Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
1999-09-24
2001-01-23
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...
C430S191000, C430S192000, C430S193000, C430S326000, C430S330000
Reexamination Certificate
active
06177225
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to positive photosensitive resin compositions. More specifically, the present invention relates to positive-working, aqueous base developable photosensitive polybenzoxazole (PBO) precursor compositions that are suitable for applications in the field of microelectronics.
BACKGROUND OF THE INVENTION
In microelectronic applications, polymers that demonstrate high temperature resistance are generally well known. Precursors of such polymers, such as polyimides and polybenzoxazoles can be made photoreactive with suitable additives. The precursors are converted to the desired polymer by known techniques such as exposure to high temperatures. The polymer precursors are used to prepare protective layers, insulating layers, and relief structures of highly heat-resistant polymers.
Conventional positive-working photosensitive polybenzoxazoles (PBO) contain an alkaline soluble PBO precursor and a diazoquinone photoactive compound as shown in U.S. Pat. No. 4,371,685. The diazoquinone compound inhibits the solubility of the PBO precursor in an aqueous base. After exposure to light, the diazoquinone compound undergoes photolysis and converts to indenecarboxylic acid, which promotes the aqueous base solubility of the PBO precursor.
SUMMARY OF THE INVENTION
The present invention provides a positive photosensitive resin composition comprising:
(a) a capped polybenzoxazole precursor polymer having the structure;
wherein Ar
1
is a tetravalent aromatic group, aliphatic group, heterocyclic group, or mixtures thereof; Ar
2
is a divalent aromatic, heterocyclic, or aliphatic group that may or may not contain silicon; Ar
3
is a divalent aromatic group, aliphatic group, heterocylic group, or mixtures thereof; Z is one of the following groups:
x is 10 to 1000; y is 0 to 900; and b is 0.10 to 350;
(b) a photosensitive agent; and (c) a solvent. The benefits of the positive photosensitive formulations prepared according to the present invention compared to the prior art are: (1) a reduction in the amount of photosensitive agent required in a formulation, to obtain useful dark film dissolution rates; and (2) the optical absorbance of films prepared from the formulations that is due to the diazonapthaquinone moiety in the photosensitive agent is decreased. Consequently, the films prepared according to the present invention have higher optical transparency toward i-line and g-line radiation, resulting in improved photospeed.
DETAILED DESCRIPTION OF THE INVENTION
One or more capped polybenzoxazole precursor polymers are formed by the reaction of a polybenzoxazole precursor (G) with a diazoquinone compound.
The polybenzoxazole precursor has a polymerization degree of 10-1000 and is synthesized by the reaction of monomers (A), (B), and (C) in the presence of a base:
wherein Ar
1
, Ar
2
, Ar
3
, x, and y are as previously defined, and W is Cl, OR, or H; wherein R is alkyl or cycloalkyl, such as —CH
3
, —C
2
H
5
, n-C
3
H
7
, i-C
3
H
7
, n-C
4
H
9
, t-C
4
H
9
, cyclohexyl, and the like.
The ratio of [(A)+(B)]/(C) is generally between about 0.9 to 1.1. Monomer (A) is about 10-1000 mole % of [(A)+(B)] and monomer (B) is about 0-90 mole % of [(A)+(B)]. The resulting polymer (G) is then reacted with about 1-35 mole % of a diazoquinone to produce capped polybenzoxazole precursor (F).
wherein Ar
1
, Ar
2
, Ar
3
, Z, x, y, and b are as previously defined.
In monomer (A), which is a constituent (G) and (F), Ar
1
is a tetravalent aromatic, aliphatic, or heterocyclic group, and can include, for example, the following moieties:
wherein X
1
is —O—, —S—, —C(CF
3
)
2
—, —CH
2
—, —SO
2
—,
R
1
alkyl or cycloalkyl, such as —CH
3
, —C
2
H
5
, n-C
3
H
7
, i-C
3
H
7
, n-C
4
H
9
, t-C
4
H
9
, cyclohexyl, and the like. However, Ar
1
is not restricted to these groups. Furthermore, monomer (A) may be a mixture of two or more monomers.
