JP4720124B2 - POLYAMIDE RESIN, POSITIVE PHOTOSENSITIVE RESIN COMPOSITION, SEMICONDUCTOR DEVICE AND DISPLAY ELEMENT USING THE SAME, AND METHOD FOR PRODUCING THEM - Google Patents

Description

  The present invention relates to a polyamide resin, a positive photosensitive resin composition thereof, a semiconductor device and a display element using the same, and a method for producing them.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process, a positive photosensitive resin obtained by combining the polybenzoxazole resin or polyimide resin with a photosensitive diazoquinone compound is also used (for example, see Patent Document 1). In recent years, various chemical solutions are used for processing in wafer process steps due to downsizing of semiconductor elements, multilayer wiring by high integration, transition to chip size package (CSP), wafer level package (WLP), and the like. It has become like this. In particular, WLP uses Ti as a barrier metal or the like. that time. In many cases, hydrofluoric acid is used as an etchant for Ti, and there is a problem that these positive photosensitive resins are peeled off from the substrate during etching. Therefore, in order to solve the peeling, it has been studied to add a silane coupling agent or an adhesion aid, but a positive photosensitive resin having a weak effect and having resistance to further hydrofluoric acid is desired. .
Japanese Examined Patent Publication No. 1-46862

  The present invention relates to a polyamide resin intended to provide a polybenzoxazole resin or polyimide resin excellent in resistance to hydrofluoric acid or a copolymer resin thereof, and a positive photosensitive resin composition excellent in development characteristics using them. Product, a method for producing a patterned resin film using the composition, a semiconductor device and a display element using the polyamide resin or the composition, and a method for producing the semiconductor device and the display element.

Such an object is achieved by the present invention described in the following [1] to [10].
[1] A polyamide resin having a structure represented by the general formula (1), wherein 0.1 mol% to 30 mol% of the total amount of Y in the general formula (1) is represented by the general formula (2). Polyamide resin characterized by having a structure.

[2] A polyamide resin, wherein the structure represented by the general formula (2) according to [1] is any of the following structures.

[3] A positive photosensitive resin composition comprising the polyamide resin (A) according to [1] or [2] and a photosensitive diazoquinone compound (B).
[4] The positive photosensitive resin composition according to [3], further comprising a compound (C) having a phenolic hydroxyl group.
[5] The positive photosensitive resin composition according to [4], wherein the compound (C) having a phenolic hydroxyl group has the following structure.

[6] A step of applying the positive photosensitive resin composition according to any one of [3] to [5] onto a substrate to form a composition layer, and an active energy ray on the composition layer. A method for producing a patterned resin film, comprising: a step of forming a pattern by irradiation and contact with a developer; and a step of heating the composition.
[7] A semiconductor device manufactured using the positive photosensitive resin composition according to any one of [1] to [5].
[8] A display element manufactured using the positive photosensitive resin composition according to any one of [1] to [5].
[9] The positive photosensitive resin composition according to any one of [1] to [5] is applied on a semiconductor element so that the film thickness after heating is 0.1 to 50 μm, and prebaked. A method for manufacturing a semiconductor device, which is obtained by exposure, development and heating.
[10] The positive photosensitive resin composition according to any one of [1] to [5] is applied onto a display element substrate so that the film thickness after heating is 0.1 to 50 μm. A method for producing a display element, which is obtained by pre-baking, exposing, developing and heating.

  According to the present invention, a polybenzoxazole resin or polyimide resin excellent in resistance to hydrofluoric acid, or a polyamide resin intended to provide a copolymer resin thereof, and a positive photosensitive resin excellent in development characteristics using them. A composition, a method for producing a patterned resin film using the composition, a semiconductor device and a display element using the polyamide resin or the composition, and a method for producing the semiconductor device and the display element can be obtained.

The polyamide resin of the present invention is a polyamide resin having a structure represented by the general formula (1), wherein X in the general formula (1) represents a divalent to tetravalent organic group, and R ₁ represents a hydroxyl group. or a _{O-R 3,} m is an integer of 0-2. Each R ₁ may be the same or different. Y in the general formula (1) represents a divalent to hexavalent organic group, R ₂ is a hydroxyl group, a carboxyl group, O—R ₃ or COO—R ₃ , and n is an integer of 0 to 4. Each R ₂ may be the same or different. Here, R ₃ is an organic group having 1 to 15 carbon atoms. However, when there is no hydroxyl group as R _1, R ₂ is at least one 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 of the present invention is characterized in that, in the total amount of Y in the general formula (1), 0.1 mol% or more and 30 mol% or less as an essential component has a structure represented by the general formula (2). If it is less than 0.1 mol%, the effect of resistance to hydrofluoric acid, which is a feature of the present invention, is not observed. Moreover, when it exceeds 30 mol%, since the mechanical characteristics of a cured film will fall, it is not preferable.

