JP2007101795A - Photosensitive resin composition, method for producing pattern forming resin layer, and semiconductor device and display device including the photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which excels in light blocking effect and can be patterned without generating scum; and also to provide a semiconductor device and a display device. <P>SOLUTION: The positive photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photosensitizing agent and (C) titanium black. The titanium black (C) preferably has a particle diameter of 30-200 nm, the alkali-soluble resin (A) is preferably a polyamide resin or a polybenzoxazole precursor resin, and the photosensitizing agent (B) is preferably selected from a quinonediazido compound and a dihydropyridine compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a method for producing a pattern forming resin layer, and a semiconductor device and a display element including the photosensitive resin composition.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements. 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 agent is also used (Patent Document 1).
These photosensitive resins change to polybenzoxazole resin or polyimide resin through a thermosetting reaction after pattern formation. The film after the thermosetting reaction has a brown color, and the circuit of the semiconductor element appears to be transmitted. With regard to the transparency of the resin layer, an opaque positive photosensitive resin is recently required 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 in these display elements is an important material used between colored pixels and 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 is added with a pigment, an initiator, and a cross-linking agent (Patent Document 2), but these acrylic resin-based black matrices contain a large amount of pigment that is not soluble in the developer. The developability is poor and it remains as a scum at the bottom of the pattern or the development time becomes extremely long, which causes a problem in practical use. Moreover, although carbon black is generally used as the black pigment, there has been a problem of causing a decrease in electrical characteristics.
JP-A-1-46862 JP-A-9-184911

However, the prior art described in the above literature has room for improvement in the following points.
First, the resin composition to which no pigment is added has a problem that the circuit of the semiconductor element is seen through after the resin is cured, and the confidentiality cannot be maintained.
Secondly, as seen in the field of display elements, when a commonly used negative photosensitive resin black matrix material is used, the developability is poor and it remains as a scum at the bottom of the pattern. There was a problem that would become extremely long.
Third, when carbon black is used as the black matrix material, there is a problem that the conductivity of the resin is increased, resulting in poor conduction.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an opaque positive photosensitive resin. Another object of the present invention is to suppress the occurrence of scum and shorten the development time.

