JP4507850B2 - Positive photosensitive resin composition, pattern formation method using the same, semiconductor device manufacturing method, and display device manufacturing method - Google Patents

Description

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

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical and mechanical properties have been used for surface protective films and interlayer insulating films of semiconductor elements.
Here, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound of a photosensitive material is combined with these resins is also used (Patent Document 1). ).
However, this positive photosensitive resin composition has the following problems.
When such a positive photosensitive resin composition is used, the sensitivity of the positive photosensitive resin composition is particularly important. If the sensitivity is low, the exposure time becomes long and the throughput decreases. Therefore, in an attempt to improve the sensitivity of the positive photosensitive resin composition, for example, if the molecular weight of the base resin is decreased, the film thickness of the unexposed area is increased during development, so that the required film thickness cannot be obtained. There arises a problem that the pattern shape collapses. Conversely, if the diazoquinone compound, which is a photosensitive material, is increased in order to increase the dissolution inhibition of the unexposed area, a development residue called scum may occur at the bottom of the pattern after development.
As described above, in the positive photosensitive resin composition, it was difficult to reduce scum while maintaining good sensitivity.
JP-A-1-46862

The prior art described in the above literature has room for improvement in the following points.
First, as a result of insufficient sensitivity, there has been a problem that the exposure time becomes longer and the throughput is lowered.
Secondly, there is a problem that a development residue called scum occurs at the bottom of the pattern after development.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a positive photosensitive resin composition having good sensitivity. Another object of the present invention is to reduce undeveloped residue called scum.

According to the present invention,
(A) an alkali-soluble resin,
(B) a diazoquinone compound,
(C) γ-butyrolactone and
(D) Compounds having a dipole moment of 3.5 debye or more (excluding γ-butyrolactone)
Only contains the component (A) is, polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a resin containing a polyimide precursor structure or a polyamide acid ester structure, component (D) is dimethyl sulfoxide or N , N-dimethylacetamide, and the content of component (C) is 40% by weight or more and 95% by weight or less of the total amount of component (C) and component (D) Things are provided.
Since the positive photosensitive resin composition of the present invention uses the specific component (D), it is possible to suppress the occurrence of scum while maintaining good sensitivity during development.

According to the present invention,
Applying the positive photosensitive resin composition according to any of the above to a substrate to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
A step of bringing a developer into contact with the resin layer after irradiation with active energy rays, and then heating the resin layer;
A pattern forming method is provided.

Also according to the invention,
A semiconductor substrate, a semiconductor element provided on the semiconductor substrate, and an insulating film provided on the semiconductor element;
A semiconductor device is provided in which the insulating film is a film formed by applying and drying the positive photosensitive resin composition described above.

Also according to the invention,
A display element substrate, an insulating film covering the surface, and a display element provided on the display element substrate;
The display device is characterized in that the insulating film is a film formed by applying and drying the positive photosensitive resin composition as described above.

Also according to the invention,
A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a positive photosensitive resin composition on the semiconductor chip to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
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;
And a method of manufacturing a semiconductor device, wherein the positive photosensitive resin composition is the positive photosensitive resin composition.

Also according to the invention,
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 positive photosensitive 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
There is provided a method for producing a display device, wherein the positive photosensitive resin composition is the positive photosensitive resin composition.

  By using the positive photosensitive resin composition of the present invention, a high-sensitivity positive photosensitive resin composition is provided, so that the processing time during exposure is reduced and an improvement in throughput is achieved. Further, by using the positive photosensitive resin composition of the present invention, generation of scum is suppressed, and a highly reliable semiconductor device and display device are manufactured.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which can suppress generation | occurrence | production of the scum at the time of patterning, maintaining a high sensitivity, and a semiconductor device and a display apparatus using the same can be obtained.

The present invention includes an alkali-soluble resin (A), a diazoquinone compound (B), γ-butyrolactone (C), and a compound having a dipole moment of 3.5 debye or more (excluding γ-butyrolactone) (D). The present invention relates to a characteristic positive photosensitive resin composition.
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 containing a polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a polyimide precursor structure or a polyamic acid ester structure, and has a main chain or a side chain. It is a resin having a hydroxyl group, a carboxyl group, or a sulfonic acid group. Specific examples include a cresol type novolac resin, polyhydroxystyrene, and a polyamide resin including a structure represented by the general formula (1). The structure represented by the general formula (1) from the viewpoint of heat resistance after the final heating. Polyamide resin containing is preferable.