As a structure represented by the general formula (2) that can be used in the present invention, for example,

However, it is not limited to these.

Among these, preferred are those having the structures shown below.

  The polyamide resin containing the structure represented by the general formula (1) is, for example, a compound selected from a diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the like and a structure of Y. (2) It is obtained by reacting a compound selected from tetracarboxylic anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. . 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 _{(1), 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 R ₃ which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or 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 resin, polybenzoxazole resin, or copolymerization of both.

X in general formula (1)
For example,

However, it is not limited to these.

Among these, particularly preferred are:

Two or more types may be used.

Further, Y that can be used other than the group represented by the general formula (2) of the polyamide resin containing the structure represented by the general formula (1) is, for example,

However, it is not limited to these.

Among these, particularly preferred are:

Two or more types 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 a 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 (1). Specifically, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the like, and a tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid having a structure of Y After synthesizing a polyamide resin having a structure represented by the general formula (1) obtained by reacting with a compound selected from acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. It is preferable to cap the terminal amino group contained in the polyamide resin as an amide using an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. 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 types 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

The present invention relates to a polyamide resin (A) and a photosensitive diazoquinone compound (B) in which 0.1 mol% or more and 30 mol% or less of the total amount of Y in the general formula (1) is a structure represented by the general formula (2). And a positive-type photosensitive resin composition.

  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 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 polyamide resins. If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

Furthermore, in the present invention, it is preferable to use a compound (C) having a phenolic hydroxyl group in combination so that it can be patterned with a high sensitivity and a high resolution without developing residue (scum) during development. As for the compounding quantity of the compound which has a phenolic hydroxyl group, 1-30 weight part is preferable with respect to 100 weight part of polyamide resins. Preferred phenol compounds are those represented by the general formula (3). Specific examples of the general formula (3) include the following, but are not limited thereto.

Of these, preferably

It is chosen from.

The polyamide resin of the present invention is 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, the composition is first 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 50 μm. If the film thickness is less than the lower limit value, it will be difficult to fully function as a protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. Takes a long time to reduce throughput. Examples of the coating method 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 the display device application include an interlayer insulating film for TFT, a TFT element flattening film, a color filter flattening film, a protrusion for an MVA liquid crystal display device, and a cathode partition for an organic EL element. The usage method is based on forming the patterned photosensitive resin composition layer on the substrate on which the display element and the color filter are formed in accordance with the above-described method. 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.

  The positive photosensitive resin composition according to the present invention is not only used for semiconductors, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, interlayer insulation films for elements in display elements, etc. Is also useful. As other semiconductor device manufacturing methods, known methods can be used.

Example 1
[Synthesis of polyamide resin]
3.31 g (0.0128 mol) of diphenyl ether-4,4′-dicarboxylic acid, 0.98 g (0.0032 mol) of dicarboxylic acid (D-1) having the following structure and 1-hydroxy-1,2,3-benzo A mixture (0.016 mol) of a dicarboxylic acid derivative obtained by reacting 4.32 g (0.032 mol) of triazole with hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 7 .33 g (0.020 mol) was put into a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 57.0 g of N-methyl-2-pyrrolidone was added. Dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 1.31 g (0.008 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 7 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 poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-1) was obtained.

[Preparation of resin composition]
After dissolving in 10 g of the synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1), and 70 g of γ-butyrolactone, the solution was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Obtained.

[Developability evaluation]
This positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 10 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon Corporation i-line stepper NSR-4425i The exposure amount was increased by 200 mJ / cm ² to 10 mJ / cm ² steps. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. As a result of observing the pattern, it was confirmed that the exposure was 500 mJ / cm ² and a 7 μm pattern was satisfactorily opened. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 2
[Synthesis of polyamide resin]
In the synthesis of the polyamide resin of Example 1, 3.31 g (0.0128 mol) of diphenyl ether-4,4′-dicarboxylic acid and 0.98 g (0.0032 mol) of dicarboxylic acid (D-1) having the following structure Example 1 except that 1 mol of diphenyl ether-4,4'-dicarboxylic acid was changed to 2.48 g (0.0096 mol) and 1.96 g (0.0064 mol) of dicarboxylic acid (D-1) having the following structure. In the same manner, a polyamide resin was synthesized (A-2).

[Production of resin composition, evaluation of developability]
Using the obtained polyamide resin (A-2), a positive photosensitive resin composition was prepared and evaluated in the same manner as in Example 1. The exposure amount was 520 mJ / cm ² and the development time was 80 seconds. It was confirmed that the pattern was well opened up to a pattern of 8 μm. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 3
[Synthesis of polyamide resin]
In the synthesis of the polyamide resin in Example 1, 0.98 g (0.0032 mol) of the dicarboxylic acid (D-1) having the following structure was changed to 1.20 g (0.0032 mol) of the dicarboxylic acid (D-2) having the following structure. A polyamide resin (A-3) was synthesized in the same manner as in Example 1 except for changing to.

