JP3319000B2 - Actinic radiation sensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an actinic radiation-sensitive composition, and more particularly to an improvement in a photosensitive polyimide composition.

[0002]

2. Description of the Related Art As a photosensitive polyimide composition, a polyamic acid which can be dimerized or polymerized by actinic radiation is used.
A composition to which a compound containing a carbon double bond and an amino group or a quaternary salt thereof is added (for example, JP-B-59-5282).
No. 2) or a polyimide precursor composition in which photosensitivity is introduced into a polyamic acid by an ester group (for example, US Pat.
No. 12 and US Pat. No. 4,408,831) are known.

However, such a conventional composition has a negative-type behavior in which an exposed portion remains after development. In the case where such a negative photosensitive polyimide composition is used, if dust or the like adheres to a mask or the like used at the time of exposure, the portion becomes a defect and a pinhole or the like is formed. There is a problem that this defective portion causes insulation failure, and a positive photosensitive polyimide composition in which the exposed portion is dissolved by development has been demanded.

[0004] Conventionally, a positive photosensitive polyimide is obtained by adding a naphthoquinonediazide compound having a specific structure to a polyamic acid having a specific structure and performing a baking treatment in a specific temperature range after exposure. Are known (for example, Proceedings of the Society of Polymer Science, Vol. 40, No. 3, 82
1 (1991)).

However, in the above-mentioned method, only a polyamic acid having a specific structure can be made only a positive type, which is not practical.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive polyimide composition having high practicality.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Polymer (A) having structural unit represented by general formula [1]
This is achieved by an actinic radiation-sensitive composition characterized by containing:

[0008]

Embedded image (Q represents at least one group in the polymer (A) representing a naphthoquinonediazidosulfonylamide group, and the other group represents a hydroxyl group or a monovalent organic group. R ¹ is a trivalent group having at least two carbon atoms or A tetravalent organic group, R ² represents a divalent organic group having at least two carbon atoms.
n is 1 or 2. ) Polymer (A) in the present invention
Is a compound that generates a carboxyl group by light.
That is, the present invention utilizes the feature that the portion of the general formula [1] is solubilized in an alkaline solution to generate a carboxyl group by light irradiation.

[0009] In the general formula [1], Q represents at least one naphthoquinonediazidosulfonylamide group in the polymer (A), and the other group represents a hydroxyl group or a monovalent organic group. The naphthoquinonediazidosulfonylamide group is a group that generates an acid by light, and the position of the diazide is preferably 1,2-, and the position of 2,1- is not preferable because of low sensitivity. The position of the sulfonylamide group is preferably the 4- or 5-position. Therefore, a 1,2-naphthoquinonediazide-4-sulfonylamido group and a 1,2-naphthoquinonediazido-5-sulfonylamido group are preferred. Examples of the other monovalent organic group include an alkoxy group having 1 to 6 carbon atoms, a halogenated alkoxy group, a phenoxy group, a substituted phenoxy group, and the like. Specifically, a methoxy group, an ethoxy group,
Examples include, but are not limited to, a propoxy group, a phenoxy group, a halogen-valent phenoxy group, and a halogenated methoxy group.

In the general formula [1], R ¹ represents a trivalent or tetravalent organic group having at least two carbon atoms. R
Preferred specific examples of ¹ include a pyromellitic acid residue,
Benzophenonetetracarboxylic acid residue, biphenyltetracarboxylic acid residue, diphenylethertetracarboxylic acid residue, diphenylsulfonetetracarboxylic acid residue,
(Hexafluoroisopropylidene) bis (phenyldicarboxylic acid) residue and the like, but are not limited thereto.

In the polymer (A) of the present invention, R ¹ may be composed of one of these, or may be a copolymer composed of two or more.

In the general formula [1], R ² represents a divalent organic group having at least two carbon atoms. Preferred examples of R ² include an ethylenediamine residue, a hexamethylenediamine residue, a cyclohexyldiamine residue, a phenylenediamine residue, a diaminodiphenylether residue, a diaminodiphenylmethane residue, a diaminodiphenylsulfone residue, and a diaminodiphenylsulfide residue. ,
Bis (aminophenoxy) benzene residues, bis (aminophenoxy) diphenyl propane residue, bis (aminophenoxy) diphenyl sulfone residue, bis (aminopropyl) but such disiloxane residues include, but are not limited to.

