JP4569211B2 - Phenol compound, positive photosensitive resin composition, semiconductor device and display element, and method for manufacturing semiconductor device and display element - Google Patents

Description

  The present invention relates to a phenol compound, a positive photosensitive resin composition having high sensitivity and high resolution using the phenol compound, a semiconductor device and a display element using the positive photosensitive resin composition, and a method for manufacturing the semiconductor device and the display element. .

Conventionally, polyimide resin having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like has been used for the surface protection film and interlayer insulating film of the semiconductor element. Due to the thinning and miniaturization of semiconductor devices and the transition to surface mounting by solder reflow, there is a demand for significant improvements in characteristics such as heat cycle resistance and heat shock resistance, and higher performance resins are required. I came.
On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has attracted attention, and examples thereof include a photosensitive polyimide resin represented by the following formula (7).

If this is used, a part of the pattern creation process can be simplified, and there is an effect of shortening the process and improving the yield. However, since a solvent such as N-methyl-2-pyrrolidone is required for development, safety and handling There is a problem with sex.
Therefore, a positive photosensitive resin composition that can be developed with an alkaline aqueous solution has recently been developed. For example, Patent Document 1 discloses a positive photosensitive resin composition composed of a polybenzoxazole precursor as a base resin and a diazoquinone compound as a photosensitive material. This has high heat resistance, excellent electrical properties, and fine processability, and has the potential as a resin composition for interlayer insulation as well as for wafer coating. The development mechanism of this positive photosensitive resin composition is as follows. The unexposed portion of the diazoquinone compound is insoluble in the aqueous alkali solution and has resistance against this by interacting with the base resin. On the other hand, upon exposure, the diazoquinone compound undergoes a chemical change, becomes soluble in an alkaline aqueous solution, and dissolves the base resin. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a coating film pattern of only the unexposed portion can be created.

  When these photosensitive resin compositions are actually used, the sensitivity of the photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long and the throughput decreases. Therefore, in order to improve the sensitivity of the photosensitive resin composition, for example, when the molecular weight of the base resin is reduced, the film thickness of the unexposed area is increased during development, so that the required film thickness cannot be obtained, or the pattern There arises a problem that the shape collapses. Recently, the trend of reducing the size of semiconductor elements has been accelerated, and it has become important to be able to form higher resolution patterns. If priority is given to the sensitivity as described above, the pattern shape of the unexposed portion is destroyed, so that a pattern having a narrow width cannot be formed, resulting in low resolution. Conversely, if the molecular weight of the base resin is increased or the amount of the photosensitive diazoquinone compound, which is a photosensitive material, is increased, the exposed area becomes difficult to dissolve in an alkaline aqueous solution so that the unexposed area does not collapse. Or the remaining of the photosensitive resin composition (scum) occurs at the bottom of the pattern after development. Thus, in general, sensitivity and resolution are in a trade-off relationship, and development of a photosensitive resin composition that satisfies the characteristics of both has recently been strongly desired.

Japanese Examined Patent Publication No. 1-46862

  The present invention provides a phenol compound, a positive photosensitive resin composition having high sensitivity and high resolution using the phenol compound, a semiconductor device and a display element using the positive photosensitive resin composition, and a method for manufacturing the semiconductor device and the display element. Objective.

Such an object is achieved by the present invention described in the following [1] to [8].
[1] 100 parts by weight of the alkali-soluble resin (A) having the structure represented by the general formula (4), 1 to 50 parts by weight of the photosensitive diazoquinone compound (B), and the general formula (1) (2) or (3) the phenol compound (C) 1 to 30 parts by weight having the structure represented by a free Mupo di photosensitive resin composition, wherein X in the general formula (4) is selected from the group of the formula (5), A positive photosensitive resin composition, wherein Y is a polyamide resin selected from the group of formula (6) or formula (7).

