JP2005266420A - Photosensitive resin composition, and semiconductor device and display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has high sensitivity and superior light-shielding properties and which can be patterned, without producing scums, and to provide a semiconductor device and a display element. <P>SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photosensitive material and (C) a substance which can develop light shielding properties by heat treatment. For the alkali-soluble resin, polyamide resin is preferable. For the substance which can develop the light-shielding property by heat treatment, a melamine dye precursor which turns into black by heat treatment is preferable; and for the melamine dye precursor, tyrosine, dopa, dopaquinone, leucodopachrome, dopachrome, 5,6-dihydroxyindole, indole-5,6-quinone or the like can be used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition, a semiconductor device using the same, and a display element.

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 photosensitive resin in which a precursor of polybenzoxazole resin or polyimide resin is combined with a diazoquinone compound as a photosensitive material is also used (see, for example, Patent Document 1). The development mechanism of this photosensitive resin composition is hardly soluble in an alkaline aqueous solution in the unexposed area due to the effect of inhibiting the dissolution of the diazoquinone compound in a resin such as polybenzoxazole resin or polyimide resin. On the other hand, in the exposed area, the diazoquinone compound undergoes a chemical change and becomes soluble in an alkaline aqueous solution. 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. These photosensitive resins are heat-cured after pattern formation and cyclized to convert polybenzoxazole resin or polyimide resin. These heat-cured films have a brown color, and the semiconductor element circuit appears to be transparent. Recently, however, there is a demand for an opaque positive photosensitive resin from the viewpoint of circuit design confidentiality.
On the other hand, in the field of display elements, liquid crystal display devices, organic EL display devices, and plasma display devices have begun to spread due to demand for personal computers and large-sized televisions. The black matrix used for these display elements is used between the colored pixels and is an important material used for improving contrast and preventing deterioration of transistor characteristics due to light. In general, a metal-chromium thin film has been used as the black matrix material, but in recent years, a photosensitive resin black matrix obtained by adding a black pigment to a resin has been used. Generally, an acrylic resin contains a pigment, an initiator, and a crosslinking agent. However, these acrylic resin-based black matrices contain a large amount of a pigment that is not soluble in a developer, and thus developability is poor. There is a problem in practicality because it remains as a scum at the bottom of the pattern or the development time becomes extremely long.
Japanese Examined Patent Publication No. 1-46862

  An object of the present invention is to provide a photosensitive resin composition, a semiconductor device, and a display element that have excellent light shielding properties and can be patterned without scum.

［５］ 熱処理によって遮光性が発現できる物質（Ｃ）が、メラニン色素前駆体である［１］〜［４］項のいずれか１項に記載の感光性樹脂組成物。
［６］ 感光材（Ｂ）がキノンジアジド化合物及び／又はジヒドロピリジン化合物を含んでなる［１］〜［５］項のいずれか１項に記載の感光性樹脂組成物。
［７］ ［１］〜［６］項のいずれか１項に記載の感光性樹脂組成物を用いて製作されてなることを特徴とする半導体装置。
［８］ ［１］〜［６］項のいずれか１項に記載の感光性樹脂組成物を用いて製作されてなることを特徴とする表示素子。
［９］ ［１］〜［６］項のいずれか１項に記載の感光性樹脂組成物を加熱脱水閉環後の膜厚が、０．１〜３０μｍになるように半導体素子上に塗布し、プリベーク、露光、現像、必要に加熱して得られることを特徴とする半導体装置の製造方法。
［１０］ ［１］〜［６］項のいずれか１項に記載の感光性樹脂組成物を加熱脱水閉環後の膜厚が、０．１〜３０μｍになるように表示素子用基板上に塗布し、プリベーク、露光、現像、必要に加熱して得られることを特徴とする表示素子の製造方法。 Such an object is achieved by the present invention described in the following [1] to [10].
[1] A photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive material (B), and a substance (C) capable of exhibiting light-shielding properties by heat treatment.
[2] The photosensitive resin composition according to item [1], wherein the alkali-soluble resin (A) is a polyamide resin.
[3] The photosensitive resin composition according to item [2], wherein the polyamide resin 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.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the substance (C) capable of exhibiting light shielding properties by heat treatment is a melanin precursor.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the photosensitive material (B) comprises a quinonediazide compound and / or a dihydropyridine compound.
[7] A semiconductor device manufactured using the photosensitive resin composition according to any one of items [1] to [6].
[8] A display element manufactured using the photosensitive resin composition according to any one of items [1] to [6].
[9] The photosensitive resin composition according to any one of [1] to [6] is applied on a semiconductor element so that a 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, exposure, development, and heating as necessary.
[10] The photosensitive resin composition according to any one of [1] to [6] 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 a pre-baking, exposure, development, and heating as necessary.

  According to the present invention, it is possible to obtain a photosensitive resin composition, a semiconductor device, and a display element that have excellent light shielding properties and can be patterned without scum.

  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 of the polyamide resin having the structure represented by the general formula (1) represents a divalent to tetravalent organic group, R ₁ is a hydroxyl group or O—R ₃ , and m is an integer of 0 to 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 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 having the structure represented by the general formula (1) is, for example, a compound selected from diamine having an X structure or bis (aminophenol), 2,4-diaminophenol, and the like, and a tetracarboxylic acid having a Y structure. It is obtained by reacting with a compound selected from anhydride, trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. 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 by R ₃ which is an organic group having 1 to 15 carbon atoms, and if necessary, a hydroxyl group or a carboxyl group may be protected. 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 300 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.

等であるが、これらに限定されるものではない。 As X in the general formula (1), for example,

However, it is not limited to these.

より選ばれるものであり、又２種類以上用いても良い。 Among these, particularly preferred are:

Two or more types may be used.