In the polymer (A) of the present invention, R ² may be composed of one of these, or may be a copolymer composed of two or more.

Further, n is 1 or 2.

The polymer (A) may be composed of only the structural unit represented by the general formula [1] or may be a copolymer with another structural unit. It is desirable to select the type and amount of the structural unit used for copolymerization within a range that does not significantly impair the heat resistance of the polymer (A) obtained by the final heat treatment.

Specific examples of the polymer (A) include pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. 4'-diaminodiphenyl ether, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether,
Pyromellitic dianhydride and 3,3 '(or 4,4')
-Diaminodiphenyl sulfone, pyromellitic dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3' (or 4,4 ')-diaminodiphenyl sulfone, 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride and 3,3 '(or 4,4')-diaminodiphenyl sulfone, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride and 3,
3 '(or 4,4')-diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4, 4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride Thing and paraphenylenediamine,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride and paraphenylenediamine , Pyromellitic dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine,
3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 4,4'-diamino diphenyl ether, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and paraphenylenediamine, butane tetra Carboxylic acid dianhydride and 1,3-bis (3-aminophenoxy) benzene, cyclopentanetetracarboxylic dianhydride and 4,4'-diaminodiphenylmethane, pyromellitic dianhydride and 4,4'-diaminodiphenyl ether And 1,2 of polyamic acid synthesized from bis (3-aminopropyl) tetramethyldisiloxane and the like.
Amide-substituted compounds such as -naphthoquinonediazide-5-sulfonylamino compound and 1,2-naphthoquinonediazide-4-sulfonylamino compound are preferably used.

It is also possible to blend one or more kinds of polyamic acid or ester type polyimide precursor polymers with the polymer (A). A preferable blend ratio is 1 to 80% by weight based on the polymer (A).
It is.

Specific examples of the polyamic acid polymer include "Pyralin" manufactured by DuPont, "Semicofine" manufactured by Toray Industries, Inc., "PIQ" and "PI" manufactured by Hitachi Chemical Co., Ltd.
X "and" CRC series "manufactured by Sumitomo Bakelite Co., Ltd. Specific examples of the ester type polyimide precursor include" Pyralin "manufactured by DuPont.

A sensitizer can be added to the actinic radiation-sensitive composition of the present invention, if necessary. Sensitizers suitable for the present invention include N-phenyldiethanolamine and N-phenyldiethanolamine.
-Aromatic amines such as phenylglycine and Michler's ketone; aromatic monoazides such as azido anthraquinone and azidobenzal acetophenone; 3,3'-carbonylbis (diethylamino coumarin); Those used as charge transfer agents for electrophotography can be preferably used. The sensitizer is preferably added in the range of 0.1 to 5% by weight based on the whole polymer. If the ratio is outside this range, the photosensitivity is reduced and the mechanical properties of the polymer are reduced. These sensitizers can be used alone or in combination of two or more.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion aid include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organosilicon compounds such as methacryloxypropyltrimethoxysilane; aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate; aluminum tris (acetylacetonate); and titanium bis (acetylacenate)
Titanium chelate compounds and the like are preferably used.

As other additives, an adhesion improving agent to the substrate may be contained in a range where the sensitivity and heat resistance are not significantly reduced.

An example of the method for producing the composition of the present invention will be described.

First, tetracarboxylic acid or a dianhydride thereof is mixed with ammonium carbonate or urea, and the mixture is allowed to react at 100 to 300 ° C. for 30 minutes to 10 hours as a solid or by adding a solvent. Thereby, a diimide compound can be obtained. Next, the obtained diimide compound is reacted with a naphthoquinonediazide halogenated sulfone compound in a solvent, and a polymer is obtained by reacting a diamine compound, and if necessary, a tetracarboxylic dianhydride and a tetracarboxylic acid chloride. (A) can be obtained.