[2] a polyamide resin containing the structure represented by the general formula (4) is alkenyl or according to end-capped by derivative containing an aliphatic group or cyclic compound group having at least one alkynyl group [1] A positive photosensitive resin composition.
[ 3 ] The photosensitive diazoquinone compound (B) is an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. The positive photosensitive resin composition according to [1] or [2].
[4] [1] a step of forming a composition layer of the positive photosensitive resin composition was coated on a substrate according to any one of - [3], an active energy ray to the composition layer a step of irradiating to form a pattern in contact with the developing solution, process for producing the patterned shaped resin film characterized by having a step of heating the composition.
[ 5 ] A semiconductor device manufactured using the positive photosensitive resin composition according to any one of [1] to [3] .
[ 6 ] A display element produced by using the positive photosensitive resin composition according to any one of [1] to [3] .
[ 7 ] The positive photosensitive resin composition according to any one of [1] to [3] is applied on a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm. A method for producing a semiconductor device, which is obtained by pre-baking, exposing, developing, and heating.
[ 8 ] The positive photosensitive resin composition according to any one of [1] to [3] is formed on the display element substrate so that the film thickness after heating and dehydration and ring closure is 0.1 to 30 μm. A method for producing a display element, which is obtained by applying, pre-baking, exposing, developing, and heating.

  The positive-type photosensitive resin composition of the present invention has high sensitivity and high resolution with the characteristics that there is little film loss, the pattern shape does not collapse, and there is no remaining (scum) of the photosensitive resin composition in the exposed area. It has an excellent feature.

The phenol compound having the structure represented by the formula (1), formula (2) or formula (3) of the present invention can be obtained by the method described in Examples 1 to 3 described later, and the positive type of the present invention. It can use suitably for the photosensitive resin composition.
The alkali-soluble resin used in the present invention is a resin having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain, and examples thereof include a cresol type novolak resin, polyhydroxystyrene, and the like. From the viewpoint of properties, a polyamide resin containing a structure represented by the general formula (4) is preferable.

X in the polyamide resin including the structure represented by the general formula (4) represents a divalent to tetravalent organic group, R ₁ is a hydroxyl group, O—R ₃ , m is an integer of 0 to 2, and these are It may be the same or different. Y represents a divalent to hexavalent organic group, R ₂ is a hydroxyl group, a carboxyl group, with _{O-R 3, COO-R} 3, n is an integer of 0 to 4, which may be the same or different. Here, R ₃ is an organic group having 1 to 15 carbon atoms. However, when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. When R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.

  The polyamide resin containing the structure represented by the general formula (4) is, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, etc., and a structure of Z blended as necessary. And a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative having the structure of Y. Is obtained. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

In the polyamide resin containing the structure represented by the general formula _{(4), O-R 3} , COO-R 3 as a substituent of O-R _3, Y as a substituent of X is a hydroxyl group, an alkaline aqueous solution of the carboxyl group Is a group protected with an organic group having 1 to 15 carbon atoms for the purpose of adjusting the solubility in the solvent, and a hydroxyl group and a carboxyl group may be protected as necessary. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.
When this polyamide resin is heated at about 250 to 400 ° C., it is dehydrated and closed, and a heat resistant resin is obtained in the form of polyimide, polybenzoxazole, or copolymerization of both.

X of the polyamide resin containing the structure represented by the general formula (4) of the present invention is, for example,
However, it is not limited to these.

Among these, as particularly preferred,
Two or more kinds may be used.

Moreover, Y of the polyamide resin containing the structure represented by the general formula (4) is, for example,

However, it is not limited to these.

Among these, particularly preferred are:

Two or more kinds may be used.

In the present invention, it is desirable to seal the end from the viewpoint of storage stability. For sealing, a derivative having an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (4). Specifically, a diamine having a structure of X or a compound selected from bis (aminophenol) and 2,4-diaminophenol, a silicone diamine having a structure of Z and a tetracarboxylic having a structure of Y, which are blended as necessary. It is represented by the general formula (4) obtained by reacting a compound selected from acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. After synthesizing a polyamide resin containing a structure, an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group as the terminal amino group contained in the polyamide resin is used. And capping as an amide. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

However, it is not limited to these.

Among these, particularly preferred are:
Two or more of these may be used. The method is not limited to this method, and the terminal acid contained in the polyamide resin is capped as an amide using an amine derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. You can also

Furthermore, Z of the polyamide resin including the structure represented by the general formula (4) used as necessary is, for example,
However, the present invention is not limited to these, and two or more kinds may be used.

  Z of the polyamide resin including the structure represented by the general formula (4) is used when particularly excellent adhesion is required to a substrate such as a silicon wafer, for example. Up to%. If it exceeds 40 mol%, the solubility of the resin in the exposed area will be extremely lowered, developing residue (scum) will occur, and pattern processing will not be possible, which is not preferred.

  The photosensitive diazoquinone compound (B) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is known from US Pat. Nos. 2,729,975, 2,797,213 and 3,669,658. It is a substance. For example, the following are mentioned.