Moreover, as Y of general formula (1), for example,

等であるが、これらに限定されるものではない。

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:

等が挙げられるが、これらに限定されるものではない。

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

  As the photosensitive material used in the present invention, a photosensitive material capable of positive patterning can be used, and specifically, a diazoquinone compound or a dihydropyridine compound can be used. The diazoquinone compound is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from US Pat. 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.

  Examples of the dihydropyridine compound used in the present invention 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.

  As the substance (C) capable of exhibiting light-shielding properties by heat treatment that can be used in the present invention, a substance that can be added to the photosensitive resin composition and exhibit desired light-shielding properties can be used. Further, in order to avoid a decrease in sensitivity and occurrence of scum due to patterning due to coloring, it is preferable that the resin composition transmit visible light and ultraviolet light during patterning and turn black after patterning. Therefore, as a substance that can exhibit light-shielding properties by heat treatment, a melanin pigment precursor that becomes black by heat treatment is preferable. Examples of the melanin pigment precursor include tyrosine, dopa, dopaquinone, leucodopachrome, dopachrome, 5,6-dihydroxyindole, indole-5,6-quinone and the like.

  In the present invention, the alkali-soluble resin (A), the photosensitive material (B), and the substance (C) capable of developing light-shielding properties by heat treatment 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.

  As for the dissolution method, in addition to a general mixer, a disperser, and a three roll, a bead mill, an annular bead mill, a beadless disperser, or the like is preferably used to improve dispersibility.

  The photosensitive resin composition of the present invention can be used by first using the composition with a suitable support, for example, a semiconductor substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, soda glass, Pyrex (R) glass, It apply | coats to substrates for display elements, such as alkali glass. 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 below 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. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, 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 an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance. In order to make it transparent using the bleaching characteristic of the photosensitive material, curing may be performed after the entire surface is exposed before curing.

  The photosensitive resin composition according to the present invention can be used for a surface protective film of a semiconductor, an interlayer insulating film, or an interlayer insulation of a multilayer circuit. It is also useful as an interlayer insulating film or black matrix in organic EL elements and liquid crystal display elements.

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 A mixture of acid 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, Into a four-necked separable flask equipped with 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, 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]
10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, and 10 g of dopa are mixed and dispersed in 40 g of γ-butyrolactone using three rolls, and a filter made of 2 μm fluororesin And a translucent photosensitive resin composition was obtained.

[Developability evaluation]
This photosensitive resin composition was applied to 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 4 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn) is passed through Nikon g-line stepper NSR-1553G3A. The exposure was performed at an exposure amount of 400 mJ / cm ² . Next, the development time was adjusted in a 2.38% tetramethylammonium hydroxide aqueous solution so that the film slip during development was 1.5 μm, and the exposed portion was dissolved and removed, followed by rinsing with pure water for 30 seconds. When the pattern was observed, it was confirmed that the 10 μm pattern had no scum and the pattern was well opened.

[Transmittance evaluation]
The prepared pattern was heated in an oven at 300 ° C./30 minutes, and after curing, a film of about 2 μm was obtained. At this time, it was confirmed that the film was changed to black. The film was peeled off by dipping in a 2% hydrofluoric acid aqueous solution, and the transmittance at 400 nm was measured. As a result, the film showed a good light shielding property of 9.5%.

Example 2
Instead of 2 g of the photosensitive diazoquinone (B-1) used in Example 1, 2,6-dimethyl-3,5-dicarboxymethyl-4- (2′-nitrophenyl) -1,4-dihydropyridine (abbreviated as DHPM) ) (B-2) 3.0 g was used, and the others were evaluated in the same manner as in Example 1.
Example 3
[Synthesis of polyamide resin]
Thermometer containing 17.06 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 8.15 g (0.110 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 44.7 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane are added together with 70 g of N-methyl-2-pyrrolidone at room temperature. Stir for 2 hours. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 3.94 g (0.024 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 hours to complete the reaction. In the same manner as in Example 1, reprecipitation and purification were performed to synthesize the target polyamide resin (A-2).

[Production of resin composition, developability, transmittance evaluation]
10 g of the synthesized polyamide resin (A-2), 1.5 g of photosensitive diazoquinone (B-3) having the following structure, and 12 g of dopa are mixed and dispersed in 40 g of γ-butyrolactone using three rolls, and a 1 μm fluororesin. It filtered with the filter made from, and obtained the photosensitive resin composition. Evaluation of developability and transmittance was carried out in the same manner as in Example 1.

<< Comparative Example 1 >>
In place of 10 g of dopa used in Example 1, 10 g of Kayset Black B manufactured by Nippon Kayaku was used, and other than that, evaluation was performed in the same manner as in Example 1. As a result, a 10 μm pattern was opened, but scum Was confirmed. When the transmittance at 400 nm was measured, the transmittance was 0.2%.

  The present invention provides a photosensitive resin composition, a semiconductor device, and a display element that have excellent light shielding properties and can be patterned without scum.

Claims (10)

A photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive material (B), and a substance (C) capable of exhibiting light shielding properties by heat treatment. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide resin. 3. The photosensitive resin composition according to claim 2, wherein the polyamide resin 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 photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

The photosensitive resin composition according to any one of claims 1 to 4, wherein the substance (C) capable of exhibiting light-shielding properties by heat treatment is a melanin pigment precursor. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive material (B) comprises a quinonediazide compound and / or a dihydropyridine compound. A semiconductor device manufactured using the photosensitive resin composition according to claim 1. A display element manufactured by using the photosensitive resin composition according to claim 1. The photosensitive resin composition according to any one of claims 1 to 6 is applied onto 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 as necessary. The photosensitive resin composition according to any one of claims 1 to 6 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 prebaking, exposure, A method for producing a display element, which is obtained by developing and, if necessary, heating.