JP4525202B2 - Positive photosensitive resin composition, semiconductor device and display element, semiconductor device, and display element manufacturing method - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a semiconductor device, and a 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. There is a demand for lowering the curing temperature as well as significant improvements in characteristics such as heat cycle resistance and heat shock resistance due to the thinning and downsizing of semiconductor devices and the transition to surface mounting by solder reflow, etc. Resins have become necessary. 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 (2).

  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. 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 alkaline aqueous 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.

  In recent years, some semiconductor devices that require a protective film cannot withstand high temperatures, and there are cases where display elements cannot be cured at high temperatures due to device capabilities. In that case, in the previous positive photosensitive resin composition, the formation of an imide ring or an oxazole ring becomes insufficient, resulting in a problem that the mechanical properties of the final cured film deteriorate. Therefore, it is possible to increase the cyclization rate by adding a catalyst such as p-toluenesulfonic acid that promotes cyclization. However, since such a catalyst is a strong acid, there is a problem such as aluminum corrosion in an actual device. is there. Patent Document 2 discloses a compound having a sulfone group in a positive photosensitive composition, but the sulfone compound as disclosed herein does not show the effect of promoting cyclization.

Japanese Examined Patent Publication No. 1-46862

JP2000-241974

  The present invention provides a positive photosensitive resin composition, a semiconductor device, and a display element that are excellent in low-temperature curing and less corrosive to aluminum.

Such an object is achieved by the present invention described in the following [1] to [13].
[1] A positive photosensitive resin composition comprising an alkali-soluble resin (A), a diazoquinone compound (B), and an aliphatic sulfonic acid compound (C),
[2] 100 parts by weight of alkali-soluble resin (A), 1-50 parts by weight of diazoquinone compound (B), 0.1-20 parts by weight of aliphatic sulfonic acid compound (C) A positive photosensitive resin composition,
[3] The positive photosensitive resin composition according to [1] and [2], wherein the alkali-soluble resin (A) is a polyamide resin,
[4] The alkali-soluble resin (A) is a polyamide resin comprising a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure, each alone or in combination of two or more. The positive photosensitive resin composition as described,
[5] The positive photosensitive resin composition according to any one of [1] to [4], wherein the alkali-soluble resin (A) is a polyamide resin including a structure represented by the general formula (1).

[6] The positive photosensitive resin composition according to [5], wherein X in the polyamide resin having a structure represented by the general formula (1) is selected from the following group:

[7] The positive photosensitive resin composition according to [5] or [6], wherein Y in the polyamide resin including the structure represented by the general formula (1) is selected from the following group:

[8] The polyamide resin according to any one of [3] to [7], wherein the polyamide resin is end-capped with a compound containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. A positive photosensitive resin composition,

[9] A step of coating the positive photosensitive resin composition according to any one of [1] to [8] on a substrate to form a composition layer, and an active energy ray on the approximate 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 an approximate composition.
[10] A semiconductor device manufactured using the positive photosensitive resin composition according to any one of [1] to [8],

[11] A display element manufactured using the positive photosensitive resin composition according to any one of [1] to [8],
[12] The positive photosensitive resin composition according to any one of [1] to [8] is applied on a semiconductor element so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm, and prebaked. , A method for manufacturing a semiconductor device, characterized by being obtained by exposure, development, and heating,
[13] The positive photosensitive resin composition according to any one of [1] to [8] is applied onto a display element substrate so that the film thickness after heat dehydration and ring closure is 0.1 to 30 μm. A method for producing a display element, which is obtained by pre-baking, exposing, developing and heating.

  The present invention provides a positive photosensitive resin composition excellent in low-temperature curing and less corrosive to aluminum, a semiconductor device and a display element, and a method for manufacturing the semiconductor device and the display element.

  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 is a cresol type novolak resin, polyhydroxystyrene, or polyamide resin. Of these, polyamide resins are preferred. The polyamide resin is a resin having a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure and having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain. Among these, a polyamide resin including a structure represented by the general formula (1) is preferable from the viewpoint of heat resistance after the final heating. Further, some of these resins may be ring-closed to have a polybenzoxazole structure or a polyimide structure.

