JPH11233949A - Developer solution for photosensitive polyimide precursor and manufacture of pattern using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer solution for photosensitive polyimide precursor which can shorten the developing time. SOLUTION: A developing solution for photosensitive polyimide precursor is composed of (a) a basic compound and, (b) at least one kind of organic solvent selected from among a group composed of amides, ketones, esters, lactones, halogenated hydrocarbons, and hydrocarbons and contains the compound (a) and solvent (b) are proportioned that the ratios become 0.1-20 pts.wt. and 99.9-80 pts.wt., respectively, and the total quantity becomes 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer for a photosensitive polyimide precursor and a method for producing a pattern using the same.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been.

However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board involves forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, cleaning the substrate surface, and the like. Since it is performed through complicated and various steps, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

[0004] As these materials, for example, heat-resistant light-sensitive materials based on photosensitive polyimide, cyclized polybutadiene and the like have been proposed. In particular, photosensitive polyimide has excellent heat resistance and eliminates impurities. Has attracted particular attention because of its ease of use.

[0005]

However, in the conventional photosensitive polyimide, the base polymer itself has poor solubility in an organic solvent, and when a conventional developing solution for a photosensitive polyimide precursor is used, a good pattern formation can be achieved. The time required for development tended to be enormous in order to obtain.

The present invention is directed to a photosensitive polyimide precursor developing solution and pattern manufacturing method capable of processing polyimide patterns such as an interlayer insulating film for a multilayer wiring board, an α-ray shielding film for a semiconductor memory device, and a buffer coat film in a short time. Further, in addition to this object, a developer and a pattern manufacturing method for a photosensitive polyimide precursor having a flatness of a remaining film and generating no development residue. It is intended to provide.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. The present invention provides (a) a basic compound and (b) at least one organic compound selected from the group consisting of amides, ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons. The present invention relates to a photosensitive polyimide precursor developer containing a solvent. The present invention also relates to the above-mentioned developer for a photosensitive polyimide precursor, wherein (a) is a primary, secondary or tertiary amino compound. The present invention also relates to the above-mentioned developer for a photosensitive polyimide precursor, wherein (a) is an organic compound having one amino group. The present invention also provides the photosensitive polyimide precursor developer, wherein the component (a) is 0.1 to 20 parts by weight, the component (b) is 99.9 to 80 parts by weight, and the total is 100 parts by weight. About. In the present invention, (a) is used alone at 30 ° C.
The present invention relates to the photosensitive polyimide precursor developer having a liquid form at the following temperature and having a boiling point of 50 ° C. or more at atmospheric pressure. Furthermore, the present invention irradiates an actinic ray from a mask on which a pattern is drawn on a coating film of the photosensitive polyimide precursor composition, and develops using the developer according to any of the above, and removes an unirradiated portion. And a method for producing a pattern.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the developer of the present invention, the development residue can be particularly reduced by including the basic compound (a). As the basic compound, primary,
An organic compound having a secondary or tertiary amino compound and having one amino group is preferable.
Has a liquid form alone at a temperature of 30 ° C. or less,
Those having a boiling point of 50 ° C. or higher at atmospheric pressure are preferred because of their high effect. Such examples include propylamine, butylamine, pentylamine, hexylamine,
Examples include cyclohexylamine, diethylamine, dibutylamine, methylbutylamine, ethylbutylamine, diisopropylamine, dicyclohexylamine, pyrrolidine, piperidine, pyridine, aniline, trimethylamine, triethylamine, 1-methylpyrrolidine and the like. Of these, tertiary amines are preferred because of their high effects.

In the present invention, to achieve the above object, (b) is selected from the group consisting of amides, ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons. It comprises at least one organic solvent. For example, N-methyl-2 as amides
-Pyrrolidone, N, N-dimethylacetamide, N, N
-Dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and the like; ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and esters as methyl acetate, ethyl acetate, and butyl acetate. , Diethyl oxalate, diethyl malonate and the like, lactones such as γ-butyrolactone, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1,4. -Dichlorobutane, trichloroethane, chlorobenzene, o
Hexane, heptane, octane, benzene, toluene, xylene and the like can be used as hydrocarbons. Among these, amides are preferred because of their high effect, and N-methyl-2-pyrrolidone is particularly preferred. These organic solvents are used alone or in combination of two or more. The mixing ratio of the component (a) and the component (b) is preferably from 0.1 to 0.1% in view of short-time development.
20 parts by weight; (b) 99.9 to 80 parts by weight;
It is preferably 0 parts by weight.