（Ｘ、Ｙは有機基である。ａ、ｂはモルパーセントを示し、ａ＋ｂ＝１００で、ａが６０以上１００以下、ｂが０以上〜４０以下である。Ｒ1は水酸基又は−Ｏ−Ｒ₃であり、同一でも異なっても良い。Ｒ₂は水酸基、カルボキシル基、−Ｏ−Ｒ₃、−ＣＯＯ−Ｒ₃のいずれかであり、同一でも異なっても良い。ｍは０〜２の正数、ｎは０〜４の正数である。Ｒ₃は炭素数１〜１５の有機基である。ここで、Ｒ₁として水酸基がない場合、Ｒ₂は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_２としてカルボキシル基がない場合、Ｒ_１は少なくとも１つは水酸基でなければならない。Ｚは−Ｒ_４−Ｓｉ（Ｒ_６）（Ｒ_７）−Ｏ−Ｓｉ（Ｒ_６）（Ｒ_７）−Ｒ_５−で表され、Ｒ₄、Ｒ₅は２価の有機基であり、Ｒ₆、Ｒ₇は１価の有機基である。）
［７］
感光剤（Ｂ）がキノンジアジド化合物、又はジヒドロピリジン化合物を含んでなる［１］〜［６］のいずれかに記載の感光性樹脂組成物。
［８］
［１］〜［７］のいずれかに記載の樹脂組成物を基材上に塗布して樹脂層を形成する工程と、該樹脂層の所望の部分に活性エネルギー線を照射する工程と、活性エネルギー線照射後の該樹脂層に現像液を接触させ、次いで該樹脂層を加熱する工程と、を含むことを特徴とするパターン形成方法。
［９］
半導体基板と、該半導体基板に設けられた半導体素子と、該半導体素子の上部に設けられた絶縁膜とを備え、
前記絶縁膜は、［１］〜［７］のいずれかに記載の樹脂組成物を塗布、乾燥して形成された膜であることを特徴とする半導体装置。
［１０］
表示素子用基板と、その表面を覆う絶縁膜と、前記表示素子用基板の上部に設けられた表示素子とを備え、
前記絶縁膜は、［１］〜［７］のいずれかに記載の樹脂組成物を塗布、乾燥して形成された膜であることを特徴とする表示装置。
［１１］
半導体チップとその表面を覆う保護膜とを備える半導体装置の製造方法であって、
前記半導体チップ上に樹脂組成物を塗布、乾燥して樹脂層を形成する工程と、
樹脂層の所望の部分に活性エネルギー線を照射する工程と、
活性エネルギー線照射後の該樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記保護膜を形成する工程と、
を含み、
前記樹脂組成物が［１］〜［７］のいずれかに記載の樹脂組成物であることを特徴とする半導体装置の製造方法。
［１２］
基板と、その表面を覆う平坦化膜と、前記表示素子用基板の上部に設けられた表示素子とを備える表示装置の製造方法であって、
前記基板上に樹脂組成物を塗布、乾燥して樹脂層を形成する工程と、
該樹脂層の所望の部分に活性エネルギー線を照射する工程と、
活性エネルギー線照射後の該樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記平坦化膜を形成する工程と、
を含み、
前記樹脂組成物が［１］〜［７］のいずれかに記載の樹脂組成物であることを特徴とする表示装置の製造方法。 Such an object is achieved by the present invention described in the following [1] to [12].
[1]
(A) an alkali-soluble resin,
(B) a photosensitive agent,
(C) A positive photosensitive resin composition containing titanium black.
[2]
The photosensitive resin composition according to [1], wherein the particle size of titanium black (C) is 30 to 200 nm.
[3]
The photosensitive resin composition in any one of [1] and [2] whose addition amount of titanium black (C) is 1-70 weight part with respect to 100 weight part of alkali-soluble resin (A).
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the alkali-soluble resin (A) is a polyamide resin.
[5]
The photosensitive resin composition according to [4], wherein the polyamide resin comprises a structure selected from the group consisting of a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure.

[6]
The photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

(X and Y are organic groups. A and b are mole percentages, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. R1 is a hydroxyl group or —O—R _3. R ₂ is a hydroxyl group, a carboxyl group, —O—R ₃ , or —COO—R ₃ , and may be the same or different, and m is a positive number from 0 to 2. , N is a positive number from 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, where when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when there is no carboxyl group as R ₂ , at least one R ₁ must be a hydroxyl group, Z is —R ₄ —Si (R ₆ ) (R ₇ ) —O—Si (R ₆ ) (R ₇ ) —R ₅ —, wherein R ₄ and R ₅ are divalent organic groups, and R ₆ and R ₇ are monovalent. Organic group.)
[7]
The photosensitive resin composition in any one of [1]-[6] in which a photosensitive agent (B) comprises a quinonediazide compound or a dihydropyridine compound.
[8]
A step of applying the resin composition according to any one of [1] to [7] on a substrate to form a resin layer, a step of irradiating a desired portion of the resin layer with active energy rays, and an activity And a step of bringing a developer into contact with the resin layer after irradiation with energy rays and then heating the resin layer.
[9]
A semiconductor substrate, a semiconductor element provided on the semiconductor substrate, and an insulating film provided on the semiconductor element;
The semiconductor device, wherein the insulating film is a film formed by applying and drying the resin composition according to any one of [1] to [7].
[10]
A display element substrate, an insulating film covering the surface, and a display element provided on the display element substrate;
The display device, wherein the insulating film is a film formed by applying and drying the resin composition according to any one of [1] to [7].
[11]
A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a resin composition on the semiconductor chip and drying to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
Forming a protective film by bringing a developer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer;
Including
The method of manufacturing a semiconductor device, wherein the resin composition is the resin composition according to any one of [1] to [7].
[12]
A manufacturing method of a display device comprising a substrate, a planarization film covering the surface thereof, and a display element provided on the display element substrate,
Applying a resin composition on the substrate and drying to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
A step of bringing the developer layer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
Including
A method for producing a display device, wherein the resin composition is the resin composition according to any one of [1] to [7].