As the solvent used in the above production method, a polar solvent is preferably used in view of the solubility of the polymer, and an aprotic polar solvent is particularly preferable. Examples of aprotic polar solvents include N-methyl-2-pyrrolidone, N, N
-Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorotriamide, γ-butyrolactone and the like are preferably used. In addition, ether solvents such as tetrahydrofuran and dioxane, and phenol solvents such as phenol and cresol can also be preferably used.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Examples of the material of the support include metal, glass, semiconductor, metal oxide insulator, silicon nitride, and the like.

As the coating method, means such as spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating and the like are possible. The coating film thickness can be adjusted by the coating means, the solid content concentration of the composition, the viscosity and the like.
m.

Next, the composition of the present invention formed into a coating film on the support is irradiated with actinic radiation in a desired pattern. Examples of the actinic radiation include X-rays, electron beams, ultraviolet rays, visible light, and the like.
That is, those having a wavelength range of 200 to 500 nm are preferable.

Next, a relief pattern is obtained by dissolving and removing the light-exposed portion with a developing solution. An appropriate developer can be selected according to the structure of the polymer, but an aqueous solution of an alkali such as ammonia, triethanolamine, methylamine, sodium hydroxide, potassium carbonate, or tetramethylammonium hydroxide is preferable. Particularly, an aqueous solution of an organic alkali such as ammonia or triethanolamine is preferable because there is no possibility of mixing of metal components. Further, a mixture of a solvent of the composition and a non-solvent such as an alcohol, a hydrocarbon, or an aromatic hydrocarbon can also be used.

The development can be carried out by a method such as spraying the above-mentioned developing solution onto the coating film surface, immersing in the developing solution, or applying ultrasonic waves while immersing.

Next, it is desirable to wash the relief pattern formed by development with a rinsing liquid. As the rinsing liquid, water is preferably used when developing with an aqueous alkali solution. When developing with an organic solvent, methanol, ethanol,
Isopropyl alcohol, butyl acetate and the like are preferably used.

The relief pattern polymer obtained by the above treatment is a heat-resistant polyimide-based polymer precursor, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. As the heat treatment temperature,
It is preferably performed at 135 to 400 ° C. The heat treatment is usually performed stepwise or continuously while increasing the temperature.

The actinic radiation-sensitive composition of the present invention can be used for a passivation film of a semiconductor, a buffer coat film of a passivation film, an interlayer insulation film of a multilayer integrated circuit, an interlayer insulation film or a surface protection film of a hybrid integrated circuit, and a solder of a printed circuit. It is used for forming a protective film, an alignment film for liquid crystal, an interlayer insulating film of a mounting substrate, and the like. Further, it is also possible to apply a metal as a highly heat-resistant photoresist or a dry etching process. It can be applied to other known uses of polyimide.

[0035]

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 32.2 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 50 g of urea were reacted with 200 g of N-methyl-2-pyrrolidone at 200 ° C. for 3 hours. Thereafter, the mixture was cooled to 30 ° C. and 1,2-naphthoquinonediazide-
53.7 g of 5-sulfonyl chloride and triethylamine
30 g was added and reacted at 50 ° C. for 3 hours. This was poured into water, and the precipitate was filtered off and dried, and N, N'-1,
2-Naphthoquinonediazide-5-sulfonylbenzophenonetetracarboxylic imide was obtained (compound a).

Compound 78.5 g and 3,3 ', 4,4'-
Benzophenonetetracarboxylic dianhydride 32.2 g,
38.0 g of 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane
2.48 g was added and reacted at 50 ° C. for 3 hours to obtain a polymer solution.