[Production of resin composition, evaluation of developability]
It was dissolved in 10 g of the synthesized polyamide resin (A-3), 1.5 g of photosensitive diazoquinone (B-2) having the following structure, and 70 g of γ-butyrolactone having the following structure, and then filtered through a 0.2 μm fluororesin filter. As a result, a positive photosensitive resin composition was obtained.

When developing property evaluation was performed, it was confirmed that a 7 μm pattern was satisfactorily opened with an exposure amount of 480 mJ / cm ² and a developing time of 80 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 4
[Synthesis of polyamide resin]
6.82 g (0.022 mol) of 4,4′-oxydiphthalic anhydride, 14.08 g (0.033 mol) of acid anhydride (D-3) having the following structure, and 12.22 g of 2-methyl-2-propanol (0.165 mol) and 10.9 g (0.138 mol) of pyridine were placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube. 150 g of 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 carried out in the same manner as in Example 1 except that the reaction was carried out at 75 ° C. for 12 hours using an oil bath to synthesize the target polyamide resin (A-4).

[Production of resin composition, evaluation of developability]
It was dissolved in 10 g of the synthesized polyamide resin (A-4), 2.0 g of photosensitive diazoquinone (B-1) having the following structure, and 70 g of γ-butyrolactone having the following structure, and then filtered through a 0.2 μm fluororesin filter. As a result, a positive photosensitive resin composition was obtained.

When developing property evaluation was carried out, it was confirmed that a pattern of 8 μm was satisfactorily opened with an exposure amount of 520 mJ / cm ² and a development time of 70 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

  The production of the resin compositions in Examples 1 to 4 was evaluated by adding the compound (C) having a phenolic hydroxyl group as follows.

Example 5
[Production of resin composition, evaluation of developability]
10 g of the polyamide resin (A-1) obtained in Example 1, 2 g of photosensitive diazoquinone (B-1) having the following structure, and 1.5 g of the compound having a phenolic hydroxyl group (C-1) were converted to 70 g of γ-butyrolactone. After dissolution, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a 3 μm pattern was satisfactorily opened with an exposure amount of 420 mJ / cm ² and a development time of 50 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 6
[Production of resin composition, evaluation of developability]
10 g of the polyamide resin (A-2) obtained in Example 2, 2 g of photosensitive diazoquinone (B-1) having the following structure, and 0.5 g of a compound having a phenolic hydroxyl group (C-2) were converted to 70 g of γ-butyrolactone. After dissolution, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a pattern of 4 μm was satisfactorily opened with an exposure amount of 400 mJ / cm ² and a development time of 40 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 7
[Production of resin composition, evaluation of developability]
10 g of the polyamide resin (A-3) obtained in Example 3, 1.5 g of photosensitive diazoquinone (B-2) having the following structure, and 1.0 g of a compound (C-3) having a phenolic hydroxyl group were added to γ-butyrolactone. After dissolving in 70 g, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a 3 μm pattern was satisfactorily opened with an exposure amount of 430 mJ / cm ² and a development time of 40 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 8
[Production of resin composition, evaluation of developability]
10 g of the polyamide resin (A-4) obtained in Example 4, 2.0 g of photosensitive diazoquinone (B-1) having the following structure, and 1.5 g of the compound (C-1) having a phenolic hydroxyl group were converted to γ-butyrolactone. After dissolving in 70 g, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a 3 μm pattern was satisfactorily opened with an exposure amount of 430 mJ / cm ² and a development time of 40 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, even when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 15 minutes, no peeling of the pattern was observed.

Example 9
[Preparation of display element and characteristics evaluation]
After forming an ITO film on the glass substrate by vapor deposition, the ITO film was divided into stripes by an ordinary photolithography method using a photoresist. On top of this, the positive photosensitive resin composition obtained in Example 1 was applied to form a resin layer having a thickness of about 2 μm. Next, using a parallel exposure machine (light source: high-pressure mercury lamp), exposure was performed through a glass mask for 10 seconds at an exposure intensity of 25 mW / cm 2. Thereafter, the resin layer was immersed and developed in a 2.38% tetramethylammonium hydroxide aqueous solution for 25 seconds to expose portions other than the ITO edge on each stripe, and the ITO edge portion and the ITO removed portion were exposed. Processing was performed so that the resin layer was formed only on the top. Thereafter, the entire resin layer was subjected to post-exposure for 40 seconds at an exposure intensity of 25 mW / cm ² using the parallel exposure machine used at the time of exposure, and then heated at 250 ° C. in air using a hot air circulation dryer. Time-hardening was performed.
After depositing copper phthalocyanine as a hole injection layer and bis-N-ethylcarbazole as a hole transport layer on this substrate under a reduced pressure of 1 × 10 ⁻⁴ Pa or less, N, N′-diphenyl was used as a light emitting layer. -N, N'-m-toluyl-4,4'-diamino-1,1'-biphenyl and tris (8-quinolinolate) aluminum were deposited in this order as an electron injection layer. Further, after an aluminum layer is deposited on the second electrode as a second electrode, the aluminum layer is formed into a stripe shape in a direction perpendicular to the stripe of the ITO film by a normal photolithography method using a photoresist. Divided. After the obtained substrate was dried under reduced pressure, the sealing glass plate was bonded using an epoxy adhesive to produce a display element. This display element was treated at 80 ° C. for 200 hours and then applied to both electrodes to drive sequentially. However, the element emitted light without any problem.

