Coating processes – Direct application of electrical – magnetic – wave – or... – Pretreatment of substrate or post-treatment of coated substrate
Reexamination Certificate
2003-08-07
2004-11-16
Padgett, Marianne (Department: 1762)
Coating processes
Direct application of electrical, magnetic, wave, or...
Pretreatment of substrate or post-treatment of coated substrate
C427S555000, C428S421000, C526S249000, C430S270100, C430S913000, C430S945000
Reexamination Certificate
active
06818258
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a novel fluorinated resist composition. More particularly, it relates to a chemical amplification type resist composition useful for fine processing employing far ultraviolet rays such as KrF or ArF excimer laser, or vacuum ultraviolet rays such as F
2
excimer laser.
BACKGROUND ART
In recent years, along with the progress in fine circuit patterns in the process for producing semiconductor integrated circuits, a photoresist material having high resolution and high sensitivity is desired. As the circuit patterns become fine, a short wavelength of a light source for an exposure apparatus becomes essential. In an application to lithography employing an excimer laser of 250 nm or shorter, a polyvinyl phenol type resin, an alicyclic acrylic type resin or a polynorbornene type resin has, for example, been proposed, but no adequate resolution and sensitivity have been obtained.
It is an object of the present invention to provide a resist composition which is particularly excellent in transparency to a radiation and in dry etching properties, as a chemical amplification type resist and which gives a resist pattern excellent in sensitivity, resolution, evenness, heat resistance, etc.
DISCLOSURE OF THE INVENTION
The present invention is the following invention which has been made to solve the above-described problems.
1) A resist composition comprising a fluoropolymer (A) which is a fluoropolymer having repeating units formed by cyclopolymerization of a fluorinated diene represented by the formula (1) and which has blocked acidic groups, provided that in a case where Q is a bivalent organic group having a group which can be converted to a blocked acidic group, said group is converted to a blocked acidic group after the cyclopolymerization, an acid-generating compound (B) which generates an acid under irradiation with light, and an organic solvent (c):
CF
2
═CR
1
—Q—CR
2
═CH
2
(1)
wherein each of R
1
and R
2
which are independent of each other, is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Q is a bivalent organic group having a blocked acidic group capable of forming an acidic group by an acid or a group which can be converted to such a blocked acidic group.
2) The resist composition according to 1), wherein Q is a bivalent organic group represented by the formula (2):
—R
3
—C(R
5
)(R
6
)—R
4
— (2)
wherein each of R
3
and R
4
which are independent of each other, is a single bond, an oxygen atom, an alkylene group having at most 3 carbon atoms, which may have an etheric oxygen atom, or a fluoroalkylene group having at most 3 carbon atoms, which may have an etheric oxygen atom, R
5
is a hydrogen atom, a fluorine atom, an alkyl group having at most 3 carbon atoms or a fluoroalkyl group having at most 3 carbon atoms, and R
6
is a blocked acidic group, an acidic group, or a monovalent organic group having a blocked acidic group or an acidic group.
3) The resist composition according to 1) or 2), wherein the acidic group is an acidic hydroxyl group, and the blocked acidic group is a blocked acidic hydroxyl group.
4) The resist composition according to 1), 2) or 3), wherein the fluorinated diene is a fluorinated diene represented by the formula (4) or (5):
CF
2
═CFCF
2
C(—X
2
)(CF
3
)CH
2
CH═CH
2
(4)
CF
2
═CFCF
2
CH(—(CH
2
)
p
C(CF
3
)
2
—X
2
)CH
2
CH═CH
2
(5)
wherein X
2
is O(t-C
4
H
9
), OCH
2
OCH
3
, OCOO(t-C
4
H
9
), OCH(CH
3
)OC
2
H
5
or a 2-tetrahydropyranyloxy group, and p is an integer of from 1 to 3.