X in the polyamide resin containing the structure represented by the general formula (1) 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 (1) 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, etc. 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 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 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, 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 (1) 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 (1) 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 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, 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 (1) obtained by reacting with a compound selected from acid anhydride, trimellitic 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, the terminal amino group contained in the polyamide resin is converted into an amide using an acid anhydride containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. It is preferable to cap. Examples of the group derived from an acid anhydride 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 kinds 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 a cyclic compound group having at least one alkenyl group or alkynyl group. You can also

Furthermore, Z of the polyamide resin containing the structure represented by the general formula (1) 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 having the structure represented by the general formula (1) is used when particularly excellent adhesion to a substrate such as a silicon wafer is required, 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 diazoquinone compound (B) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from U.S. Pat. It is. 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 diazoquinone compound (B) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin. 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.

  As the aliphatic sulfonic acid compound (C) used in the present invention, one having a structure in which a sulfur atom of a sulfonic acid group is bonded to an aliphatic group can be used. In the present invention, as the sulfonic acid, 2-methyl-a- [5-[[(octylsulfonyl) oxy] imino] -2 (5H) -thienylidene]-(9C1), 2-isopropylethyl ester, 1,3 -Butane sultone, methanesulfonic acid methyl ester, methanesulfonic acid ethyl ester, methanesulfonic acid phenyl ester, methanesulfonic acid 2-isopropylethyl ester and the like can be mentioned, but are not limited thereto. In the present invention, it is used to promote cyclization.

  The blending amount of the sulfonic acid compound (C) in the present invention is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). If the blending amount of the acid generator (C) is less than 0.1 parts by weight, the effect of increasing the cyclization rate is weak, and if it exceeds 20 parts by weight, the electrical insulation may be lowered.

  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, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form a polyimide ring, an oxazole ring, or both a polyimide ring and an oxazole ring, thereby obtaining a final pattern rich in heat resistance.
The positive 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, liquid crystal alignment films and interlayer insulation films in display elements. is there.

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 example of an enlarged 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>
Synthesis of polyamide resin 41.3 g (0.16 mol) of diphenyl ether-4,4′-dicarboxylic acid was reacted with 43.2 g (0.32 mol) of 1-hydroxy-1,2,3-benzotriazole. A mixture (0.16 mol) of the obtained dicarboxylic acid derivative and 73.3 g (0.20 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were thermometer, stirrer, Into a four-necked separable flask equipped with a raw material inlet and a dry 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, 13.11.31 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of N-methyl-2-pyrrolidone was added, and the reaction was completed after 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, dried under vacuum, and the desired polyamide resin ( A-1) 100.5 g was obtained.

Production of positive photosensitive resin composition 100 g of synthesized polyamide resin (A-1), 18 g of photosensitive diazoquinone compound having the structure of the following formula (B-1), sulfonic acid having the structure of the following formula (C-1) 7 g of the compound was dissolved in 250 g of γ-butyrolactone, and then filtered through a 0.2 μm Teflon (R) filter to obtain a positive photosensitive resin composition.

Processability Evaluation A positive photosensitive resin composition was applied to a bare silicon wafer using a spin coater, and prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 7.5 μm. Next, using mask aligner PLA-600A (made by Canon), it exposed by 200 mJ / cm <2> by h line | wire. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 20 seconds, and then rinsed with pure water for 10 seconds. As a result, it was confirmed that a 5 μm pattern was opened. Thereafter, using a clean oven manufactured by Koyo Lindbergh, the film was heated and cured at 230 ° C. for 60 minutes in a nitrogen atmosphere to obtain a coating film having a thickness of about 5 μm. When the obtained appearance was observed, there was no abnormality.

