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
2001-02-23
2003-08-19
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
C430S905000, C430S323000, C560S120000, C556S465000, C526S281000
Reexamination Certificate
active
06607867
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to norbornene monomers containing an organometal and its manufacturing method, especially to norbornene monomers with a novel functional group containing an organometal used for the manufacturing of a photoresist, and its manufacturing method.
Furthermore, the present invention relates to photoresist and its manufacturing method, especially to phtoresist which can form high resolution patterns in deep-UV wavelength region by copolymerizing aforementioned norbornene monomers or by copolymerizing norbornene monomers with other material, and its manufacturing method.
Still furthermore, the present invention relates to a method forming the aforementioned phtoresist patterns.
2. Description of the Prior Art
With increasing integration of semiconductor devices, there may be a heightened need to form finer patterns of subquarter micron in photolithographic processes. According to the request of fine patterns, processes that can form patterns utilizing deep-UV light from KrF eximer laser with wavelength of 248 nm or ArF eximer laser with wavelength of 193 nm which have shorter wavelength than existing g-line with wavelength of 436 nm or I-line with wavelength of 365 nm came to be necessary.
The photoresist containing Novolac-naphtoquinonediazide compounds utilized in the g-line and I-line has strong absorption in the deep-UV region and is low in sensitivity that it can not be applied in the deep-UV wavelength region. Therefore, the development of new photoresist is required.
New photoresist should satisfy various requirements such as high sensitivity, contrast, high resolution, and resistance to dry etching process. Among them, the sensitivity is the most important in the development of photoresist and the concept of chemical amplification is introduced to enhance sensitivity.
The chemically amplified photoresist is comprised of photosensitive acid generator (PAG) and a polymer combined with dissolution inhibitor.
The exposure of the chemically amplified photoresist hydrolyzes dissolution inhibitor on a polymer main chain by the catalytic reaction of acid from photosensitive acid generator, and the polarity of polymer is changed. Its development in polar or nonpolar solvent yields positive or negative type photoresist patterns. U.S. Pat. No. 4,991,628 discloses the use of polyvinylphenol protected by t-butoxycarbonyl functional group for the application in the chemically amplified photoresist.
However, both the conventional positive or negative type chemically amplified photoresists have several problems. Major problems are deformation and collapse of resist pattern in a wet developing and rinsing according to the increase of aspect ratio of a pattern.
To overcome the problems, the strength of matrix polymer contained in photoresist and the adhesion of photoresist to substrate must be good and appropriate developing and rinsing solution should be selected. However, the solution has also limits because the increase of aspect ratio is inevitable and adhesion has limit, too.
SUMMARY OF THE INVENTION
Therefore, the first object of the present invention is to provide norbornene monomers containing novel organometal for the manufacuture of photoresist, which can form high resolution patterns in deep-UV wavelength region.
The second object of the present invention is to provide a norbornene monomer manufacturing method containing appropriate organometal to achieve the above described object.
The third object of the present invention is to provide photoresist utilizing norbornene monomers supplied by achieving the first object.
The fourth object of the present invention is to provide a photoresist manufacturing method suitable to achieve the third object.
The fifth object of the present invention is to provide a method for forming patterns of photoresist, which is supplied by achieving the third object.
Norbornene monomer containing organometal for photoresist according to one embodiment of the present invention to achieve the above first object is presented in the following Formula (I),
wherein R
1
to R
8
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl or —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy.
Norbornene monomer containing organometal for photoresist according to another embodiment of the present invention to achieve the above first object is presented in the following Formula (II),
wherein R
1
to R
10
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy.
The norbornene monomer manufacturing method according to one embodiment of the present invention to achieve the above second object is characterized as follows; Alcohol containing organometal as shown in the Formula (XII) or (XIII) is synthesized. The alcohol is reacted with 2-chlorocarbonyl-5-norbornene derivative at 0° C. at ambient atmosphere for 1~2 hours, and then further reacted at room temperature and ambient atmosphere for 5~6 hours to yield norbornene monomer as shown in Formula (I) or (II). The synthetic methods for alcohol with Formula (XII) or (XIII) are reported previously (J. Organomet. Chem. 49(1973) C9-C12, J. Org. Chem 45(1980) 3571-3578, Tetrahedron Lett. (1976) 1591-1594, J. Organomet. Chem. (1981) 33-47),
wherein R
1
to R
10
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl or —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy.
The photoresist according to one embodiment of the present invention to achieve the above third object is characterized to comprise a polymer and a photosensitive acid generator as shown in the following Formula (III),
wherein R
1
to R
8
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl or —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy; n is degree of polymerization and is between 1 to 100.
The photoresist according to another embodiment of the present invention to achieve the above third object is characterized to comprise a polymer and a photosensitive acid generator (not shown) as shown in the following Formula (IV),
wherein R
1
to R
10
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl or —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy; n is degree of polymerization and is between 1 to 100.
The photoresist according to another embodiment of the present invention to achieve the above third object is characterized to comprise a polymer and a photosensitive acid generator as shown in the following Formula (V),
wherein, A represents the following Formula (VII) or (VIII), and
wherein R
1
to R
10
independently represent hydrogen, alkyls having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl or —MR′
3
; M is either Si, Ge, Sn or OSi; and R′ is either alkyl having from 1 to 4 carbon atoms, alkoxy having from 1 to 4 carbon atoms, phenyl, benzyl or phenoxy; x,y,z are mole ratio of a polymer and x+y+z=1.
The photoresist according to another embodiment of the present invention to achieve the above third object is characterized to comprise a polymer and a photosensitive acid generator as shown in the following Formula (VI),
wherein
Kang Jae-Sung
Kim Jin-Baek
Lee Jae-Jun
Ashton Rosemary
Foley & Lardner
Korea Advanced Institute of Science and Technology
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