<< Comparative Example 1 >>
[Synthesis of polyamide resin]
Dicarboxylic acid obtained by reacting 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid with 4.32 g (0.032 mol) of 1-hydroxy-1,2,3-benzotriazole Mixture of derivatives (0.016 mol) and 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were thermometer, stirrer, raw material inlet, and drying. Into a four-necked separable flask equipped with a nitrogen gas inlet tube, 57.0 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, 1.31 g (0.008 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 7 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 poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-5) was obtained.

[Preparation of resin composition]
10 g of the synthesized polyamide resin (A-5), 2 g of photosensitive diazoquinone (B-1) having the following structure, 0.5 g of γ-glycidoxypropyltrimethoxysilane as a silane coupling, 50 g of N-methyl-2-pyrrolidone Then, it was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

[Developability evaluation]
Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a 7 μm pattern was satisfactorily opened with an exposure amount of 500 mJ / cm ² and a development time of 80 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven.
Next, peeling of the pattern was observed when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 7 minutes.

<< Comparative Example 2 >>
[Production of resin composition, evaluation of developability]
10 g of the polyamide resin (A-5) synthesized in Comparative Example 1, 2 g of photosensitive diazoquinone (B-1) having the following structure, and 0.5 g of the compound having a phenolic hydroxyl group (C-2) having the following structure The ring was dissolved in 70 g of N-methyl-2-pyrrolidone, and then filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition. Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that a 3 μm pattern was satisfactorily opened with an exposure amount of 420 mJ / cm ² and a development time of 50 seconds. Next, the obtained pattern was cured at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1000 ppm or less using a clean oven. Next, peeling of the pattern was observed when the cured wafer was immersed in a 1% hydrofluoric acid solution at room temperature for 9 minutes.

The present invention relates to a polyamide resin intended to provide a polybenzoxazole resin or polyimide resin excellent in resistance to hydrofluoric acid or a copolymer resin thereof, and a positive photosensitive resin composition excellent in development characteristics using them. An object, a semiconductor device, a display element, and a method for manufacturing the semiconductor device and the display element are provided.

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 (10)

A polyamide resin having a structure represented by the general formula (1), wherein 0.1 mol% to 30 mol% of the total amount of Y in the general formula (1) is a structure represented by the general formula (2). Yes, in the case where Y in the general formula (1) has a structure represented by the general formula ( ₂ ), _n of (R ₂ ) _n in the general formula (1) is 0 .

The polyamide resin according to claim 1, wherein the structure represented by the general formula (2) is one of the following structures.
  A positive photosensitive resin composition comprising the polyamide resin (A) according to claim 1 or 2 and a photosensitive diazoquinone compound (B).   Furthermore, the positive photosensitive resin composition of Claim 3 containing the compound (C) which has a phenolic hydroxyl group. The positive photosensitive resin composition according to claim 4, wherein the compound (C) having a phenolic hydroxyl group has the following structure.
  A step of coating the positive photosensitive resin composition according to any one of claims 3 to 5 on a substrate to form a composition layer, and irradiating the composition layer with active energy rays to develop a developer. A method for producing a patterned resin film, comprising: a step of forming a pattern by contacting with a substrate; and a step of heating the composition. A semiconductor device manufactured using the positive photosensitive resin composition according to any one of claims 3 to 5. A display element manufactured using the positive photosensitive resin composition according to any one of claims 3 to 5. The positive photosensitive resin composition according to any one of claims 3 to 5 is applied onto a semiconductor element so that the film thickness after heating is 0.1 to 50 µm, and prebaking, exposure, development, A method for manufacturing a semiconductor device, which is obtained by heating. The positive photosensitive resin composition according to any one of claims 3 to 5 is applied onto a display element substrate so that the film thickness after heating is 0.1 to 50 µm, and prebaking, exposure, A method for producing a display element, which is obtained by developing and heating.