Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2001-01-16
2004-11-30
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...
C430S281100, C430S287100, C430S288100, C430S296000
Reexamination Certificate
active
06824948
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a negative-working resist composition suitably used for super-micro lithographic processes such as the productions of VLSI and high-capacity microchips, etc., and other photofabrication processes. More specifically, the invention relates to a negative-working photoresist composition capable of forming highly fined patterns using X-rays, electron beams, etc., and particularly to a negative-working resist composition which can be suitably used for fine working of semiconductor devices using a high energy such as electron beams, etc.
BACKGROUND OF THE INVENTION
In integrated circuits, the degree of integration is more and more increased and in the production of s semiconductor substrate of VLSI, etc., working of super-fine patters made of line width of finer than half micron has been required. For satisfying the requirement, the using wavelength of a light exposure apparatus used for a photolithography is more and more shortened and at present, the use if a far ultraviolet light and an excimer laser (XeCl, KrF, ArF, etc.) has been investigated. Furthermore, the formation of finer patterns by electron beams or X-rays has been investigated.
Particularly, electron beams or X-rays have been positioned as the advanced pattern-forming technique or further advanced pattern-forming technique and the development of a negative-working resist having a high sensitivity, and capable of attaining a profile form of a high resolution and rectangular form has been desired.
In the electron beam lithography, in the course that accelerated electron beams cause collision and scattering to the atoms constituting the resist material, an energy is supplied to the compound to cause the reaction of the resist material, whereby images are formed. By using a highly accelerated electron beams, the straight going property is increased, the influence of electron scattering becomes less, and the formation of patterns of a high-resolution and a rectangular form becomes possible but on the other hand, the permeability of electron beams is increased and the sensitivity is lowered. As described above, in an electron beam lithography, the sensitivity is in the relation of trade off with the resolution•resist form and it is a problem how they can be coexisted.
As the resist material for these problems, for the purpose of improving the sensitivity, a chemical amplification type resist mainly utilizing an acid catalyst reaction is used and as a negative-working resist, a chemical amplification type composition made of an alkali-soluble resin, an acid generator, and an acid crosslinking agent as the main constituents is effectively used.
Hitherto, for a negative-working chemical amplification type resist, various alkali-soluble resins are proposed. For example, Japanese Patent No. 2505033, JP-A-3-170554 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) and JP-A-6-118646 disclose novolac type phenol resins, JP-A-7-311463 and JP-A-8-292559 disclose polyvinyl phenol resins having narrowed molecule weight distributions, JP-A-3-87746 and JP-A-8-44061 disclose phenol resins a part of which is converted to a cyclic alcohol structure by a hydrogenation, JP-A-7-295220 and JP-A-8-152717 disclose resins formed by protecting a part of the OH groups of polyvinyl phenol with an alkyl group, JP-A-339086 discloses a polyvinyl phenol resin having a protective group inert to an acid, such as an acyl group, JP-A-6-67431 and JP-A-10-10733 discloses polyvinyl phenol resins each copolymerized with styrene, JP-A-9-166870 discloses a polyvinyl phenol resin copolymerized with a (meth)acrylate monomer, and further JP-A-8-240911 discloses a resin having a carboxyl group.
Also, as the acid generator, JP-B-8-3635 (the term “JP-B” as used herein means an “examined Japanese patent publication”) discloses organic halogen compounds, JP-A-2-52348 discloses aromatic compounds substituted with Br or Cl, JP-A-4-367864 and JP-A-4-367865 disclose aromatic compounds having an alkyl group and alkoxy group substituted with Br or Cl, JP-A-2-150848 and JP-A-6-199770 discloses iodonium compounds and sulfonium compounds, JP-A-3-87746 discloses haloalkane sulfonate compounds, JP-A-4-210960 and JP-A-4-217249 disclose diazodisulfone compounds or diazosulfone compounds, JP-A-4-336454 discloses Br- or I-substituted alkyltriazine compounds, JP-A-4-291258 discloses sulfonamide compounds and sulfonimide compounds, JP-A-4-291259 discloses sulfonic acid compounds of polyhydric phenols, JP-A-4-291260, JP-A-4-291261, and JP-A-6-202320 disclose naphthoquinonediazido-4-sulfonate compounds, JP-A-5-210239 discloses disulfone compounds, JP-A-6-236024 discloses N-oxyimidosulfonate compounds, and U.S. Pat. No. 5,344,742 discloses benzylsulfonate compounds, etc.
Furthermore, as the acid crosslinking agent, JP-A-3-75652, JP-A-5-181277, and JP-A-7-146556 disclose methoxymethylmelamine compounds, JP-A-4-281455, JP-A-5-232702, and JP-A-6-83055 disclose compounds having an alkoxymethyl ether group, JP-A-5-281715 discloses oxazine compounds, JP-A-5-134412 and JP-A-6-3825 disclose aromatic compounds having an alkoxyalkyl group, JP-A-6-194838 discloses trioxane compounds, JP-A-1-293339 discloses alkoxymethyluryl compounds, etc.
However, in any combinations of these compounds, it is difficult to obtain a sufficiently high sensitivity under an electron beam irradiation or X-ray irradiation in a high-accelerated voltage condition, and also it becomes a problem to coexist the sensitivity, the resolution, and the resist form in the level capable of satisfying.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to solve the problems of the technique of improving the performance in fine working of semiconductor devices using electron beams or X-rays, and to provide a negative-working chemical amplification type resist composition for electron beams or X-rays satisfying the sensitivity, the resolution, and the resist form for the use of electron beams or X-rays.
Furthermore, further object of the invention is to provide an electron beam or X-ray negative-working chemical amplification type resist composition showing a high sensitivity, aiming at the improvement of the through put of an advanced EB irradiation apparatus suitable of the mass production of semiconductor devices and capable of coping with an EB block irradiating machine or an EB stepper (successively reducing projector).
As the result of various investigations taking care of the above-described various characteristics, the present inventors have found that the objects of the invention can be fairly attained by using the following specific compositions and have accomplished the present invention.
The is, the present invention provides the following constructions.
(1) A negative-working resist composition for electron beams or X-rays comprising (A) a compound generating an acid and/or radical species by the irradiation of electron beams or X-rays, (B) a resin which is insoluble in water and soluble in an alkali aqueous solution, (C) a crosslinking agent causing crosslinking with the resin of component (B) by the action of an acid, and (D) a compound having at least one unsaturated bond capable of being polymerized by an acid and/or a radical.
(2) The negative-working resist composition for electron beams or X-rays described in the above item (1), wherein the resist composition further contains (E) an organic basic compound.
(3) The negative-working resist composition for electron beams or X-rays described in the above item (1) or (2), wherein the resin of component (B) is the resin having a repeating unit shown by the following formula (a):
wherein R
1
represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent; R
2
represents a hydrogen atom, or an alkyl, cycloalkyl, aryl, aralkyl, or acyl group which may have a substituent; R
3
and R
4
, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl,
Adegawa Yutaka
Aoai Toshiaki
Yagihara Morio
Chu John S.
Fuji Photo Film Co. , Ltd.
Sughrue & Mion, PLLC
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