  Among these, an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Examples of these include, but are not limited to, the following. Two or more of these may be used.

  The addition amount of the photosensitive diazoquinone compound (B) used by this invention is 1-50 weight part with respect to 100 weight part of alkali-soluble resin. If it is less than 1 part by weight, the patterning property of the polyamide resin becomes poor, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

  In the positive photosensitive resin composition of the present invention, it is important to contain a phenol compound having a structure represented by the general formula (1), (2) or (3).

  Examples of techniques for adding a phenol compound to a positive resist composition include, for example, JP-A-3-200251, JP-A-3-200262, JP-A-3-200263, JP-A-3-200244, These are disclosed in, for example, Kaihei 4-1650, JP-A-4-11260, JP-A-4-12356, and JP-A-4-12357. However, when the phenolic compounds as shown in these are used in a positive photosensitive resin composition based on the polyamide resin in the present invention, the effect of improving the sensitivity is small. However, when the phenolic compound having the structure represented by the general formula (1), (2) or (3) in the present invention is used, the dissolution rate of the exposed portion in the developer is higher than when other phenolic compounds are used. The speed is increased, the sensitivity is improved, and the occurrence of scum is further suppressed. In addition, the film loss at the unexposed area as seen when the sensitivity is improved by reducing the molecular weight is very small.

The positive photosensitive resin composition of the present invention may contain other phenolic compounds as necessary for the purpose of improving sensitivity. Examples include the following, but are not limited thereto.

  The addition amount of the phenol compound (C) represented by the general formula (1) (2) or (3) is 1 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. If it is less than 1 part by weight, the sensitivity at the time of development is lowered, and if it exceeds 30 parts by weight, the film of the unexposed part is significantly reduced during development, or precipitation occurs during freezing storage, resulting in lack of practicality.

  The positive photosensitive resin composition of the present invention may contain a dihydropyridine derivative in order to enhance the photosensitive characteristics as necessary. Examples of the dihydropyridine derivative include 2,6-dimethyl-3,5-diacetyl-4- (2′-nitrophenyl) -1,4-dihydropyridine, 4- (2′-nitrophenyl) -2,6-dimethyl. -3,5-dicarboethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine, etc. be able to.

The positive photosensitive resin composition in the present invention may contain additives such as a leveling agent and a silane coupling agent as necessary.
In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  In the method of using the positive photosensitive resin composition of the present invention, first, the resin composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is less than 0.1 μm, it will be difficult to sufficiently function as a protective surface film of the semiconductor element, and if it exceeds 30 μm, it will be difficult to obtain a fine processed pattern. Application methods include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. As the developer, 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, di-n Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, heat treatment is performed to form an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

  The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films and liquid crystal alignment films, interlayer insulation films for elements in display elements, etc. It is.

  Examples of specific uses for semiconductors include a passivation film obtained by forming the above-described photosensitive resin composition film on a semiconductor element, and a photosensitive resin composition described above on a passivation film formed on a semiconductor element. Examples thereof include a buffer coat film formed by forming a physical film, and an interlayer insulating film formed by forming the above-described photosensitive resin composition film on a circuit formed on a semiconductor element.

  Among them, as one application example in which the photosensitive resin composition of the present invention is used in a semiconductor device, application to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, a passivation film 3 is formed on an input / output Al pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3. Further, a positive photosensitive resin (buffer coating film) 4 is formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and the metal film 5 is formed of solder bumps. The periphery of 10 is etched to insulate between the pads. A barrier metal 8 and a solder bump 10 are formed on the insulated pad.

  Examples of display device applications include TFT interlayer insulating films, TFT element flattening films, color filter flattening films, protrusions for MVA liquid crystal display devices, and cathode partitions for organic EL elements. The usage method is based on forming the photosensitive resin composition layer patterned on the board | substrate which formed the display body element and the color filter by said method according to a semiconductor use. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but by introducing a post-exposure process before curing the photosensitive resin composition layer, it is excellent in transparency. A resin layer can be obtained, which is more preferable in practical use.

