Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-03-11
2003-03-25
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S273000, C526S311000, C526S312000, C526S326000, C560S004000, C560S005000, C560S019000
Reexamination Certificate
active
06538090
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an organic anti-reflective coating (“ARC”) material which allows the stable formation of ultrafine patterns suitable for 64M, 256M, 1 G, 4 G and 16 G DRAM semiconductor devices. More particularly, the present invention relates to an organic anti-reflective coating material which contains a chromophore with high absorbance at the wavelengths useful for submicrolithography. A layer of said anti-reflective material can prevent the back reflection of light from lower layers of the semiconductor chip, as well as eliminate the standing waves caused by light and thickness changes of the photoresist layer itself, while conducting a submicrolithographic process using a 248 nm KrF, 193 nm ArF or 157 nm F
2
laser. Also, the present invention is concerned with an anti-reflective coating composition comprising such a material, an anti-reflective coating made therefrom and a preparation method thereof.
2. Description of the Prior Art
During a submicrolithographic process, one of the most important processes for fabricating highly integrated semiconductor devices, there inevitably occur standing waves and reflective notching due to the optical properties of lower layers on the wafer and to changes in the thickness of the photosensitive film applied thereon. In addition, the submicrolithographic process generally suffers from a problem of the CD (critical dimension) being altered by the diffracted light and reflected light from the lower layers.
To overcome these problems, it has been proposed to introduce a film, called an anti-reflective coating, between the substrate and the photosensitive film to prevent light reflection from the lower layer. Generally, anti-reflective coatings are classified into “organic” and “inorganic” by the materials used and into “absorption” and “interference” by the mechanisms involved. In microlithographic processes using an I-line light source (365 nm in wavelength), inorganic anti-reflective coatings are usually used, for example TiN or amorphous carbon coatings are applied when advantage is taken of an absorption mechanism, and SiON coatings are applied when an interference mechanism is desired. The SiON anti-reflective coatings are also adapted for submicrolithographic processes which uses KrF light sources.
Recently, extensive and intensive research has been and continues to be directed to the application of organic anti-reflective coatings for such submicrolithography. In view of the present development status, organic anti-reflective coatings, to be useful, must satisfy the following fundamental requirements:
First, peeling of the photoresist layer due to dissolution in solvents should not take place when conducting a lithographic process with an organic anti-reflective coating. In this regard, the organic anti-reflective coating materials have to be designed so that their cured films have a cross-linked structure without producing by-products.
Second, there should be no migration of chemical materials, such as amines or acids, into and from the anti-reflective coatings. If acids are migrated from the coatings, the photosensitive patterns are undercut while the egress of bases, such as amines, causes a “footing” phenomena.
Third, faster etch rates should be realized in the anti-reflective coatings than in the upper photosensitive film, allowing an etching process to be conducted smoothly with the photosensitive film serving as a mask.
Finally, the organic anti-reflective coatings should be as thin as possible while playing an excellent role in preventing light reflection.
As varied as anti-reflective coatings are, those which are satisfactorily applied to submicrolithographic processes using ArF light have not been found, thus far. As for inorganic anti-reflective coatings, there have been reported no materials which can control interference at the wavelength of ArF light, that is, 193 nm. As a result, active research has been conducted to develop organic materials which can form superb anti-reflective coatings. In fact, in most cases of submicrolithography, the coating of photosensitive layers is necessarily accompanied by the coating of organic anti-reflective layers which prevent the standing waves and reflective notching occurring upon light exposure and eliminate the influence of back diffraction and reflective light from lower layers. Accordingly, the development of such anti-reflective coating materials showing high absorption properties at specific wavelengths is one of the hottest and most urgent issues in the art.
SUMMARY OF THE INVENTION
The present invention overcomes the problems encountered in the prior art and provides a novel organic compound which can be used in an anti-reflective coating for submicrolithography processes using 193 nm ArF and 248 nm KrF lasers.
The present invention provides a method for preparing an organic compound which prevents the diffusion and reflection caused by light exposure in submicrolithography process.
The present invention further provides an anti-reflective coating composition containing such a diffusion/reflection-preventive compound and a preparation method therefor.
The present invention also provides an anti-reflective coating formed from such a composition and a preparation method therefor.
The present invention pertains to acrylate polymer resins (also referred to herein as “polymers” or “resins”) which can be used as an anti-reflective coating. The polymer resins contain a chromophore which shows high absorbance of light having wavelengths of 198 nm and 248 nm. In addition, a cross-linking mechanism between alcohol groups and other functional groups is introduced into the polymer resins, so that a cross-linking reaction takes place when the coatings of the polymer resins are “hard baked,” i.e., heated at a temperature of 100-300° C. for 10-1,000 seconds. As a result, a great improvement can be effected in the formation, tightness and dissolution properties of the anti-reflective coatings. Particularly, maximal cross-linking reaction efficiency and storage stability are realized in the practice of the present invention.
The anti-reflective coating resins of the present invention have superior solubility in all hydrocarbon solvents, in order to form a coating composition, yet are of such high solvent resistance after hard baking that they are not dissolved in any solvent at all. These advantages allow the resins to be coated without any problem to form an anti-reflective coating which prevents undercutting and footing problems when images are formed on the overlying photosensitive layer. Furthermore, coatings made of the acrylate polymers of the invention are higher in etch rate than the photosensitive film coatings, thereby improving the etch selection ratio therebetween.
REFERENCES:
patent: 4424270 (1984-01-01), Erdmann et al.
patent: 4822718 (1989-04-01), Latham et al.
patent: 5525457 (1996-06-01), Nemoto et al.
patent: 5674648 (1997-10-01), Brewer et al.
patent: 0 277 038 (1988-01-01), None
patent: WO00/01752 (2000-01-01), None
Baik Ki-Ho
Hong Sung-Eun
Jung Min-Ho
Hyundai Electronics Industries Co,. Ltd.
Pezzuto Helen L.
Townsend and Townsend / and Crew LLP
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