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

  The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and titanium black (C). Hereinafter, each component of the positive photosensitive resin composition of the present invention will be described in detail. The following is an example, and the present invention is not limited to the following.

The alkali-soluble resin (A) 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.
As alkali-soluble resin (A) used by this invention, what is represented by General formula (1) is preferable.

For example, X of the polyamide resin having a structure represented by the general formula (1) of the present invention is preferably represented by the following structure.

_{（式中Aは、−CH2}−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−、又は単結合である。R₈はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。また、R₉は水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを表す。）

_{(In the formula, A represents} —CH ₂ —, —C (CH ₃ ) ₂ — _{, —O—, —S—} , —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or R ₈ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2. ₉ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.)

  Among these, particularly preferred are those represented by the following formula. These may be used alone or in combination of two or more.

_（Ｒ10はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。）

_(R10 represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2.)

Moreover, as Y of General formula (1), what is represented by a following formula is mentioned, for example.

_{(式中A：−CH2}−、−C(CH₃)₂−、−O−、−S−、−SO₂−、−CO−、−NHCO−、−C(CF₃)₂−、又は単結合である。R₁₁はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。）

_{(Wherein A: -CH2 -, - C (} CH 3) 2 -, - O -, - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 -, or a single R ₁₁ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2.)

  Among these, particularly preferred are those represented by the following formula. These may be used alone or in combination of two or more.

_（Ｒ12はアルキル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なってもよい。ｒ＝０〜２の整数である。）

_(R12 represents one selected from an alkyl group and a halogen atom, and each may be the same or different. R is an integer of 0 to 2.)

  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 a compound selected from acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative and the like. After synthesizing a polyamide resin containing a structure, an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group as the terminal amino group contained in the polyamide resin is used. And capping as an amide. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include those represented by the following formulae: It is done.

  Among these, particularly preferred are those selected from the following formulae. These may be used alone or in combination of two or more.

  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

  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, and the use ratio c is 40 mol at the maximum. 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.

  As the photosensitizer (B) used in the present invention, a photosensitizer 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.

（式中Ｑは、水素原子、式（２）、式（３）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（２）、式（３）である。）

(In the formula, Q is selected from a hydrogen atom, formula (2), and formula (3). Here, at least one of Q of each compound is represented by formula (2) or formula (3). .)

  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. For example, the following may be mentioned. These may be used alone or in combination of two or more.

（式中Ｑは、水素原子、式（２）、式（３）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（２）、式（３）である。）

(In the formula, Q is selected from a hydrogen atom, formula (2), and formula (3). Here, at least one of Q of each compound is represented by formula (2) or formula (3). .)

  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.

  The amount of the photosensitizer (B) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 10-30 weight part. If it is less than 1 part by weight, the patterning property of the polyamide resin becomes poor, and if it exceeds 50 parts by weight, the sensitivity is greatly lowered, which is not preferable.

The titanium black (C) that can be used in the present invention can be added to the photosensitive resin composition and can exhibit the desired light-shielding property. Titanium black means low-order titanium oxide or titanium oxynitride represented by Ti _n O _2n-1 (n is an integer of 1 or more) obtained by oxidation of titanium or reduction of titanium dioxide. In addition, the surface of the titanium black particles may be treated with an insulating material or the like to further improve the electrical characteristics. The average particle size of titanium black is preferably 30 nm to 200 nm, more preferably 40 nm to 120 nm, from the viewpoint of light shielding properties and patterning properties. If the particle size is 30 nm or less, aggregation tends to occur, and if it is 200 nm or more, a residue is easily generated during patterning, which is not preferable. Moreover, the usage-amount of titanium black becomes like this. Preferably it is 1-70 weight part with respect to 100 weight part of alkali-soluble resin (A). More preferably, it is 10-35 weight part. If the amount is 1 part by weight or less, the light shielding property is insufficient, and if it is 70 parts by weight or more, patterning is not preferable.