Hereinafter, the present invention will be described specifically by way of examples.
<Example 1>
A 300 ml four-necked flask was charged with 50 g (0.40 mol) of salicyl alcohol and 44 g (0.40 mol) of resorcinol, the inside of the system was replaced with nitrogen, and the mixture was heated at 100 ° C. for 5 hours. After cooling, the obtained solid was separated by silica column chromatography to obtain 13.0 g of 1,3-dihydroxy-4- (2′-hydroxybenzyl) benzene (formula (1)) as a target product. The yield was 15% and the purity was 90% (GC area).
The obtained 1,3-dihydroxy-4- (2′-hydroxybenzyl) benzene is subjected to ¹ H-NMR spectrum, melting point and mass spectrometry, and the results are shown below. In addition, each measurement was performed using the following apparatus.

[measuring device]
1H-NMR spectrum: manufactured by JEOL Ltd. JNM-EX270WB
Melting point: DSC6200 manufactured by SII
Mass spectrometry: JMS-700 manufactured by JEOL Ltd.
[Measurement result]
[ ¹ H-NMR spectrum]
400MHz, solvent acetone-d6, standard TMS
3.84 (s, 2H), 6.29 (dd, 1H), 6.39 (d, 1H), 6.74 (td, 1H), 6.82 (d, 1H), 6.95 (d , 1H), 7.00 (td, 1H), 7.10 (dd, 1H), 8.28 (bs, 3H)
[Melting point]
196-200 ° C
[Mass spectrometry]
m / z: 216 (M +)

<Example 2>
The reaction was carried out in the same manner as in Example 1 except that 50.4 g (0.40 mol) of phloroglucinol was used in place of resorcinol. After the reaction, the reaction product was separated by silica column chromatography, and 1,3,5- 7.8 g of trihydroxy-4- (2′-hydroxybenzyl) benzene (formula (2)) was obtained. The yield was 8.5% and the purity was 91% (GC area). The results of ¹ H-NMR spectrum, melting point, and mass spectrometry performed in the same manner as in Example 1 are shown below.
[ ¹ H-NMR spectrum]
400MHz, solvent acetone-d6, standard TMS
3.84 (s, 2H), 6.12 (s, 2H), 6.72 (td, 1H), 6.78 (dd, 1H), 6.98 (td, 1H), 7.35 (dd , 1H), 7.92 (bs, 1H), 8.49 (bs, 2H), 8.59 (bs, 1H)
[Melting point]
205 ° C (decomposition)
[Mass spectrometry]
m / z: 230 (M +)

<Example 3>
The reaction was carried out in the same manner as in Example 1 except that 49.6 g (0.40 mol) of 2-methylresorcinol was used in place of resorcinol. 11.0 g of dihydroxy-4- (2′-hydroxybenzyl) -2-methylbenzene (formula (3)) was obtained. The yield was 12% and the purity was 91% (GC area). The results of ¹ H-NMR spectrum, melting point, and mass spectrometry performed in the same manner as in Example 1 are shown below.
[ ¹ H-NMR spectrum]
400MHz, solvent acetone-d6, standard TMS
2.10 (s, 3H), 3.83 (s, 2H), 6.35 (d, 1H), 6.76 (t d, 1H), 6.86 (d, 2H), 7.02 ( td, 1H), 7.17 (dd, 1H), 7.72 (bs, 1H), 7.89 (bs, 1H), 8.97 (bs, 1H)
[Melting point]
175-178 ° C
[Mass spectrometry]
m / z: 232 (M +)

<Example 4>
A thermometer containing 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 12.4 g (0.167 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) of pyridine Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise to this reaction solution together with 30 g of N-methyl-2-pyrrolidone, and then 22.7 g (0.110 mol) of dicyclohexylcarbodiimide. Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature. Thereafter, 27.1 g of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. (0.055 mol) and 44.8 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane with 70 g of N-methyl-2-pyrrolidone are added at room temperature. Stir for 2 hours. Thereafter, the reaction was terminated by stirring for 12 hours at 75 ° C. using an oil bath. 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 to obtain the general formula (4) And X is the following formula X-1, Y is the following formulas Y-1 and Y-2, and a polyamide resin (A-1) having a = 100 and b = 0 was synthesized.

Preparation of positive photosensitive resin composition 100 g of synthesized polyamide resin (A-1), 16 g of photosensitive diazoquinone compound having the structure of the following formula (Q-1), phenol compound having the structure of the following formula (C-1) 10 g was dissolved in 150 g of γ-butyrolactone and then filtered through a 0.2 μm Teflon (R) 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 pre-baked on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 13 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), and an i-line stepper (manufactured by Nikon Corporation, 4425i). ) And changed the exposure amount.
Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 110 seconds, and then rinsed with pure water for 10 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 360 mJ / cm ² . (Sensitivity is 360 mJ / cm ² ). The resolution was as high as 3 μm.

