were evaluated in the same manner as in Example 1.

Comparative Example 1 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 1-hydroxy-1,2,3-
Dicarboxylic acid derivative (active ester) obtained by reacting with 2 mol of benzotriazole (352.4 g, 0.8)
8 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 366.3 g (1
Mol) and N were placed in a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and N
-Methyl-2-pyrrolidone (3000 g) was added and dissolved. Then, the reaction was carried out at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the reaction was terminated by further stirring for 12 hours. Otherwise, the reaction is performed in the same manner as in Example 1, represented by the general formula (1), X is the following formula X-1, Y is a mixture of the following formulas Y-3 and Y-4, and a = 100, b =
The target polyamide resin (A-
3) was synthesized. Synthesized polyamide resin (A-3) 1
0 g, 2 g of a photosensitive diazoquinone compound having the structure of the following formula (Q-1) and 0.6 g of a phenol compound having the structure of the following formula (F-1) were dissolved in 25 g of γ-butyrolactone, and then 0.2 μm of fluorine was added. Except that a positive photosensitive resin composition was obtained by filtering with a resin filter, the same procedure as in Example 1 was carried out, and the same evaluation as in Example 1 was performed.

<Comparative Example 2> In the synthesis of the polyamide resin in Example 1, the reaction amount of the polyamide resin was changed by changing the dropping amount of di-tert-butyl dicarbonate from 13.1 g to 1.3 g (0.006 mol). A-4) was used to prepare a positive photosensitive resin composition in the same manner as in Example 1,
The same evaluation as in Example 1 was performed. <Comparative Example 3> In the synthesis of the polyamide resin in Example 1, the dropping amount of di-tert-butyl dicarbonate was set to 13.
A positive-type photosensitive resin composition was prepared in the same manner as in Example 1 except that the polyamide resin (A-5) reacted from 1 g to 39.3 g (0.18 mol) was used. Similar evaluation was performed. <Comparative Example 4> The same evaluation as in Example 1 was performed except that the addition amount of the compound (D) in Example 1 was changed to 0 g.

Below, X-1 and Y- of Examples and Comparative Examples
1, Y-2, C-1, C-2, F-1, F-2, Q-1
Shows the structure of.

[Chemical 27]

[0051]

[Chemical 28]

[0052]

[Chemical 29]

The evaluation results are shown in Table 1.

[Table 1]

[0054]

The positive photosensitive resin composition of the present invention is characterized by high sensitivity and high resolution, a small amount of film loss in the unexposed area after development, and an excellent profile.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA01 AA02 AB16 AC01 AC04                       AC05 AC06 AD03 BE00 BG00                       CC03 CC20 FA03 FA12 FA17                 4J027 AD02 AD06 AJ02 CB10 CC03                       CD10

Claims (11)

[Claims] 1. A polyamide resin (A) represented by the general formula (1), a compound (B) which generates an acid by light, and an acid labile substance which is decomposed in the presence of an acid to increase its solubility in an aqueous alkaline solution. A positive photosensitive resin composition comprising a compound (C) protected by a group, a compound (D) which further generates an acid in the presence of an acid, and a solvent (E). [Chemical 1] 2. The positive photosensitive resin composition according to claim 1, wherein X in the polyamide resin represented by the general formula (1) is selected from the group of the formula (2). [Chemical 2] 3. The positive photosensitive resin composition according to claim 1, wherein Y in the polyamide resin represented by the general formula (1) is selected from the group of the formula (3). [Chemical 3] 4. The polyamide resin (A) represented by the general formula (1) is bound at the terminal with an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. Positive type photosensitive resin composition. 5. A compound (C) protected by an acid labile group that decomposes in the presence of an acid and has increased solubility in an aqueous alkaline solution is an alkoxycarbonyl group having 2 to 20 carbon atoms,
Protected by a substituent selected from an alkoxycarbonylmethyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group. The positive photosensitive resin composition according to claim 1, which is at least one selected from a phenol compound and an ester compound substituted with an alkyl group having 2 to 20 carbon atoms. 6. The solvent (E) is a cyclic ketone having 3 to 10 carbon atoms, a cyclic lactone having 3 to 10 carbon atoms, dimethyl sulfoxide, propylene glycol monoalkyl ether,
The positive photosensitive resin composition according to claim 1, which is at least one selected from propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether, methyl lactate, ethyl lactate, and butyl lactate. 7. The positive photosensitive resin composition according to claim 1, further comprising a phenol compound (F). 8. The positive photosensitive resin composition according to claim 7, which contains 1 to 30 parts by weight of the phenol compound (F) with respect to 100 parts by weight of the polyamide resin (A). 9. The positive photosensitive resin composition according to claim 7, wherein the phenol compound (F) is selected from the following structures. [Chemical 4] [Chemical 5] [Chemical 6] 10. A semiconductor device manufactured by using the positive photosensitive resin composition according to claim 1. 11. The positive photosensitive resin composition according to any one of claims 1 to 9 has a film thickness of 0.1 after heat dehydration ring closure.
A semiconductor device obtained by applying on a semiconductor element so as to have a thickness of about 30 μm, prebaking, exposing, heating after exposure, developing, and heating.