Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2000-03-24
2001-04-10
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...
C430S192000, C430S193000, C430S270100, C430S326000
Reexamination Certificate
active
06214516
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 polyirnides 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 containing a silane diol such as diarylsilane diol or dialkylsilane diol, one or more polybenzoxazole precursors, a photosensitive agent (e.g. diazoquinone compound, dihydropyridine, or mixtures thereof), and a solvent.
In the present invention, a silane diol compound is an essential component of the positive acting, photoactive resin composition. In the present invention, the silane diol surprisingly acts as a dissolution inhibitor. This behavior is contrary to what one would expect, since in other systems such as those described in U.S. Pat. No. 5,856,065, a silane diol functions as a dissolution enhancer.
The present invention provides a positive photosensitive resin composition comprising a silane diol, one or more polybenzoxazole precursors, a photosensitive agent, and a solvent. The composition of the present invention exhibits several improvements over prior art compositions. For example, dissolution inhibition and crack resistance are noticeably improved. Furthermore, there is a decrease in swelling and skinning during exposure to aqueous developers, as compared to other compositions at a similar inhibition level. These improvements allow longer, more controlled development times resulting in increased develop process latitude.
DETAILED DESCRIPTION OF THE INVENTION
The positive photosensitive resin composition of the present invention contains (a) a silane diol such as diarylsilane diol or dialkylsilane diol, (b) one or more polybenzoxazole precursors, (c) a photosensitive agent (e.g. diazoquinone compound, dihydropyridine, or mixtures thereof), and (d) a solvent.
The silane diol compound can be, for example, a diarylsilane diol or a dialkylsilane diol, or mixtures thereof. Most preferred is a diphenylsilane diol. The silane diol is included in the composition at about 0.1 wt. % to 10.0 wt. %, preferably at about 0.5 wt. % to 7.5 wt. %, and most preferably at about 1 wt. % to 5 wt. %.
The photosensitive resin composition has one or more polybenzoxazole precursors having the structure shown in (D):
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 x is 10 to 1000, and y is 0 to 900; Ar
1
is a tetravalent aromatic, aliphatic, or heterocyclic group; Ar
2
is a divalent aromatic, heterocyclic, alicyclic or aliphatic group; Ar
3
is a divalent aromatic, aliphatic or heterocyclic group, and W is Cl, OR and H; wherein R is an alkyl group 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
, or a cyclohexyl group.
The ratio of [(A)+(B)]/(C) is generally between about 0.9 to 1.1. Monomer (A) is about 10-100 mole % of [(A)+(B)] and monomer (B) is about 0-90 mole % of [(A)+(B)].
In monomer (A), which is a constituent of polymer (D), Ar
1
is a tetravalent aromatic, aliphatic, or heterocyclic group, and can include the following moieties:
R
1
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. 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 polybenzoxazole precursor (D), 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, 3,3′-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′-diaminodiphenylethne, 4,4′-diaminodiphenylethne, and 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-methyoxyaniline), 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 (D), Ar
3
is a divalent aromatic or heterocyclic group, and includes, for example:
wherein X
2
is —O—, —S—, —C(CF
3
)
2
—, —CH
2
—, —SO
2
—, or —NHCO—. However, Ar
3
is not restricted to these groups. Furthermore, monomer (C) may be a mixture of two or more monomers.
The preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), &ggr;-butyrolactone (GBL), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethylsulfoxide (DMSO), sulfolane, and diglyme. Most preferred are N-methyl-2-pyrrolidone (NMP) and &ggr;-butyrolactone (GBL).
Any suitable reaction for reacting such dicarboxylic acid or its dichloride or diester with at least one aromatic and/or heterocyclic dihydroxydiamine, and optionally, with at least one diamine may be used. Generally, the reaction is carried out at about 10° C. to about 50° C. for abou
Hsu Steve Lien-Chung
Naiini Ahmad
Waterson Pamela J.
Weber William D.
Arch Specialty Chemicals, Inc.
Chu John S.
Ohlandt Greeley Ruggiero & Perle LLP
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