In monomer (B), which is a constituent of precursor (G) and capped precursor (F), Ar
2
is a divalent aromatic, heterocyclic, alicyclic, or aliphatic group that may or may not contain silicon. The Ar
2
containing monomer (B) includes, for example, 5(6)-diamino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI), m-phenylenediamine, p-phenylenediamine, 2,2′-bis(trifluoromethyl)-4,4′-diamino-1,1′-biphenyl, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 2,4-tolylenediamine, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ketone, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 1,3-bis (4-aminophenoxy)benzene, 1,3-bis(3-amino-phenoxy)benzene, 1,4-bis(&ggr;-aminopropyl)tetramethyldisiloxane, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p- xylylenediamine, methylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 2,5-dimethylnonamethylenediamine, decamethylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, 1,10-diamino-1,10-dimethyldecane, 2,11-diaminidodecane, 1,12-diaminooctadecane, 2,17-diaminoeicosane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, bis(4-aminocyclohexyl)methane, 3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,6-diamino-4-trifluoromethylpyridine, 2,5-diamino-1,3,4-oxadiazole, 1,4-diaminocyclohexane, piperazine, 4,4′-methylenedianiline, 4,4′-methylene-bis(o-choloroaniline), 4,4′-methylene-bis(3-methylaniline), 4,4′-methylene-bis(2-ethylaniline), 4,4′-methylene-bis(2-methoxyaniline), 4,4′-oxy-dianiline, 4,4′-oxy-bis-(2-methoxyaniline), 4,4′-oxy-bis-(2-chloroaniline), 4,4′-thio-dianiline, 4,4′-thio-bis-(2-methylaniline), 4,4′-thio-bis-(2-methoyoxyaniline), 4,4′-thio-bis-(2-chloroaniline, 3,3′sulfonyl-dianiline, 3,3′sulfonyl-dianiline, and mixtures thereof. However, it should be understood that monomer (B) is not restricted to these compounds.
In monomer (C), which is a constituent of polybenzoxazole precursor (G) and capped precursor (F), Ar
3
is a divalent aromatic, aliphatic, or heterocyclic group, and includes, for example the following moieties:
wherein X
2
is —O—, —S—, —C(CF
3
)
2
—, —CH
2
—, —SO
2
—, —NHCO—. However, Ar
3
is not restricted to these groups. Furthermore, monomer (C) may be a mixture of two or more monomers.
The diazoquinone compound that is reacted with the PBO precursor (G) can be one of the following:
or mixtures thereof.
The preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), &ggr;-butyrolactone (GBL), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl-2-piperiodone, dimethylsulfoxide (DMSO), sulfolane, and diglyme. The most preferred solvents are N-methyl-2-pyrrolidone (NMP) and &ggr;-butyrolactone (GBL).
Any conventional reaction for reacting dicarboxylic acid or its chloride or ester with at least one aromatic and/or heterocyclic dihydroxydiamine, and optionally, with at least one diamine may be used. Examples of suitable dicarboxylic acids are selected from the group consisting of 4,4′-diphenyletherdicaboxylic acid, terephthalic acid, isophthalic acid and mixtures thereof. Examples of suitable dihydroxydiamine compounds are 3,3′-dihydroxy-4,4′-diaminodiphenylether, 3,3-dihydroxylbenzidine, hexafluoro-2,2-bis-3-amino-4-hydroxyphenylpropane and mixtures thereof. Generally, the reaction is carried out at about −10° C. to about 30° C. for about 6 to 48 hours. The molar ratio of diacid to (diamine+dihydroxydiamine) should be about 0.9-1.1:1.
The
Hsu Steve Lien-Chung
Naiini Ahmad
Waterson Pamela J.
Weber William D.
Arch Specialty Chemicals, Inc.
Chu John S.
Ohlandt Greeley Ruggiero & Perle L.L.P.
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