<Example 5>
Synthesis of polyamide resin 360.4 g of dicarboxylic acid derivative (active ester) obtained by reacting 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole (0.9 mol) and 366.3 g (1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. It was put into a four-necked separable flask, and 3000 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 32.8 g (0.2 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was put into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, and then dried under vacuum to obtain the general formula (4) Where X is a mixture of the following formula X-1, Y is a mixture of the following formulas Y-3 and Y-4, and the target polyamide resin (A-2) having a = 100 and b = 0 was obtained.

Production of positive photosensitive resin composition 100 g of synthesized polyamide resin (A-2), 21 g of photosensitive diazoquinone compound having the structure of the following formula (Q-1), phenol compound having the structure of the following formula (C-2) 10 g was dissolved in 150 g of γ-butyrolactone and then filtered through a 0.2 μm Teflon (R) filter to obtain a positive photosensitive resin composition. Otherwise, the same evaluation as in Example 4 was performed.

<Example 6>
In the synthesis of the polyamide resin in Example 5, hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was reduced to 348.0 g (0.95 mol), and 1,3-bis ( 3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (12.4 g, 0.05 mol) is added, and is represented by the general formula (4). A mixture of formulas Y-3 and Y-4, Z was the following formula Z-1, and a polyamide resin (A-3) comprising a = 95 and b = 5 was synthesized. Further, the same as in Example 5 except that the addition amount of the photosensitive diazoquinone compound (Q-1) was changed to the amount shown in Table 1 and the phenol compound was changed to 10 g of a phenol compound having the structure of the following formula (C-3). A positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 4.

<Example 7>
Evaluation similar to Example 4 was performed except having changed the addition amount of the phenolic compound (C-1) in Example 4 into the quantity shown in Table 1.
<Comparative Examples 1-2>
A positive photosensitive resin composition was produced in the same manner as in Example 4 at the blending ratio in Table 1, and evaluated in the same manner as in Example 4. The polyamide resin used in Comparative Example 1 is the same as that in Example 4, and the polyamide resin used in Comparative Example 2 is the same as that in Example 5. Example 4 corresponds to Comparative Example 1, and Example 5 corresponds to Comparative Example 2.
Below, the structure of X-1, Y-1 to Y-4, Z-1, Q-1, and C-1 to C-4 of Examples 4 to 7 and Comparative Examples is shown.

It is an expanded sectional view of a pad part of an example of a semiconductor device which has a bump of the present invention.

Explanation of symbols

1 Silicon wafer 2 Al pad 3 Passivation film 4 Buffer coat film 5 Metal (Cr, Ti, etc.) film 6 Wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Solder bump

Claims (7)

100 parts by weight of an alkali-soluble resin (A) containing the structure represented by the general formula (4), 1 to 50 parts by weight of the photosensitive diazoquinone compound (B), and a structure represented by the general formula (1) (2) or (3) A positive photosensitive resin composition comprising 1 to 30 parts by weight of a phenol compound (C) having the formula: wherein X in the general formula (4) is selected from the group of formula (5), and Y is represented by the formula ( A positive photosensitive resin composition, which is a polyamide resin selected from the group of 6) or formula (7).
Claim sensitive light diazoquinone compound (B) is an ester compound of a phenolic compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid 2. The positive photosensitive resin composition according to 1. A step of coating the positive photosensitive resin composition according to claim 1 or 2 on a substrate to form a composition layer, and irradiating the composition layer with active energy rays to contact with a developer to form a pattern. A process for producing a patterned resin film, comprising: a step of forming a film; and a step of heating the composition. The semiconductor device characterized by comprising been fabricated using the positive photosensitive resin composition according to claim 1 or 2. Display element characterized by comprising been fabricated using the positive photosensitive resin composition according to claim 1 or 2. The positive photosensitive resin composition according to claim 1 or 2 is applied onto a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm, and prebaked, exposed, developed and heated. A method for manufacturing a semiconductor device, which is obtained. The positive photosensitive resin composition according to claim 1 or 2 is applied onto a display element substrate so that the film thickness after heat-dehydration and ring closure is 0.1 to 30 μm, and prebaked, exposed, developed, and heated. A method for manufacturing a display element, characterized by being obtained in the above manner.