Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-10-16
2002-11-05
Owens, Amelia (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S363000, C549S430000, C560S128000
Reexamination Certificate
active
06476240
ABSTRACT:
BACKGROUND OF THE INVENTION
As alkaline soluble resins, there have heretofore been known novolac resin, phenolic resin, and polymers having acrylic acid or methacrylic acid as a structural component, and they have been used in photo prints and as the resist materials for electronics industries, and among them many polymers have been put into practical use. The following is typical examples; UV lights including g-line light (wavelength of 436 nm) and i-line light (wavelength of 365 nm) have been used as an exposure source in lithography field and further excimer laser beams (KrF excimer laser beams; A wavelength of 248 nm and ArF excimer laser beams; wavelength of 193 nm) has recently been used for this purpose, and as the base polymers of the resist materials in accordance with the exposure source, novolac resin is mainly used as resist materials for g-line light and i-line light and phenolic resin is mainly used as resist materials for KrF, and both of those resins contain phenolic hydroxy groups (pKa of about 12) as functional groups which can be developed by an alkaline developing solution.
On the other hand, an acrylic acid derivative type or a methacrylic acid derivative type resins have mainly been used as a base polymer of ArF resist materials which have still been under developing stage (For instance, Japanese Patent Application Kokai (Laid-Open) Nos. (JP-A-) 7-199467, JP-A-8-82925 and JP-A-7-234511). The reason is that resins having aromatic rings so far being used is low in their transparency in far ultraviolet range and particularly it becomes completely non-transparent at the wavelength of ArF excimer laser beams, i.e.193 nm. However, those resist materials wherein acrylic acid resin or methacrylic acid resin is used as the base polymer show high acidity (pKa of about 5) because a carboxylic group is used as a soluble group, which results in higher dissolving speed upon the development by alkaline substance as compared with known polymer wherein phenol groups are used as a soluble group, and therefore those resist materials are accompanied with such defects that a film is peeled off upon fine pattern formation and even non-exposured parts are dissolved out when a known alkaline developing solution, 2.38% tetramethylammonium hydroxide (TMAH), is used without diluting and thus no good pattern can be obtained.
Further, the main alkaline developing solution so far applied in actual production lines of semiconductor apparatuses is the above mentioned 2.38% TMAH, and it is actually very difficult to use the developing solution in diluted state in the production lines wherein resist materials belonging to different generations, such as both of i-line lights resist and KrF resist and both of KrF resist and ArF resist are applied together.
SUMMARY OF THE INVENTION
The present invention has been accomplished taking into consideration the above mentioned circumstances and has the object to provide a novel polymer showing high transmittance against deep-ultraviolet lights having a wavelength of 220 nm or less, particularly ArF excimer laser beams, which can give, upon using, for instance, as a polymer for a resist composition, a resist film showing high etching resistance and to provide a novel monomer usable as a starting material of the said polymer.
The present invention relates to a novel polymer useful as a resist composition used in the production of semiconductor elements and so on and to a novel monomer useful as a starting material of the said polymer.
More particularly, the present invention relates to a monomer shown by the general formula [1]
(wherein X′ is a cyclic hydrocarbon residue containing polymerizable double bond(s), which may have a substituent, Z is a spacer or a direct bond and R is a substituted alkyl or alkenyl group having one or two protected hydroxyl groups as substituent).
Further, the present invention relates to a polymer, which contains, as a constituent unit, a monomer unit shown by the general formula [1a]
(wherein X is a cyclic hydrocarbon residue which may have a substituent, and Z and R have the same meaning as above).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
For the purpose of attaining the above mentioned objects, the present inventors have extensively studied to find out a novel polymer containing, as a structural unit, a monomer unit shown by the above general formula [1a] having high transmittance in a wavelength region of 220 nm or less, which can give, upon using a resist material, a resist film showing high etching resistance, and the present invention has been accomplished on the basis of this finding.
The cyclic hydrocarbon residue containing polymerizable double bond(s), which may have a substituent, shown by X′ in the general formula [1] includes cyclic groups shown by the following general formulae [2] to [4]
(wherein R
16
and R
17
are each independently a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group, an aryl group, an aralkyl group or a carbamoyl group, and n is 0 or 1),
(wherein R
18
and R
19
are each independently a hydrogen atom, an alkyl group, a cyano group, an alkyloxycarbonyl group, an aryl group, an aralkyl group or a carbamoyl group, and ‘a’ is 0 or 1),
(wherein b is 0 or 1).
The cyclic hydrocarbon residue which may have a substituent, shown by X in the general formula [1a] is derived from the cyclic hydrocarbon residue containing polymerizable double bond(s), which may have a substituent, shown by X′ in the general formula [1], and it includes the groups shown by the following general formulae [2a] to [4a]
(wherein R
16
, R
17
and n have the same meaning as above),
(wherein R
18
, R
19
and ‘a’ have the same meaning as above),
(wherein b has the same meaning as above).
The alkyl group shown by R
16
to R
19
may be straight chained, branched or cyclic, and includes one having 1 to 20 carbon atoms, which is specifically exemplified by a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 3,3-dimethylbutyl group, a 1,1-dimethylbutyl group, a 1-methylpentyl group, an n-hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.
The alkyloxycarbonyl group may be straight chained, branched or cyclic.
The straight chained or branched one includes one having 2 to 19 carbon atoms, which is specifically exemplified by a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, a tert-butyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, etc.
The cyclic one may be monocyclic or polycyclic and includes alicyclic one having 6 to 14 carbon atoms, which is specifically exemplified by a cyclohexyloxycarbonyl group, a tricyclodecanyloxycarbonyl group, an adamantyloxycarbonyl group, a norbomyloxycarbonyl group, a bicyclo[3.2.1]octenyloxycarbonyl group, a bicyclo[2.2.2]octyloxycarbonyl group, a methyloxycarbonyl group, an isobornyloxycarbonyl group, etc.
The aryl group is specifically exemplified by a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a trimethylphenyl group, etc.
The aralkyl group includes one having 7 to 15 carbon atoms, which is specifically exemplified by a benzyl group, a phenethyl group, a naphthylmethyl group, etc.
The cyclic hydrocarbon residue containing polymerizable double bond(s) which may have a substituent, shown by X′ in the general formula [1] includes a monocyclic hydrocarbon residue, which is specifically exemplified
Armstrong Westerman & Hattori, LLP
Owens Amelia
Wako Pure Chemical Industries Ltd.
LandOfFree
Monomer and a polymer obtained therefrom does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Monomer and a polymer obtained therefrom, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Monomer and a polymer obtained therefrom will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2941832