（Ｘは２〜４価の有機基、Ｙは２〜６価の有機基である。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の整数、ｎは０〜４の整数である。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。）

(X is a divalent to tetravalent organic group, Y is a divalent to hexavalent organic group, a and b are mole percent, a + b = 100, a is 60 to 100, and b is 0 to 40. R ₁ is a hydroxyl group or —O—R _3, which may be the same or different, R ₂ is any one of a hydroxyl group, a carboxyl group, —O—R ₃ , —COO—R ₃ , and the same However, m is an integer of 0 to 2, n is an integer of 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, where R ₁ has no hydroxyl group. ₂ must be at least one carboxyl group, and if R ₂ has no carboxyl group, R ₁ must be at least one hydroxyl group, Z is —R ₄ —Si (R ₆ ) (R _{7) -O-Si (R 6} ) (R 7) -R 5 - is represented by, R _4, R ₅ is a divalent organic A group, R _6, R ₇ is a monovalent organic group.)

  The polyamide resin containing the structure represented by the general formula (1) is, for example, a compound selected from diamine containing X or bis (aminophenol), 2,4-diaminophenol, and the like, tetracarboxylic acid anhydride containing Y, It is obtained by reacting with a compound selected from 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 the _-O-R 3, Y as a substituent of X is a hydroxyl group, a carboxyl group for the purpose of adjusting the solubility in an alkali aqueous solution, a protected group R ₃ is an organic group having 1 to 15 carbon atoms, a hydroxyl group if necessary, may be protected carboxyl group. Examples of R ₃ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

  When this polyamide resin is heated at about 250 to 400 ° C., it is dehydrated and closed, and a heat-resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.

Examples of X in the general formula (1) include those represented by the following formula.

（式中Aは、−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO ₂−、−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 —, 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. R 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.

  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−、−SO ₂−、−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: -CH 2 -, - C} (CH 3) 2 -, - O -, - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 -, or R ₁₁ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, which 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.

（R_１２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。）

(R ₁₂ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R = 0 is an integer of 0 to 2.)

In the general formula (1), b, which is a mole percent of repeating units including Z and Y, may be zero. However, the presence of the repeating unit (b is not zero) has an advantage that the resin properties are improved.

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 end-capping functional group include those represented by the following formula.

  Among these, a functional group represented by the following formula is particularly preferable. 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 a cyclic compound group having at least one alkenyl group or alkynyl group. You can also

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 US Pat. Nos. 2,722,975, 2,797,213 and 3,669,658. It is.
For example, the compound represented by the following formula is 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. Specific examples thereof include the following formula. 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).

  A preferred addition amount of the diazoquinone compound (B) used in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the resin (A). 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.

  In the present invention, γ-butyrolactone (C) is used as a solvent. γ-butyrolactone is a good solvent for alkali-soluble resin and photosensitive diazoquinone, and in the present invention, γ-butyrolactone is 40 wt% or more and 95 wt% of the total amount of component (C) and component (D). Is preferred.

Component (D) used in the present invention is a compound having a dipole moment of 3.5 debye or more. By using this component, high sensitivity as a positive photosensitive resin composition can be achieved.
As the compound (D) having a dipole moment of 3.5 debyes or more, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, ε-caprolactam, acetonitrile, acrylonitrile , Benzonitrile, butanenitrile, crotonaldehyde, ethylene carbonate, formamide, isobutylnitrile, methacrylonitrile, N-methylacetamide, 4-methylbutanenitrile, N-methylformamide, pentanenitrile, pentaneacetonitrile, propanenitrile, propiononitrile, 2-Pyrrolidinone, 1,3-dimethyl-2-imidazole can be used.
Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and dimethylacetamide are preferable.
As described above, the solvent is shown as a specific example of the component (D). However, in the present invention, the component (D) is not limited to the organic solvent, and may be a liquid organic compound other than the organic solvent, or a solid compound.
The compound (D) having a dipole moment of 3.5 debye or more used in the present invention may be used alone or in combination of two or more.

