Monomer having fluorine-containing acetal or ketal structure, polymer thereof, and chemical-amplification-type resist composition as well as process for formation of pattern with use of the same
As a polymer exhibiting improved transparency which is suitable for a resist resin used in a chemical-amplification-type resist being applicable for photolithography using exposure light at 180 nm or shorter, this invention provides a polymer comprising a repeating unit resulting from polymerization of a monomer exhibiting a polymerization activity, wherein the monomer has a fluorine-containing acetal or ketal structure represented by general formula (1): wherein R represents an atomic group containing a carbon-carbon double bond exhibiting polymerization activity; at least one of R 1 and R 2 is fluorinated alkyl group or fluorinated aryl group having 1 to 20 carbon atoms; and R 3 represents a radical selected from the group consisting of hydrogen atom, alkyl group, alkoxy-substituted alkyl group, fluorinated alkyl group, aryl group, fluorinated aryl group, aralkyl group and fluorinated aralkyl group having 1 to 20 carbon atoms.
1. A monomer containing a carbon-carbon double bond exhibiting polymerization activity thereby and having a fluorine-containing structure in the molecule,
wherein the monomer is a (meth)acrylate derivative having a fluorine-containing structure represented by general formula (2):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a fluorinated alkyl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom; and
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
2. A polymer being producible by polymerization of one or more monomer materials containing a carbon-carbon double bond exhibiting polymerization activity thereby, wherein the polymer comprises a repeating unit being obtainable by addition polymerization of at least one of the monomer as claimed in claim 1 , as one of the repeating units contained in the polymer.
3. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer therefor, wherein the composition comprises the polymer as claimed in claim 2 as said resist resin.
4. A monomer containing a carbon-carbon double bond exhibiting polymerization activity thereby and having a fluorine-containing structure in the molecule,
wherein the monomer is a norbornene derivative or tetracyclododecene derivative having a fluorine-containing structure represented by general formula (3):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
X 1 and X 2 independently represent a hydrogen atom or a methyl group;
Z represents —CO—; and
m is 0 or 1.
5. A polymer being producible by polymerization of one or more monomer materials containing a carbon-carbon double bond exhibiting polymerization activity thereby, wherein the polymer comprises a repeating unit being obtainable by ring-opening metathesis polymerization of at least one of the monomer as claimed in claim 4 and then hydrogenating a —CH═CH— moiety resulting therefrom, as one of the repeating units contained in the polymer.
6. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer therefor, wherein the composition comprises the polymer as claimed in claim 5 as said resist resin.
7. A monomer containing a carbon-carbon double bond exhibiting polymerization activity thereby and having a fluorine-containing structure in the molecule,
wherein the monomer is a tricyclononene derivative having a fluorine-containing structure represented by general formula (4):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; and
Z represents —CO—, a methylene group or a linking group composed of a carbon-oxygen bond.
8. A polymer being producible by polymerization of one or more monomer materials containing a carbon-carbon double bond exhibiting polymerization activity thereby, wherein the polymer comprises a repeating unit being obtainable by ring-opening metathesis polymerization of at least one of the monomer as claimed in claim 7 and then hydrogenating a —CH═CH— moiety resulting therefrom, as one of the repeating units contained in the polymer.
9. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer therefor, wherein the composition comprises the polymer as claimed in claim 8 as said resist resin.
