Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
2000-12-27
2004-04-27
Hoff, Mark F. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C430S326000, C430S905000, C430S914000
Reexamination Certificate
active
06727036
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a positive-working radiation-sensitive composition used for lithographic printing plates, production processes of semiconductors such as IC, etc., productions of circuit substrates such as liquid crystal, thermal head, etc., and further other photofabrication processes.
BACKGROUND OF THE INVENTION
As a resist used for a pattern formation of lithographs using a far-ultraviolet light or an excimer laser light, there are chemical amplification type resist compositions described in U.S. Pat. No. 4,491,628, European Patent 29139, etc. The chemical amplification type positive-working resist composition is a pattern-forming material of forming an acid at the light-exposed portions by the irradiation of a radiation such as a far-ultraviolet light, etc., changing the solubility of the irradiated portions by the active radiation and non-irradiated portions in a developer by the reaction using the acid as a catalyst, and forming a pattern on a substrate.
The above-described chemical amplification type positive-working resist composition is largely classified into a three-component system comprising an alkali-soluble resin, a compound generating an acid by the exposure of a radiation (the compound is referred to as photo-acid generator), and a dissolution-inhibiting compound having an acid-decomposing group to the alkali-soluble resin; a two-component system comprising a resin having a group which becomes alkali-soluble by decomposing by the reaction with an acid and the photo-acid generator; and a hybrid system comprising a resin having a group which becomes alkali-soluble by decomposing by the reaction with an acid, a low-molecular weight dissolution-inhibiting compound having an acid decomposing group, and the photo-acid generator.
JP-A-2-19847 (the term “JP-A” as used herein means an unexamined published Japanese Patent application) discloses a resist composition containing a resin wherein the phenolic hydroxy group of a poly(p-hydroxystyrene) is wholly or partially protected by a tetrahydropyranyl group.
JP-A-4-219757 similarly discloses a resist composition containing a resin wherein from 20 to 70% of the phenolic hydroxy group of poly(p-hydroxystyrene) is replaced with an acetal group.
Furthermore, JP-A-5-249682 similarly discloses a photoresist composition using a resin protected with an acetal group. Also, JP-A-8-123032 discloses a photoresist composition using a terpolymer containing a group substituted by an acetal group.
Furthermore, JP-A-8-253534 discloses a photoresist composition using a partially crosslinked polymer containing a group substituted by an acetal group.
Also, in JP-A-5-323590, it is described to use two kinds of photo-acid generators, in U.S. Pat. No. 5,403,695, it is described to use a photo-acid generator generating a strong acid and a photo-acid generator generating a weak acid, and in JP-A-11-125907, it is described to use a compound generating a carboxylic acid having a boiling point of at least 150° C. and a compound generating an acid other than a carboxylic acid.
However, in the above-described techniques, there was a room to be improved in the pitch dependency (iso/dense bias). Because as the tendency of recent devices, various patterns are contained, various performances have been demanded for resists. One of them is the pitch dependency. In a device, there exist a portion of closed lines, a pattern having a wide space compared with lines, and further an isolated line. Accordingly, it is important to resolve various lines with a high reproducibility. However, in the present state, it is not always easy by an optical factor to reproduce various lines and a resolution method by a resist is not clear.
Furthermore, in the exposure margin, the requirement of further improving has also been strong. In this case, the exposure margin is a phenomenon that when the exposure amount is changed, the line width of the pattern obtained according to the change is changed.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a positive-working radiation-sensitive composition excellent in the pitch dependency.
A further object of the invention is to provide a positive-working radiation-sensitive composition excellent in the exposure margin.
The above-described objects of the invention are attained by the following constructions.
That is, the 1st aspect of the invention is a positive-working radiation-sensitive composition comprising
(a) a resin having an acid-decomposing group represented by the following formula (I), which is decomposed by the action of an acid to increase the solubility in an alkali developer,
(b-1) at least one kind of compounds each generates an acid by the irradiation of an active light or radiation and contributes to the decomposition reaction of the above-described acid-decomposing group,
(b-2) at least one kind of compounds each generates an acid by the irradiation of an active light or radiation but does not contribute to the decomposition reaction of the above-described acid-decomposing group,
(c) a surface active agent, and
(d) a solvent;
wherein, R
1
represents an alkyl group having from 1 to 4 carbon atoms; W represents an organic group containing at least one kind of atoms selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom, and at least one carbon atom, an amino group, an ammonium group, a mercapto group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted cyclic alkyl group; and n represents an integer of from 1 to 4.
A second aspect of the invention is the positive-working radiation-sensitive composition of the first aspect, wherein the above-described resin (a) is a resin in which at least a part of a phenolic hydroxy group of an alkali-soluble resin having the phenolic hydroxy group is protected by the acid-decomposing group shown by the above-described formula (I).
A third aspect of the invention is the positive-working radiation-sensitive composition of the first aspect, wherein W of the above-described formula (I) is at least one kind of a substituent selected from the group of the substituents shown below;
wherein, R
2
represents a straight chain, branched or cyclic alkyl group having from 1 to 6 carbon atoms, a straight chain, branched, or cyclic alkenyl group having from 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group; R
3
represents a hydrogen atom, a straight chain, branched or cyclic alkyl group having from 1 to 6 carbon atoms, a straight chain, branched or cyclic alkoxy group having from 1 to 6 carbon atoms, a halogen atom, a nitro group, an amino group, a hydroxy group, or a cyano group; X represents a halogen atom; R
4
represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cyclic alkyl group having from 3 to 15 carbon atoms; and m represents a natural number of from 1 to 4.
A fourth aspect of the invention is the positive-working radiation-sensitive composition of the first aspect, wherein the compound (b-1) is a compound generating a sulfonic acid by the irradiation of an active light or radiation and the compound (b-2) is a compound generating a carboxylic acid by the irradiation of an active light or radiation.
A fifth aspect of the invention is the positive-working radiation-sensitive composition of any one of the first to fourth aspects, wherein the composition further contains an organic basic compound.
In the positive-working radiation-sensitive composition of the invention, by using the acid-decomposing resin having an acetal group having at the terminal a substituent of a specific structure as an acid-decomposing group together with a combination of a compound contributing to the decomposition of the above-described specific acid-decomposing group with a compound of not contributing to the decomposition as a compound generating an acid by the irradiation of an active light or radiation, the pitch dependency is greatly improved
Kanna Shinichi
Kodama Kunihiko
Fuji Photo Film Co. , Ltd.
Hoff Mark F.
Lee Sin J.
Sughrue & Mion, PLLC
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