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
2000-06-28
2002-05-07
Ashton, Rosemary (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
C326S044000
Reexamination Certificate
active
06383715
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to strongly water-soluble photoacid generator resist compositions that eliminate post-development defects in resist technology, and more particularly, to pattern-forming resist materials in which the resist patterns are formed on a substrate base material, i.e., a semiconductor material during production of semiconductor devices that are used in dynamic random access memory (DRAM) and logic devices.
2. Description of Related Art
As the minimum feature size of semiconductor devices becomes smaller and smaller, defect control becomes more important and the challenge to achieve a high product yield becomes more formidable. Starting from the qualification of 256M DRAM technology, a class of special defects so called “Blob Defects” was discovered on a nested contact hole level called CB using a chrome on glass mask and JSR M20G resist.
Later on blob defects were observed to a varying degree with all DUV resists, such as Shipley UV2HS, UV6Hs and JSR M60G, regardless of whether the resist chemistry was tert-butoxycarbonyl (t-BOC) or acetal-based. It was found that, the better the resist contrast and surface inhibition, the higher the blob defect density. Therefore, the selection of contact hole resist for patterning even a smaller contact hole size must face a compromise between defect density and lithographic performance, which is not compatible with the trend of IDW k1 printing. Moreover, no resist evaluated so far shows zero blob defect density. Nevertheless, blob defects of necessity becomes a limiting factor in resist selection and yield enhancement.
U.S. Pat. No. 4,245,029 discloses that oxirane containing aliphatically unsaturated organic materials can be cured by a simultaneous free-radical and cationic mechanism, to obtain improved characteristics in the final product; namely, solvent resistance. Simultaneous free-radical and cationic cure of oxirane containing aliphatically unsaturated materials are achieved by using triarylsulfonium salts in the oxirane containing aliphatically unsaturated organic materials and the exposure of the photocurable compositions to radiant energy such as ultraviolent light.
Photoacid generators(PAGs) and use of the same in chemically amplified resist compositions are disclosed in U.S. Pat. No. 5,733,704. The resist composition is one in which high resolution patterns can be formed in a lithography process, due to its high sensitivity to light and large difference in solubilities in a developing solution before and after exposure to light. The resist composition is suitable for manufacturing highly integrated semiconductor chips.
U.S. Pat. No. 5,736,296 disclose an improved, chemically-amplifying positive resist composition for radiations of UV rays, deep-UV rays, excimer laser beams, X-rays and electron beams, wherein the composition comprises a resin component whose solubility in an alkaline aqueous solution is increased by the action of acids, and a compound which generates an acid when exposed to radiations. The composition is useful for forming fine patterns in producing ultra-large scale integration (ULSIs) devices.
A process for the formation of a negative resist pattern is disclosed in U.S. Pat. No. 5,017,461, comprising preparing a mixture of water-soluble polymeric material having at least one hydroxyl group with a photoacid generator capable of releasing an acid upon radiation exposure, coating a solution of the resist material onto a substrate to form a resist layer, exposing the layer to patterned radiation, heating the exposed resist layer in the presence of an acid as a catalyst to remove water, and developing a resist layer with water to remove unexposed areas to form a resist pattern on the substrate.
None of the foregoing references provide any measures for photoacid generators (PAGs) in resist formulations that avoid blob defect formation.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a strongly water-soluble photoacid generator in resist compositions that avoids blob defect formation.
Another object of the present invention is to provide strongly water-soluble photoacid generators in resist compositions to prevent the precipitation of non-decomposed PAG in the developer composition.
A further object of the present invention is to provide a strongly water-soluble PAG in resist compositions to prevent blob defect formation by incorporating certain water-soluble groups, such as —OH into the PAG in order to enhance the PAG solubility in the developer.
A yet further object of the prevent invention is to provide a strongly water-soluble photoacid generator in resist compositions to avoid blob defect formation by replacing methoxy groups with hydroxy groups to transform the water-insoluble PAG {bis(t-butylphenyl)iodoniun 4-methoxybenzenesulfonate} to the water-soluble compound {bis(t-butylphenyl)iodonium 4-hydroxybenzenesulfonate} to prevent PAGs precipitation in the developer.
In general, the invention is accomplished by discovering and choosing strongly water-soluble photoacid generators (PAGs) and using the same in resist compositions to prevent blob defect formation. This entails incorporating strongly water-soluble PAGs in resist compositions to prevent the precipitation of non-decomposed PAG in the developer. In one embodiment, the invention process incorporates certain water-soluble groups such as —OH into the PAG to enhance PAG solubility in the developer
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patent: 5683856 (1997-11-01), Aoai et al.
patent: 5837420 (1998-11-01), Aoai et al.
patent: 5965319 (1999-10-01), Kobayashi
patent: 6051370 (2000-04-01), Kim
Gutman Alois
Lu Zhijian
Ashton Rosemary
Infineon - Technologies AG
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