Aluminum corrosion test A positive photosensitive resin composition was applied to a wafer having an aluminum wiring of about 1 μm on SiO 2 using a spin coater, and prebaked at 120 ° C. for 4 minutes on a hot plate to obtain a film thickness of about 6. A 5 μm coating film was obtained. Thereafter, using a clean oven manufactured by Koyo Lindbergh, the film was heated and cured at 230 ° C. for 60 minutes in a nitrogen atmosphere to obtain a coating film having a thickness of about 5 μm. Next, after putting it in a pressure cooker at 125 ° C. and 2.3 atm for 24 hours and observing with a microscope, no corrosion was seen in the aluminum wiring part.

Measurement of cyclization rate Separately, a positive photosensitive resin composition was applied onto a silicon wafer using a spin coater and then pre-baked at 120 ° C. for 4 minutes on a hot plate to obtain a coating film having a thickness of about 3 μm. . Next, the obtained silicon wafer was immersed in 2% hydrofluoric acid to obtain a film. Then the IR measurement, Perkin Elmer Fourier transform infrared spectrophotometer PARAGON1000 used was determined to calculate the ratio of the peak (A) associated with total aromatics 1050Cm- ¹ oxazole group and 1480cm- ^1. Next, using an oven, after heating the polyamide resin at 350/60 minutes, subjected to IR measurements in the same manner in workability evaluation, peak accompanying the wholly aromatic oxazole group and 1480Cm- ¹ of 1050Cm- ¹ The ratio (B) was calculated. The cyclization rate was a value obtained by multiplying A / B by 100. The cyclization rate thus determined was 99%.

<Example 2>
100 g of the polyamide resin (A-1) synthesized in Example 1, 18 g of the photosensitive diazoquinone compound having the structure of the following formula (B-1), and 10 g of the sulfonic acid compound having the structure of the following formula (C-2) were γ- After dissolving in 250 g of butyrolactone, the mixture was filtered through a 0.2 μm Teflon (R) filter to obtain a positive photosensitive resin composition. Thereafter, the same evaluation as in Example 1 was performed. In the workability evaluation, an opening of 5 μm was confirmed. Corrosion was not found in the aluminum corrosion evaluation. When the cyclization rate was measured, the cyclization rate was 96%.

<Example 3>
100 g of the polyamide resin (A-1) synthesized in Example 1, 20 g of the photosensitive diazoquinone compound having the structure of the following formula (B-2), and 1 g of the sulfonic acid compound having the structure of the following formula (C-3) After dissolving in 250 g of butyrolactone, the mixture was filtered through a 0.2 μm Teflon (R) filter to obtain a positive photosensitive resin composition. Thereafter, the same evaluation as in Example 1 was performed. In the workability evaluation, an opening of 5 μm was confirmed. Corrosion was not found in the aluminum corrosion evaluation. When the cyclization rate was measured, the cyclization rate was 92%.

<Comparative Example 1>
In the preparation of the positive photosensitive resin composition in Example 1, the sulfonic acid compound (C) was not added, and the same evaluation was performed. In the processability evaluation, an opening of 5 μm was formed. Although no corrosion was observed, when the cyclization rate was measured, the cyclization rate was as low as 60%, and this cyclization rate was insufficient as a property of the cured film.

<Comparative example 2>
In the preparation of the positive photosensitive resin composition in Example 1, p-toluenesulfonic acid (C-4) was added as the sulfonic acid compound (C) and the same evaluation was performed. In the measurement of the cyclization rate with an opening of 5 μm, the cyclization rate was as high as 98%. However, corrosion was observed in the aluminum corrosion evaluation, and there was a possibility of failure due to disconnection when actually applied.

<Comparative Example 3>
In preparation of the positive photosensitive resin composition in Example 1, p-toluenesulfonamide (C-5) was added as the sulfonic acid compound (C), and the same evaluation was performed. Although the opening was 5 μm and no corrosion was observed in the aluminum corrosion evaluation, when the cyclization rate was measured, the cyclization rate was as low as 67%. It is enough.

<Comparative example 4>
In the preparation of the positive photosensitive resin composition in Example 1, p-toluenesulfonanilide (C-6) was added as the sulfonic acid compound (C) and the same evaluation was performed. Although the opening was 5 μm and no corrosion was observed in the aluminum corrosion evaluation, when the cyclization rate was measured, the cyclization rate was as low as 69%. It is enough.