The development using the photosensitive polyimide precursor developer according to the present invention is performed by irradiating a coating film of the photosensitive polyimide precursor composition with actinic rays from a mask on which a pattern is drawn, followed by a dipping method, The method is performed according to a method using a single method or a combination of two or more methods such as a spray method and a paddle method.
When the development is completed, a relief pattern is formed. The formed film is rinsed with water or a poor solvent as necessary. As the rinsing liquid, a poor solvent for the polyimide precursor, which has a high affinity with the developing solution, is used. Examples of the rinsing liquid include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, and diethyl ketone. By heating the obtained pattern, a stable high heat-resistant polyimide pattern from which the photosensitive agent and the solvent have been completely removed can be obtained. In the present invention, as the photosensitive polyimide precursor to be developed, a polyamide acid having a carbon-carbon unsaturated double bond introduced into a side chain of a tetracarboxylic acid residue via an ester bond, an amide bond, or the like. Esters, polyamidoamides, and negative types such as ion-bonding polyimide precursors in which an amine having an unsaturated group is bonded to a carboxyl group of a polyamic acid via an ionic bond are preferred. Is suitable for an ion-bonding polyimide precursor. The composition is prepared by blending a photoinitiator, a sensitizer, and a solvent with a polyimide precursor.

[0011]

The present invention will be described in detail below with reference to examples.

Preparation Example of Developer for Photosensitive Polyimide Precursor 100 g of N-methyl-2-pyrrolidone and 5 g of 1-methylpyrrolidine were added to a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube. The mixture was stirred at room temperature for 1 hour to give N-methyl-2-pyrrolidone / 1-methylpyrrolidine (weight ratio 9).
5/5) A mixed solution was obtained.

Synthesis Example of Polyamic Acid Solution 9.8116 g of 4,4′-diaminodiphenyl ether was placed in a three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube.
And 75.04 g of N-methyl-2-pyrrolidone were added,
The mixture was stirred and dissolved at room temperature. To this, 15.2002 g of oxydiphthalic dianhydride was added and stirred for 8 hours to obtain a viscous polyamic acid resin solution.

EXAMPLE 10 g of the polyamic acid resin solution obtained in the above synthesis example was stirred and mixed, and the sensitizers of the following formulas AZ, CM and OX were mixed with A
Z 0.027 g, CM 0.027 g and OX0.054
g was added and dissolved by stirring, followed by filtration with a filter to obtain a photosensitive resin composition solution. This solution was dropped on a silicon wafer and spin-coated. Next, using a hot plate,
After heating at 00 ° C. for 150 seconds to form a 20 μm coating film,
The pattern was masked and exposed with an i-line stepper. this,
Further, the mixture was heated at 100 ° C. for 60 seconds, and N-methyl-
Paddle development using a mixed solution of 2-pyrrolidone / 1-methylpyrrolidine for 30 seconds and rinsing with ethanol gave a good relief pattern (20 mm through hole)
was gotten.

[0015]

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Comparative Example 1 N-methyl-2-pyrrolidone used in Examples
When only N-methyl-2-pyrrolidone was used instead of the mixed solution of 1-methylpyrrolidine (weight ratio 95/5), and processing was carried out in exactly the same manner as in the examples except for the development time. Was too short to dissolve, and no pattern was formed.

[0017]

According to the pattern production method using the developing solution for a photosensitive polyimide precursor of the present invention, an interlayer insulating film for a multilayer wiring board, an α-ray shielding film for a semiconductor memory device, a buffer coat film, etc. Polyimide pattern processing can be performed quickly and in a short time, and has flatness of the remaining film,
In addition, no development residue is generated.

Claims (6)

[Claims] 1. A basic compound and (b) amides, ketones, esters, lactones, ethers,
A developer for a photosensitive polyimide precursor, comprising at least one organic solvent selected from the group consisting of halogenated hydrocarbons and hydrocarbons. 2. The developer for a photosensitive polyimide precursor according to claim 1, wherein (a) is a primary, secondary or tertiary amino compound. 3. The developing solution for a photosensitive polyimide precursor according to claim 1, wherein (a) is an organic compound having one amino group. 4. Component (a) is 0.1 to 20 parts by weight,
Component (b) is 99.9 to 80 parts by weight, and the total is 10
4. The developer for a photosensitive polyimide precursor according to claim 1, which is 0 parts by weight. 5. (a) alone has a liquid form at a temperature of 30 ° C. or less, and has a boiling point of 50 ° C. at atmospheric pressure.
5. The developer for a photosensitive polyimide precursor according to claim 1, 2, 3, or 4. 6. Irradiating an actinic ray from a mask on which a pattern is drawn on a coating film of a photosensitive polyimide precursor composition, and developing using a developer according to any one of claims 1 to 5,
A pattern manufacturing method characterized by removing unirradiated portions.