10. A polymer comprising one or more repeating units being obtainable by addition polymerization of a (meth)acrylate derivative, wherein the unit has a fluorine-containing structure represented by general formula (2a):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a fluorinated alkyl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom; and
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
11. The polymer as claimed in claim 10 , comprising, in addition to said repeating unit having a fluorine-containing structure, one or more repeating units selected from the group consisting of
a repeating unit represented by general formula (5):
wherein
R 7 and R 8 are independently a hydrogen atom or a fluorine atom;
R 9 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
R 10 represents a radical selected from the group consisting of a hydrogen atom; a linear, branched or cyclic alkyl group and fluorinated alkyl group having 1 to 20 carbon atoms; a group removable by an acid; a bridged cyclic hydrocarbon group having 7 to 13 carbon atoms containing a group removable by an acid thereon and norbornane-2,6-carbolactone-5-yl group;
a repeating unit represented by general formula (6):
wherein R 11 represents a hydrogen atom or a group removable by an acid;
a repeating unit represented by general formula (7):
wherein R 12 represents a hydrogen atom or a group removable by an acid;
a tetrafluoroethylene radical represented by formula (8):
—CF 2 —CF 2 — (8)
a repeating unit represented by general formula (9):
wherein R 13 and R 14 independently represent a hydrogen atom or a fluorine atom; R 15 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 16 represents a hydrogen atom, a hydroxy group, hydroxy alkyl group or an acid-dissociable organic group having 20 or less carbon atoms which can generate a carboxy group therefrom by its decomposition by an acid;
a repeating unit represented by general formula (10):
wherein R 13 and R 14 independently represent a hydrogen atom or a fluorine atom; R 15 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 16 represents a hydrogen atom, a hydroxy group, a hydroxy alkyl group or an acid-dissociable organic group having 20 or less carbon atoms which can generate a carboxy group therefrom by its decomposition by an acid;
a repeating unit represented by general formula (11):
wherein R 13 and R 14 is independently a hydrogen atom or a fluorine atom; R 15 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 16 represents a hydrogen atom, a hydroxy group, a hydroxy alkyl group or an acid-dissociable organic group having 20 or less carbon atoms which can generate a carboxy group therefrom by its decomposition by an acid;
a repeating unit represented by general formula (12):
wherein R 13 and R 14 is independently a hydrogen atom or a fluorine atom; R 15 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 16 represents a hydrogen atom, a hydroxy group, a hydroxy alkyl group or an acid-dissociable organic group having 20 or less carbon atoms which can generate a carboxy group therefrom by its decomposition by an acid; and
an anhydrous succindiyl represented by formula (13):
12. The polymer as claimed in claim 10 , wherein the polymer comprises said repeating unit represented by general formula (2a) in a content of at least 5 to 90 mol % to the total number of the repeating units composing the polymer.
13. The polymer as claimed in claim 10 , wherein a weight-average molecular weight of the polymer is selected in the range of 2,000 to 200,000.
14. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer,
wherein the composition comprises one or more of the polymers as claimed in claim 10 as said resist resin and at least a photo-acid generator capable of generating an acid by exposure light as said photo-sensitizer; and
the content of the photo-acid generator to the total amount of the polymer and the photo-acid generator is selected in the range of 0.2 to 30 wt %.
15. A process for formation of pattern by photolithography utilizing a chemical-amplification-type resist, comprising at least the steps of:
forming a film of the chemical-amplification-type resist as claimed in claim 14 applied onto a substrate to be processed for formation of pattern thereon;
irradiating the substrate with light at a wavelength of 130 to 180 nm as exposure light in accordance with a pattern to be formed to expose said film of the chemical-amplification-type resist;
carrying out baking treatment for said exposed film of the chemical-amplification-type resist; and
carrying out developing treatment for said film treated by baking.
16. The process for formation of pattern as claimed in claim 15 , wherein the light at a wavelength of 130 to 180 nm used in said exposure step is F 2 excimer laser beam.
17. A polymer comprising one or more repeating units being obtainable by addition polymerization of a norbornene derivative or a tetracyclododecene derivative, wherein the unit has a fluorine-containing structure represented by general formula (3a):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
X 1 and X 2 independently represent a hydrogen atom or a methyl group;
Z represents —CO—; and
m is 0 or 1.
18. The polymer as claimed in claim 17 , wherein the polymer comprises said repeating unit represented by general formula (3a) in a content of at least 5 to 90 mol % to the total number of the repeating units composing the polymer.
19. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer,
wherein the composition comprises one or more of the polymers as claimed in claim 17 as said resist resin and at least a photo-acid generator capable of generating an acid by exposure light as said photo-sensitizer; and
the content of the photo-acid generator to the total amount of the polymer and the photo-acid generator is selected in the range of 0.2 to 30 wt %.
20. A polymer comprising one or more repeating units being obtainable by addition polymerization of a tricyclononene derivative, wherein the unit has a fluorine-containing structure represented by general formula (4a):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; and
Z represents —CO—, a methylene group or a linking group composed of a carbon-oxygen bond.
21. The polymer as claimed in claim 20 , wherein the polymer comprises said repeating unit represented by general formula (4a) in a content of at least 5 to 90 mol % to the total number of the repeating units composing the polymer.
22. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer,
wherein the composition comprises one or more of the polymers as claimed in claim 20 as said resist resin and at least a photo-acid generator capable of generating an acid by exposure light as said photo-sensitizer; and
the content of the photo-acid generator to the total amount of the polymer and the photo-acid generator is selected in the range of 0.2 to 30 wt %.
23. A process for formation of pattern by photolithography utilizing a chemical-amplification-type resist, comprising at least the steps of:
forming a film of the chemical-amplification-type resist as claimed in claim 22 applied onto a substrate to be processed for formation of pattern thereon;
irradiating the substrate with light at a wavelength of 130 to 180 nm as exposure light in accordance with a pattern to be formed to expose said film of the chemical-amplification-type resist;
carrying out baking treatment for said exposed film of the chemical-amplification-type resist; and
carrying out developing treatment for said film treated by baking.
24. A polymer comprising one or more repeating units being obtainable by ring-opening polymerization of a norbornene derivative or tetracyclododecene derivative and then hydrogenating a —CH═CH— moiety resulting therefrom, wherein the unit has a fluorine-containing structure represented by general formula (3b):
wherein
R 1 and P 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aryl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
X 1 and X 2 independently represent a hydrogen atom or a methyl group;
Z represents —CO—, a methylene group or a linking group composed of a carbon-oxygen bond; and
m is 0 or 1.
25. The polymer as claimed in claim 24 , wherein the polymer comprises said repeating unit represented by general formula (3b) in a content of at least 5 to 90 mol % to the total number of the repeating units composing the polymer.
26. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer,
wherein the composition comprises one or more of the polymers as claimed in claim 24 as said resist resin and at least a photo-acid generator capable of generating an acid by exposure light as said photo-sensitizer; and
the content of the photo-acid generator to the total amount of the polymer and the photo-acid generator is selected in the range of 0.2 to 30 wt %.
27. A process for formation of pattern by photolithography utilizing a chemical-amplification-type resist, comprising at least the steps of:
forming a film of the chemical-amplification-type resist as claimed in claim 26 applied onto a substrate to be processed for formation of pattern thereon;
irradiating the substrate with light at a wavelength of 130 to 180 nm as exposure light in accordance with a pattern to be formed to expose said film of the chemical-amplification-type resist;
carrying out baking treatment for said exposed film of the chemical-amplification-type resist; and
carrying out developing treatment for said film treated by baking.
28. A polymer comprising one or more repeating units being obtainable by ring-opening polymerization of a tricyclononene derivative and then hydrogenating a —CH═CH— moiety resulting therefrom, wherein the unit has a fluorine-containing structure represented by general formula (4b):
wherein
R 1 and R 2 independently represent a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, a fluorinated alkyl group, an aryl group and a fluorinated aryl group having 1 to 20 carbon atoms; and at least one of R 1 and R 2 is said fluorinated alkyl group or said fluorinated aryl group;
R 3 represents a radical selected from the group consisting of a hydrogen atom, a linear, branched or cyclic alkyl group, an alkoxy-substituted alkyl group, a fluorinated alkyl group, an aryl group, a fluorinated aiyl group, an aralkyl group and a fluorinated aralkyl group having 1 to 20 carbon atoms;
R 4 and R 5 independently represent a hydrogen atom or a fluorine atom;
R 6 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; and
Z represents —CO—, a methylene group or a linking group composed of a carbon-oxygen bond.
29. The polymer as claimed in claim 28 , wherein the polymer comprises said repeating unit represented by general formula (4b) in a content of at least 5 to 90 mol % to the total number of the repeating units composing the polymer.
30. A resist composition of chemical-amplification-type comprising a resist resin and a photo-sensitizer,
wherein the composition comprises one or more of the polymers as claimed in claim 28 as said resist resin and at least a photo-acid generator capable of generating an acid by exposure light as said photo-sensitizer; and
the content of the photo-acid generator to the total amount of the polymer and the photo-acid generator is selected in the range of 0.2 to 30 wt %.
31. A process for formation of pattern by photolithography utilizing a chemical-amplification-type resist, comprising at least the steps of:
forming a film of the chemical-amplification-type resist as claimed in claim 30 applied onto a substrate to be processed for formation of pattern thereon;
irradiating the substrate with light at a wavelength of 130 to 180 nm as exposure light in accordance with a pattern to be formed to expose said film of the chemical-amplification-type resist;
carrying out baking treatment for said exposed film of the chemical-amplification-type resist; and
carrying out developing treatment for said film treated by baking.