5) A process for forming a pattern, which comprises coating the resist composition as defined in 1), 2), 3) or 4) on a substrate, then removing the organic solvent (C) to form a thin film of a resist comprising the fluoropolymer (A) and the acid-generating compound (B), and then irradiating the thin film with ultraviolet rays having a wavelength of at most 200 nm capable of generating an acid from the acid-generating compound (B) to form a pattern.
BEST MODE FOR CARRYING OUT THE INVENTION
It is considered that by the cyclopolymerization of the fluorinated diene represented by the formula (1) (hereinafter referred to as the fluorinated diene (1)), the following repeating units (a) to (c) will be formed. From the results of the spectroscopic analyses, etc., the cyclized polymer of the fluorinated diene (1) is considered to be a polymer having a structure comprising repeating units (a), repeating units (b) or both of them, as the main repeating units. Here, the main chain of this cyclized polymer is meant for a carbon chain constituted by carbon atoms which constitute polymerizable unsaturated bonds (in the case of the fluorinated diene (1), the four carbon atoms which constitute polymerizable unsaturated double bonds).
In the formula (1), each of R
1
and R
2
which are independent of each other, is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R
1
is preferably a fluorine atom or a trifluoromethyl group. R
2
is preferably a hydrogen atom or a methyl group. Q is a bivalent organic group having a blocked acidic group capable of forming an acidic group (hereinafter referred to simply as a blocked acidic group) or a group which can be converted to such a blocked acidic group (hereinafter referred to as a precursor group). In a case where Q is a bivalent organic group having the precursor group, after the cyclopolymerization of the fluorinated diene (1), the precursor groups in the polymer will be converted to blocked acidic groups.
The fluoropolymer (A) in the present invention has blocked acidic groups. In a case where the fluorinated diene (1) has a blocked acidic group, the fluoropolymer (A) can be obtained by its cyclopolymerization. In a case where the fluorinated diene (1) has the precursor groups, the fluoropolymer (A) can be obtained by converting the precursor groups in the polymer obtained by its cyclopolymerization, to blocked acidic groups. The precursor group may be an acidic group or a group which can be converted to an acidic group. The acidic group can be converted to a blocked acidic group by reacting it with a blocking agent. The group which can be converted to an acidic group, may be a blocked acidic group other than the desired blocked acidic group. By conversion of the blocked portion, it can be converted to the desired blocked acidic group. The blocked ratio of the fluoropolymer (A) (i.e. the ratio of blocked acidic groups to the total of the blocked acidic groups and non-blocked acidic groups) is preferably from 10 to 100 mol %, particularly preferably from 10 to 90 mol %.
In Q, the minimum distance between connecting bonds at its both terminals corresponds preferably to from 2 to 6 atoms, particularly preferably 2 to 4 atoms, as represented by the number of atoms (the atomic chain constituting this minimum distance will be hereinafter referred to as the main chain). The atoms constituting the main chain may be composed of carbon atoms only, or carbon atoms and other bivalent or higher valent atoms. The bivalent or higher valent atoms other than carbon atoms, may, for example, an oxygen atom, a sulfur atom and a nitrogen atom substituted by a monovalent group. An oxygen atom is particularly preferred. Such an oxygen atom or the like may be present at either one or both of the two terminals, or may be present between carbon atoms in Q.
In the main chain in Q, at least one carbon atom is present, and to a carbon atom constituting the main chain in Q, a blocked acidic group, a precursor group or an organic group containing a blocked acidic group or a precursor group, is bonded. In addition to such a specific group, hydrogen atoms or halogen atoms (particularly preferably fluorine atoms) are bonded to carbon atoms, etc. constituting the main chain, and further, an alkyl group, a fluoroalkyl group, an alkoxy group, an aryl group or other organic groups may be bonded thereto. The carbon number of such an organic group is preferably at most 6.
The acidic group may, for exampl
Kaneko Isamu
Kawaguchi Yasuhide
Kodama Shun-ichi
Okada Shinji
Takebe Yoko
Asahi Glass Company Limited
Padgett Marianne
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