  The resin composition according to the present invention may contain components other than the components (A) to (D) described above. For example, in the present invention, a compound having a phenolic hydroxyl group may be used in combination in order to further increase sensitivity during development. As for the compounding quantity of the compound which has a phenolic hydroxyl group, 1-30 weight part is preferable with respect to 100 weight part of alkali-soluble resin (A). As a compound which has a phenolic hydroxyl group, the compound of a following formula can be mentioned, for example.

Among these, preferred examples are compounds represented by the following formulae.

In the method of using the positive photosensitive resin composition of the present invention, first, the 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 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. 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 an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

  The development mechanism of this positive photosensitive resin composition is hardly soluble in an alkaline aqueous solution in the unexposed area due to the effect of inhibiting 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.

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

  Examples of semiconductor device applications include a passivation film obtained by forming the above-described positive photosensitive resin composition film on a semiconductor element, and a positive 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 positive photosensitive resin composition film on a circuit formed on a semiconductor element.

  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 barriers for organic EL elements. The usage method is based on forming the positive type photosensitive resin composition layer patterned on the substrate on which the display element and the color filter are formed in accordance with the above-described method. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but by introducing a post-exposure process before curing this positive photosensitive resin composition layer, transparency It is also possible to obtain a resin layer that is excellent in practical use, which is more preferable in practical use.

[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.

（式中、ｎは１５〜２０である。）

(In the formula, n is 15 to 20.)

[Preparation of resin composition]
After dissolving in 10 g of the synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, and 20 g of a mixed solution of γ-butyrolactone / dimethylsulfoxide = 40/60 (weight ratio), 0. The mixture was filtered through a 2 μm fluororesin filter to obtain a positive photosensitive resin composition. No. Set to 1.

（式中、Ｑ１、Ｑ２、Ｑ３の７５％は式（４）であり、２５％は水素原子である。）

(In the formula, 75% of Q1, Q2 and Q3 are the formula (4), and 25% are hydrogen atoms.)

[Developability evaluation]
This positive photosensitive resin composition was applied to an 8-inch silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 10 μm. Through the resulting coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern having a width of 0.88 to 50 μm are drawn), and Nikon's i-line stepper NSR- Using 4425i, the exposure amount was increased in steps of 100 mJ / cm ² to 10 mJ / cm ² to perform exposure. 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 pattern was satisfactorily opened with no scum at an exposure amount of 280 mJ / cm ² .

  No. except that the solvent was changed. No. 1 as in No. 1. 2-9 resin compositions were obtained. The composition of the solvent is shown in Table 1. These resin compositions are also No. Evaluation was performed in the same manner as in 1.

[Example 2]
[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 together with 70 g of N-methyl-2-pyrrolidone are added 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).

（式中、ｎとｍのモル比はおよそ１：１である。）

(In the formula, the molar ratio of n to m is approximately 1: 1.)

[Production of resin composition, evaluation of developability]
After dissolving in 10 g of the synthesized polyamide resin (A-2), 2 g of photosensitive diazoquinone (B-2) having the following structure, and 20 g of a mixed solution of γ-butyrolactone / dimethylsulfoxide = 40/60, 0.2 μm fluororesin The mixture was filtered with a filter made to obtain a positive photosensitive resin composition. No. 10 is assumed. This positive photosensitive resin composition was designated as No. 1 Evaluation was performed in the same manner as in 1. The range of film thickness after coating was 0.08 μm. When exposure and development were performed, it was confirmed that the pattern was satisfactorily opened without scum at an exposure amount of 290 mJ / cm ² .

（式中、Ｑ１、Ｑ２、Ｑ３の８７．５％は式（４）であり、１２．５％は水素原子である。）

(In the formula, 87.5% of Q1, Q2, and Q3 is the formula (4), and 12.5% is a hydrogen atom.)

[Comparative example]
Using the polyamide resin (A-1), the solvents listed in Table 1 were used. As in the case of resin composition No. 11-14 were produced and evaluated.
Table 1 shows the results of the examples and comparative examples described above.