Next, an example adapted to a semiconductor device is shown below.
<Example 4>
The photosensitive resin composition obtained in Example 1 was applied on the wafer used in the aluminum corrosion test of Example 1, and holes were formed in the bonding pad portion of the wiring under the same processing conditions as in Example 1. A resin layer having a thickness of about 5 μm was formed on the aluminum wiring. This silicon wafer is cut with a dicing saw, mounted on a lead frame (42-alloy), the lead frame and the bonding pad on the silicon wafer are connected with a gold wire, and then an epoxy resin sealing material (Sumitomo Bakelite Co., Ltd.) A 26-pin SOJ type IC package was formed by sealing with EME-6300H. The obtained IC package was allowed to stand for 96 hours under conditions of a temperature of 40 ° C. and a relative humidity of 90%, and then heated at 230 ° C. for 90 seconds in an IR reflow furnace, but no change was observed. Further, the inside of the package after heating was observed with an ultrasonic flaw detector, but no peeling was observed between the layers in the package.

Next, an example in which the display element is applied will be described.
<Example 5>
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 at an exposure intensity of 25 mW / cm 2 for 10 seconds. Thereafter, the resin layer was immersed and developed in a 2.38% tetramethylammonium hydroxide aqueous solution for 20 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 230 ° C. in air using a hot air circulation dryer. Time-hardening was performed.
On this substrate, under 1 × 10 ^-4 Pa or less under reduced pressure, copper phthalocyanine as a hole injection layer, after depositing bis -N- ethylcarbazole as a hole transport layer, N as a light emitting layer, N'- diphenyl -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 orthogonal 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.

As described above, Examples 1 to 3 and 4 and 5 are excellent in providing a positive photosensitive resin composition, a semiconductor device and a display element that are excellent in low-temperature curing of the present invention and have low aluminum corrosivity, but are comparative examples. 1-4 is not appropriate.

  The positive photosensitive resin of the present invention is suitably used in the application of a surface protective film or an interlayer insulating film of a semiconductor element, an interlayer insulating film, a planarizing film or a partition wall of a display element.

FIG. 1 is an example of an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps according to 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 (11)

Alkali-soluble resin (A), the diazoquinone compound (B), aliphatic sulfonic acid compound (C) a free Mupo di photosensitive resin composition,
A positive photosensitive resin composition in which the alkali-soluble resin (A) is a polyamide resin containing a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure alone or in combination of two or more. The positive type according to claim 1, wherein the alkali-soluble resin (A) is 100 parts by weight, the diazoquinone compound (B) is 1 to 50 parts by weight, and the aliphatic sulfonic acid compound (C) is 0.1 to 20 parts by weight. Photosensitive resin composition. The positive photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (A) is a polyamide resin containing a structure represented by the general formula (1).


The positive photosensitive resin composition according to claim 3 , wherein X in the polyamide resin having a structure represented by the general formula (1) is selected from the following group.
The positive photosensitive resin composition according to claim 3 or 4 , wherein Y in the polyamide resin containing the structure represented by the general formula (1) is selected from the following group.



The positive photosensitive resin according to any one of claims 1 to 5 , wherein the polyamide resin is end-capped with a compound containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group. Resin composition. Forming a composition layer by applying onto a substrate a positive photosensitive resin composition according to any one of claims 1 to 6 developing solution by irradiation with active energy rays to the composition layer 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. The semiconductor device characterized by comprising been fabricated using the positive photosensitive resin composition according to any one of claims 1-6. Display element characterized by comprising been fabricated using the positive photosensitive resin composition according to any one of claims 1-6. The positive photosensitive resin composition according to any one of claims 1 to 6 is applied on a semiconductor element so that the film thickness after heat-dehydration and ring closure is 0.1 to 30 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 1 to 6 is applied on a display element substrate so that the film thickness after heating and dehydration and ring closure is 0.1 to 30 μm, and prebaking, exposure, A method for producing a display element, which is obtained by developing and heating.