  In the present invention, the alkali-soluble resin (A), the photosensitive agent (B), and the titanium black (C) are dissolved or dispersed in a solvent and used in a varnish form. 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, it is preferable to use a bead mill, an annular bead mill, a beadless disperser, etc. in order to enhance dispersibility, in addition to a general mixer, disperser, and three roll.

  In the method of using the photosensitive resin composition of the present invention, first, the composition is used as a suitable support, for example, a semiconductor substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, soda glass, Pyrex (registered trademark) glass, It apply | coats to substrates for display elements, such as an alkali free 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 property of the photosensitive agent, the entire surface may be exposed before being cured, and then curing may be performed.

  The developing mechanism of this photosensitive resin composition is as follows. In the unexposed area, the diazoquinone compound is hardly soluble in an alkaline aqueous solution due to the effect of inhibiting dissolution in a resin such as polybenzoxazole resin or polyimide resin. In one 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.

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

<< No. 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]
Three rolls were used for 10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, 3 g of titanium black (C-1) having an average particle diameter of 60 nm and 40 g of γ-butyrolactone. The mixture was dispersed and filtered through a 2 μm fluororesin filter to obtain a translucent photosensitive resin composition.

[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. 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%. When the light shielding property is 25% or less, good concealing property can be obtained.

[Electrical characteristics evaluation]
This photosensitive resin composition was applied on an aluminum plate using a spin coater, and then prebaked on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 13 μm. Then, after heating at 300 degreeC / 30 minutes in oven, the film of about 10 micrometers was obtained after hardening. A stainless steel electrode was pressure-bonded to the prepared sample, charged at a prescribed applied voltage for 1 minute, and measured for volume resistivity. As a result, the electrical characteristics were as good as 5 × 10 ¹⁶ Ω · cm.

<< No. 2 >>
No. 1 was used instead of 3 g of titanium black (C-1) having an average particle size of 60 nm used in No. 1, and 3 g of titanium black (C-2) having an average particle size of 50 nm was used. Evaluation was performed in the same manner as in 1.

<< No. 3 >>
No. 1 was used in place of 3 g of titanium black (C-1) having an average particle size of 60 nm and 3 g of titanium black (C-3) having an average particle size of 100 nm. Evaluation was performed in the same manner as in 1.

<< No. 4 >>
No. 2,6-dimethyl-3,5-dicarboxymethyl-4- (2′-nitrophenyl) -1,4-dihydropyridine (abbreviated as DHPM) instead of 2 g of the photosensitive diazoquinone (B-1) used in 1 B-2) 3.0 g is used, and otherwise, No. Evaluation was performed in the same manner as in 1.

<< No. 5 >>
[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. Others are No. 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 synthesized polyamide resin (A-2), 1.5 g of photosensitive diazoquinone (B-3) having the following structure, and 3 g of titanium black (C-1) are mixed and dispersed in 40 g of γ-butyrolactone using three rolls. Then, the mixture was filtered through a 1 μm fluororesin filter to obtain a photosensitive resin composition. Evaluation of developability and transmittance is No. 1 was carried out.

(式中Q_１、Q_２、Q₃の７５％は式（４）で表される官能基、２５％は水素原子である。）

(In the formula, 75% of Q ₁ , Q ₂ and Q ₃ are functional groups represented by formula (4), and 25% are hydrogen atoms.)

(式中Q_１、Q_２、Q₃、Ｑ_４の８７．５％は式（４）で表される官能基、１２．５％は水素原子である。)

(In the formula, 87.5% of Q ₁ , Q ₂ , Q ₃ and Q ₄ is a functional group represented by the formula (4), and 12.5% is a hydrogen atom.)