In Table 1, no. Nos. 1-10 are No. Compared to 11-14, good results were obtained in terms of sensitivity and scum.
In the table, GBL represents γ-butyrolactone, DMSO represents dimethyl sulfoxide, NMP represents N-methyl-2-pyrrolidone, DMAc represents N, N-dimethylacetamide, MADE represents diethyl maleate, and BA represents butyl butyrate.
The numerical value in parentheses in the column of γ-butyrolactone (C) and the compound (D) having a dipole moment of 3.5 debye or more represents the dipole moment. Dipole moment was based on Solvent Handbook (Kodansha) and LANGE'S HANDBOOK OF CHEMICTRY (McGRW-HILL BOOK COMPANY). For the solvent whose value was unknown, WinMOPAC3.0 was used to calculate the optimum structure, and the value at this time was used.

[Example 3]
One example of application of the positive photosensitive resin composition of the present invention to a semiconductor device will be described with reference to the drawings for application to a semiconductor device having bumps. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, an input / output Al pad 2 is provided on a silicon substrate 1 having semiconductor elements and wirings provided on its surface, and a passivation film 3 is further formed thereon, and the passivation film 3 A via hole is formed in the hole. On this, the positive photosensitive composition according to the present invention is applied and dried to form a positive photosensitive resin (buffer coating film) 4. Further, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and the metal film 5 etches the periphery of the solder bump 9 to insulate between the pads. A barrier metal 8 and a solder bump 9 are formed on the insulated pad.
The semiconductor device obtained as described above has a good yield and high reliability.

[Example 4]
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 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 device. When this display device was treated at 80 ° C. for 200 hours and then voltage was applied to both electrodes to drive sequentially, the display device emitted light well.
The apparatus according to the present embodiment has a good yield and high reliability.

  INDUSTRIAL APPLICABILITY The present invention provides a positive photosensitive resin composition that can be patterned without scum while maintaining high sensitivity, and can be suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, or an insulating film of a display device. it can.

It is sectional drawing of the pad part of the semiconductor device which shows the Example of this invention.

Explanation of symbols

1 Silicon substrate 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 (5)

(A) an alkali-soluble resin,
(B) a diazoquinone compound,
(C) γ-butyrolactone and
(D) Compounds having a dipole moment of 3.5 debye or more (excluding γ-butyrolactone)
Only contains the component (A) is, polybenzoxazole structure, a polybenzoxazole precursor structure, a polyimide structure, a resin containing a polyimide precursor structure or a polyamide acid ester structure, component (D) is dimethyl sulfoxide or N , N-dimethylacetamide, and the content of component (C) is 40% by weight or more and 95% by weight or less of the total amount of component (C) and component (D) object. The positive photosensitive resin composition according to claim 1 , wherein the component (A) is a resin represented by the following general formula (1).

(X is a divalent to tetravalent organic group, Y is a divalent to hexavalent organic group, a and b are mole percent, a + b = 100, a is 60 to 100, and b is 0 to 40. or less is .R ₁ is a hydroxyl group or _{-O-R 3,} it may be the same or different .R ₂ is a hydroxyl group, a carboxyl _group, -O-R 3, are either _{-COO-R 3,} the same However, m is an integer of 0 to 2, n is an integer of 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, where R ₁ has no hydroxyl group. ₂ must be at least one carboxyl group, and if R ₂ has no carboxyl group, R ₁ must be at least one hydroxyl group, Z is —R ₄ —Si (R ₆ ) (R ₇ ) —O—Si (R ₆ ) (R ₇ ) —R ₅ —, R ₄ , R ₅ is a divalent organic group, and R ₆ and R ₇ are monovalent organic groups.) Applying the positive photosensitive resin composition according to claim 1 or 2 onto a substrate to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
A step of bringing a developer into contact with the resin layer after irradiation with active energy rays, and then heating the resin layer;
A pattern forming method comprising: A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a positive photosensitive resin composition on the semiconductor chip and drying to form a resin layer;
Irradiating a desired portion of the resin layer with active energy rays;
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 positive photosensitive resin composition is a positive photosensitive resin composition according to claim 1 or 2. 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 positive photosensitive 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
Method for manufacturing a display device, wherein the positive photosensitive resin composition is a positive photosensitive resin composition according to claim 1 or 2.

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