This polymer solution was coated on a 4-inch silicon wafer and dried on a hot plate at 120 ° C. for 3 minutes.
A film having a thickness of 3 microns was formed. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 600 mJ / cm ² (ultraviolet intensity of 365 nm) through a chromium photomask. After the exposure, the film was immersed in a developing solution composed of a 2.38% aqueous solution of tetramethylammonium hydroxide, whereby the exposed portion was dissolved, and an image was formed with the unexposed portion remaining. After rinsing with water, it was dried by blowing with nitrogen. In this manner, the obtained positive pattern was heated at 130 ° C. for 2 hours.
Cure was performed in a nitrogen atmosphere at 00 ° C. and 400 ° C. for 30 minutes each to obtain a positive polyimide pattern. Example 2 21.8 g of pyromellitic dianhydride and 50 g of urea were reacted with 200 g of N-methyl-2-pyrrolidone at 200 ° C. for 3 hours. Thereafter, the mixture was cooled to 30 ° C., 53.7 g of 1,2-naphthoquinonediazido-5-sulfonyl chloride and 30 g of triethylamine were added, and the mixture was reacted at 50 ° C. for 3 hours. This is poured into water, the precipitate is filtered off, dried,
N, N'-1,2-naphthoquinonediazido-5-sulfonylpyromellitic imide was obtained (compound b).

68.1 g of compound b, 19.0 g of 4,4'-diaminodiphenyl ether and 1.24 g of bis (3-aminopropyl) tetramethyldisiloxane were added together with 200 g of N-methyl-2-pyrrolidone and reacted at 50 ° C. for 3 hours. Then, a polymer solution was obtained.

This polymer solution was coated on a 4-inch silicon wafer and dried on a hot plate at 120 ° C. for 3 minutes.
A film having a thickness of 3 microns was formed. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 600 mJ / cm ² (ultraviolet intensity of 365 nm) through a chromium photomask. After the exposure, the film was immersed in a developing solution composed of a 2.38% aqueous solution of tetramethylammonium hydroxide, whereby the exposed portion was dissolved, and an image was formed with the unexposed portion remaining. After rinsing with water, it was dried by blowing nitrogen. In this manner, the obtained positive pattern was heated at 130 ° C. for 2 hours.
Cure was performed in a nitrogen atmosphere at 00 ° C. and 400 ° C. for 30 minutes each to obtain a positive polyimide pattern. Example 3 To 100 g of the polymer solution obtained in Example 2, 75 g of "Semico Fine" SP-740 manufactured by Toray was added and mixed.

This was coated on a 4-inch silicon wafer and dried on a hot plate at 120 ° C. for 3 minutes to form a coating having a thickness of 3 μm. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 600 mJ / cm ² (ultraviolet intensity of 365 nm) through a chromium photomask. After the exposure, the film was immersed in a developing solution composed of a 2.38% aqueous solution of tetramethylammonium hydroxide, whereby the exposed portion was dissolved, and an image was formed with the unexposed portion remaining. After rinsing with water, it was dried by blowing nitrogen. In this manner, the obtained positive pattern was heated at 130 ° C. and 200 ° C.
Curing was performed in a nitrogen atmosphere at a temperature of 400 ° C. and a temperature of 400 ° C., respectively, to obtain a positive polyimide pattern.

[0042]

According to the actinic radiation-sensitive composition of the present invention,
In order to obtain a highly practical photosensitive polyimide in which the light-irradiated part dissolves, it can be used at the time of exposure, as compared with a conventional negative-type behavior in which the exposed part remains, which can be obtained. Even if dust or the like adheres to the mask or the like, the portion does not become a pinhole (defect) or the like, and a highly reliable product can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-116216 (JP, A) JP-A-4-120543 (JP, A) JP-A-4-284455 (JP, A) JP-A-2- 167550 (JP, A) JP-A-3-58048 (JP, A) JP-A-3-281535 (JP, A) JP-A-3-273029 (JP, A) JP-A-3-87745 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] 1. An actinic radiation-sensitive composition comprising a polymer (A) having a structural unit represented by the general formula [1]. Embedded image (Q is at least one of the naphthoquinonediazidosulfonylamide groups in the polymer (A) and represents a hydroxyl group or a monovalent organic group. R ¹ is a trivalent or monovalent organic group having at least 2 carbon atoms. A tetravalent organic group, R ² represents a divalent organic group having at least two carbon atoms.
n is 1 or 2. )