<< No. 6 >>
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, no. The positive photosensitive resin composition obtained in 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 for exposure, and then 1 hour at 230 ° C. in air using a hot air circulation dryer. Heat curing 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- 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.

<< No. 7 >>
No. 1 g of titanium black (C-1) having an average particle diameter of 60 nm used in No. 1 was used. Evaluation was performed in the same manner as in 1.

<< No. 8 >>
No. No. 1 was used, and 5 g of titanium black (C-1) having an average particle diameter of 60 nm used in No. 1 was used. Evaluation was performed in the same manner as in 1.

<< No. 10 >>
No. No. 1 was used without using titanium black (C-1) having an average particle diameter of 18 nm used in No. 1. When the evaluation was conducted in the same manner as in No. 1, it was confirmed that the 10 μm pattern had no scum and the pattern was well opened, but the light shielding property was lowered.

<< No. 11 >>
No. 1 was used in place of 3 g of titanium black (C-1) having an average particle size of 60 nm used in No. 1, and 3 g of carbon black having an average particle size of 50 nm was used. When the evaluation was performed in the same manner as in No. 1, it was confirmed that the 10 μm pattern had no scum and the pattern was well opened, but the electrical characteristics were deteriorated.

In Table 1, no. 1-8 are examples, no. 9 to 10 are comparative examples.

  The present invention provides a photosensitive resin composition having excellent light shielding properties and capable of patterning without scum, and a semiconductor device and a display element using the same.

Claims (12)

(A) an alkali-soluble resin,
(B) a photosensitive agent,
(C) A positive photosensitive resin composition containing titanium black.   The photosensitive resin composition according to claim 1, wherein the particle size of titanium black (C) is 30 to 200 nm.   The photosensitive resin composition according to claim 1 or 2, wherein the addition amount of titanium black (C) is 1 to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A).   The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide resin. The photosensitive resin composition according to claim 4, wherein the polyamide resin comprises a structure selected from the group consisting of a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure.
The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

(X and Y are organic groups. A and b are mole percentages, a + b = 100, a is 60 or more and 100 or less, and b is 0 or more and 40 or less. R1 is a hydroxyl group or —O—R _3. R ₂ is a hydroxyl group, a carboxyl group, —O—R ₃ , or —COO—R ₃ , and may be the same or different, and m is a positive number from 0 to 2. , N is a positive number from 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, where when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. In addition, when there is no carboxyl group as R ₂ , at least one R ₁ must be a hydroxyl group, Z is —R ₄ —Si (R ₆ ) (R ₇ ) —O—Si (R ₆ ) (R ₇ ) —R ₅ —, wherein R ₄ and R ₅ are divalent organic groups, and R ₆ and R ₇ are monovalent. Organic group.)   The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) comprises a quinonediazide compound or a dihydropyridine compound.   The process of apply | coating the resin composition in any one of Claims 1-7 on a base material, forming a resin layer, the process of irradiating an active energy ray to the desired part of this resin layer, and an active energy ray A step of bringing a developer into contact with the resin layer after irradiation and then heating the resin layer. A semiconductor substrate, a semiconductor element provided on the semiconductor substrate, and an insulating film provided on the semiconductor element;
The semiconductor device according to claim 1, wherein the insulating film is a film formed by applying and drying the resin composition according to claim 1. A display element substrate, an insulating film covering the surface, and a display element provided on the display element substrate;
The display device according to claim 1, wherein the insulating film is a film formed by applying and drying the resin composition according to claim 1. A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a resin composition on the semiconductor chip and drying to form a resin layer;
Irradiating active energy rays to a desired portion of the resin layer;
Forming a protective film by bringing a developer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer;
Including
A method for manufacturing a semiconductor device, wherein the resin composition is the resin composition according to claim 1. A manufacturing method of a display device comprising a substrate, a planarization film covering the surface thereof, and a display element provided on the display element substrate,
Applying a resin composition on the substrate and drying to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
A step of bringing the developer layer into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
Including
A method for manufacturing a display device, wherein the resin composition is the resin composition according to claim 1.