Positive photosensitive resin composition

Details Positive photosensitive resin composition Positive photosensitive resin composition

2002-01-31

2003-08-19

Chu, John S. (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Diazo reproduction, process, composition, or product

Composition or product which contains radiation sensitive...

C430S165000, C430S192000, C430S193000, C430S286100

Reexamination Certificate

active

06607865

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a positive photosensitive resin composition which can form a pattern of high resolution and high residual film ratio and has high sensitivity.
BACKGROUND ART
Polyimide resins excellent in heat resistance, electrical properties, mechanical properties, etc. have heretofore been used in the surface-protecting film or interlayer dielectric of a semiconductor device. In recent years, however, significant improvements in heat cycle resistance, thermal shock resistance, etc. have become necessary for the resins used in the above applications, because semiconductor devices have come to employ a higher integration and a larger size, packages have become thinner and smaller, and the mounting has shifted to surface mounting by solder reflow. Therefore, a resin of higher performance has come to be required.
Meanwhile, a technique of allowing a polyimide resin to have photosensitivity by itself is drawing attention. The polyimide resin allowed to have photosensitivity by such a technique, includes, for example, a photosensitive polymide resin represented by the following formula (12):
With such a resin, the step of pattern formation can be partly simplified and a shorter step and a higher yield are achieved. However, a solvent such as N-methyl-2-pyrrolidone or the like is required in the step of development, which incurs a problem in safety and handling.
Hence, there have recently been developed positive photosensitive resin compositions which can be subjected to development with an aqueous alkali solution. For example, there is disclosed, in JP-B-1-46862, a positive photosensitive resin composition constituted by a polybenzoxazole precursor, which is a base resin, and a diazoquinone compound, which is a photosensitizer. This resin composition has high heat resistance, excellent electrical properties and fine pattern formability and has a possibility of being used as a resin for wafer coating as well as for interlayer insulation. The development mechanism of this positive photosensitive resin composition is as follows. The diazoquinone compound is insoluble in an aqueous alkali solution when unexposed to a light; when exposed to a light, the diazoquinone compound gives rise to a chemical reaction to become soluble in the aqueous alkali solution; and by utilizing such difference in solubility between when exposed and when unexposed, the exposed portion is dissolved and removed, whereby a film pattern consisting of only the unexposed portion can be formed.
When these photosensitive resin compositions are used practically, particularly important is the sensitivity of each photosensitive resin composition. A low sensitivity requires a long exposure time, resulting in a low throughput. When the base resin is allowed to have a smaller molecular weight as a means for increasing the sensitivity of the photosensitive resin composition, the unexposed portion gives a large film thickness loss during development, which makes it impossible to obtain a required film thickness or incurs the collapse of pattern shape. Therefore, it is highly desired to develop a photosensitive resin composition which satisfies the above-mentioned properties and yet has high sensitivity.
DISCLOSURE OF THE INVENTION
The present invention aims at providing a positive photosensitive resin composition which can form a pattern of high resolution and high residual film ratio and has high sensitivity.
The present invention lies in a positive photosensitive resin composition comprising:
100 parts by weight of (A) a polyamide resin represented by the following general formula (1), and
1 to 50 parts by weight of (B1) a photosensitizer which is a 1,2-naphthoquinone-2-diazide-5-sulfonate or a 1,2-naphthoquinone-2-diazide-4-sulfonate, of a phenol compound having a skeletal structure represented by the following general formula (2):
wherein X is a tetravalent cyclic compound group; Y is a divalent cyclic compound group; Z is a group represented by
wherein R
1
and R
2
are each a divalent organic group, and R
3
and R
4
are each a monovalent organic group; E is an aliphatic group or a cyclic compound group, each having at least one alkenyl or alkynyl group; a and b each show a molar fraction, a+b=100 mole %, a=60 to 100 mole %, and b=0 to 40 mole %; and n is an average value and a positive number of 2 to 300, and
wherein R
5
is one atom or group selected from hydrogen atom, alkyl groups, alkoxy groups, aryl groups and substituted aryl groups; a plurality of R
6
's may be the same or different and are each one atom or group selected from hydrogen atom, hydroxyl group, alkyl groups, alkoxy groups, aryl groups and cycloalkyl groups, and at least one R
6
is hydroxyl group; a plurality of R
7
's may be the same or different and are each one atom or group selected from hydrogen atom, hydroxyl group, alkyl groups, alkoxy groups, aryl groups and cycloalkyl groups, and at least one R
7
is hydroxyl group; l is an integer of 0 to 3; m is an integer of 1 to 3; and n is an integer of 1 to 3.
DETAILED DESCRIPTION OF THE INVENTION
The polyamide resin of the general formula (1) is obtained by reacting a bis(aminophenol) having an X structure, a silicone diamine having a Z structure which is optionally used, a dicarboxylic acid or its dichloride, having a Y structure, and an acid anhydride which generates an E structure upon reaction with amino group. In order to obtain a higher yield, etc., it is possible to use a dicarboxylic acid derivative of active ester type obtained by reaction of a dicarboxylic acid with 1-hydroxy-1,2,3-benztriazole or the like. The polyamide resin, when heated at about 300 to 400° C., gives rise to dehydration and ring closure to become a polybenzoxazole which is a heat-resistant resin.
The X of the polyamide resin of the general formula (1) used in the present invention includes, for example, the followings but is not restricted thereto.
In the above, A is —CH
2
—, —C(CH
3
)
2
—, —O—, —S—, —SO
2
—, —CO—, —NHCO— or —C(CF
3
)
2
—.
Among them, particularly preferred one is selected from the followings.
The Y of the polyamide resin of the general formula (1) includes, for example, the followings but is not restricted thereto.
In the above, A is —CH
2
—, —C(CH
3
)
2
—, —O—, —S—, —SO
2
—, —CO—, —NHCO— or —C(CF
3
)
2
—.
Among them, particularly preferred one is selected from the followings.
The E of the polyamide resin of the general formula (1) includes, for example, the followings but is not restricted thereto.
Among them, particularly preferred one is selected from the followings.
In the present invention, a dicarboxylic acid or its dichloride, or its derivative having a Y structure is reacted with a bis(aminophenol) having an X structure to synthesize a polyamide resin; thereafter, each of the terminal amino groups of the polyamide resin is capped with an acid anhydride having at least one alkenyl or alkynyl group shown in the E of the general formula (1).
The Z of the polyamide resin of the general formula (1) which is used optionally, includes, for example, the followings but is not restricted thereto.
The Z of the general formula (1) is used, for example, when very high adhesion to a substrate (e.g. silicon wafer) is required. The proportion b of Z used is at most 40 mole %. A proportion of larger than 40 mole % is not preferred, because the resulting resin has very low solubility and generates scum after development, making pattern formation impossible. Each of the X, Y, E and Z may be used in one kind or admixture of two or more kinds.
The n of the general formula (1) is an average value and a positive number of 2 to 300. An n of larger than 300 is not preferred because scum may appear after development.
The examples of the phenol compound which is a skeleton of the photosensitizer (B1) used in the present invention, include the followings but are not restricted thereto.
In the phenol compound of the general formula (2) constituting the photosensitizer (B1) used in the present invention, it is preferred that 20 to 80% of the

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