Cyclic dione polymer

Details Cyclic dione polymer Cyclic dione polymer

2000-09-29

2001-10-16

Henderson, Christopher (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S240000, C526S256000, C526S265000, C526S268000, C526S274000, C526S279000, C526S281000, C526S291000, C526S316000, C528S403000

Reexamination Certificate

active

06303725

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel cyclic dione polymer, and more particularly relates to a novel cyclic dione polymer that is suitable for use in thin film coating and photoresist technology.
2. Description of the Prior Art
Nowadays, thin film coating and photoresist technology play very important roles in chemical engineering technology. A resin suitable for thin film coating should meet the requirements of not only having good film properties and good adherence to substrates, but also having good stability over a long storage time and low moisture absorbability. Therefore, a suitable resin should not have too many functional groups of high moisture absorbability. To be considered for application in IC photoresists, a suitable resin should further have other properties such as high etch and heat resistance, properties which are frequently achieved by molecular design.
To date, the most frequently used resin for thin film coating is the copolymer of a maleic anhydride derivative and norbornene, which has been disclosed in U.S. Pat. No. 3,928,497. Such a resin is suitable for being applied in IC photoresists because it has a broad processing window and linear relationship. However, since maleic anhydride easily absorbs moisture to form acid molecules, it has an inferior shelf life. Moreover, when the humidity in the air varies greatly, the E
0
(photo speed) and &ggr; (contrast) will be difficult to be controlled; therefore, a stable line width of good properties can not be obtained. Since the disadvantage of high absorbability of said resin is due to its chemical structure, incorporating a plastisizer of low moisture absorbability is the only way to date of decreasing the absorbability of the maleic anhydride derivative
orbornene copolymer. In addition, said copolymer has other disadvantages: the glass transition temperature is too high, the film properties are inferior, and the film will easily crack.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a novel resin which has a lower moisture absorbability and transition temperature, good adherence and storage stability, and can be used in thin film coating and photoresist technology.
To achieve the above object, the present invention uses specific monomers to prepare resins, so as to improve the properties of the resins. The present invention uses a cyclic dione monomer to replace the conventional maleic anhydride derivative, and further provides a resin system prepared from such a cyclic dione monomer. Since such a cyclic dione monomer has low moisture absorbability, the resin prepared from the monomer will have a decrease moisture absorbability.
The novel resin system of the present invention is a cyclic dione polymer, which is a homopolymer or a copolymer of a cyclic dione monomer selected from those represented by formulae (I) and (II)
wherein
A and B may be the same or different and are independently selected from the group consisting of halogen, hydrogen, C
3-20
cyclic or pericyclic alkyl, C
1-20
linear and branched alkyl, C
6-20
aryl, C
7-20
arylalkyl, C
7-20
alkylaryl, silyl, alkylsilyl, germyl, alkylgermyl, alkoxycarbonyl, acyl, and a heterocylic group; or, A and B are linked together to form a C
3-20
saturated or unsaturated cyclic hydrocarbon group or a substituted or unsubstituted heterocyclic group;
C is selected from the group consisting of oxygen, sulfur,
 —CH
2
—, and —SiH
2
—,
wherein each R
1
is independently selected from C
1-20
alkyl and phenyl.
Representative examples of the cyclic dione monomers of formula (I) include
Representative examples of the cyclic dione monomers of formula (II) include
The cyclic dione polymer of the present invention can also be a copolymer including a cyclic olefin comonomer. That is, the cyclic dione polymer of the present invention can be a copolymer of at least one cyclic dione monomer of formula (I) or (II) and at least one comonomer of a cyclic olefin. The cyclic olefin suitable for use can be norbornene or a norbornene derivative.
The norbornene derivative can be
The norbornene derivative can also be a compound having the following formula:
wherein m is an integer from 1 to 3; or a compound having the following formula:
wherein q is an integer from 1 to 3, and X is selected from O, N, or S.
A “chemically amplified resist” is a kind of photoresist in which the rate of dissolution in a developer can be changed by an acid produced by photoirradiation. Such a photoresist solution includes a protected resin, a photoacid generator, and a solvent. The so-called protected resin is a resin that is protected by an acid-labile protective group. The resin will be converted into alkali-soluble when the acid-labile protective group is decomposed. When the chemically amplified resist applied on a substrate is exposed to light, the photoacid generator will generate acid, and the acid will decompose the acid-labile protective group in the resin, thus making the resin soluble in an alkali developer
Therefore, if the cyclic dione polymer of the present invention is used for a chemically amplified resist, such a cyclic dione polymer preferably has an acid-labile protective group, which will be decomposed in the presence of an acid so that the cyclic dione polymer will be converted into an alkali-soluble polymer.
Such an acid-labile protective group may be present in formula (I), formula (II), a cyclic olefin comonomer that can be copolymerized with formula (I) or (II), or present in any monomer that can be copolymerized with formula (I) or (II).
For example, a cyclic olefin comonomer that can be copolymerized with formula (I) or (II) can be norbornene or a norbornene derivative. Such a norbornene derivative can have an acid-labile protective group D. Thus, when the cyclic dione polymer of the present invention is in the presence of an acid, the protective group D will be decomposed, such that the cyclic dione polymer will be converted to an alkali soluble polymer. Such norbornene derivatives include:
wherein
D is an acid-labile protective group, which is decomposed in the presence of an acid, so as to make the cyclic dione polymer alkali-soluble, and
each R
3
is independently selected from the group consisting of hydrogen, C
1-20
linear and branched alkyl, C
3-20
cyclic and pericyclic alkyl.
Representative examples of D include:
wherein R
1
is selected from the group consisting of hydrogen, C
1-20
linear and branched alkyl, C
3-20
cyclic and pericyclic alkyl.
As described above, the cyclic dione polymer of the present invention can be a copolymer of at least one cyclic dione monomer of formula (I) or (II) and at least one comonomer of a cyclic olefin. For example, formula (I) can be reacted with any above-mentioned norbornene derivative containing an acid-labile protective group via free radical polymerization. Also, formula (II) can be reacted with any above-mentioned norbornene derivative containing an acid-labile protective group via free radical polymerization. The obtained cyclic dione polymer can be represented by formula (III):
wherein
A, B, C, D, and R
3
are defined as above,
p, q, x, y, and z are the molar ratios of the corresponding monomers,
p+q+x+y+z=1,
p, q, x, y, and z are in the range of 0 to 0.5,
p+q is larger than 0, and
x+y+z is in the range of 0 to 0.8.
Particularly, the obtained cyclic dione polymer can be represented by formula (IV):
wherein
A, B, C, D, and R
3
are defined as above,
p and y are the molar ratios of the corresponding monomers,
p+y=1, and
p and y are in the range of 0.1 to 0.9.
The cyclic dione polymer of the present invention is not limited to those obtained via free radical polymerization. All homopolymers and copolymers obtained by using the cyclic dione monomer of formula (I) or (II) as the monomer are within the scope of the present invention, no matter what the polymerization is. The polymerization can be free radical polymerizati

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