Fluorine-free fused ring heteroaromatic photoacid generators and resist compositions containing the same
View Patent ↗The present invention relates to a fluorine-free photoacid generator (PAG) and a photoresist composition containing the same. The PAG is characterized by the presence of an onium cationic component and a fluorine-free fused ring heteroaromatic sulfonate anionic component containing one or more electron withdrawing substituents. The onium cationic component of the PAG is preferably a sulfonium or an iodonium cation. The photoresist composition further contains an acid sensitive imaging polymer. The photoresist composition is especially useful for forming material patterns on a semiconductor substrate using 193 nm (ArF) lithography.
1. A fluorine-free photoacid generator, said photoacid generator comprising an onium cationic component and an anionic component of formula (II):
wherein:
X is O;
Y is C;
each of G 1 -G 5 is selected from the group consisting of H; linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl; unsubstituted and substituted aromatic groups; unsubstituted and substituted heteroaromatic groups; and an electron withdrawing moiety, provided that at least one of G 1 -G 5 is an electron withdrawing moiety; and
said onium cationic component is selected from the group consisting of sulfonium cations and iodonium cations.
2. The photoacid generator of claim 1 wherein at least one of G 1 -G 5 is an electron withdrawing moiety selected from the group consisting of CN, NO, NO 2 , Cl, Br, I, SO 2 Me, and CHO.
3. The photoacid generator of claim 2 wherein at least one of G 1 -G 5 is selected from the group consisting of CN and NO 2 .
4. The photoacid generator of claim 2 wherein at least two of G 1 -G 5 are electron withdrawing moieties.
5. The photoacid generator of claim 1 wherein said onium cationic component comprises an aromatic moiety.
6. The photoacid generator of claim 5 wherein said onium cationic component has a structure selected from the group consisting of
wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of H;
linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl;
unsubstituted and substituted aromatic groups; and unsubstituted and substituted heteroaromatic groups.
7. A photoresist composition comprising:
(a) an acid sensitive imaging polymer; and
(b) a fluorine-free photoacid generator comprising an onium cationic component and an anionic component of formula (II):
wherein:
X is O;
Y is C;
each of G 1 -G 5 is selected from the group consisting of H; linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl; unsubstituted and substituted aromatic groups; unsubstituted and substituted heteroaromatic groups; and an electron withdrawing moiety, provided that at least one of G 1 -G 5 is an electron withdrawing moiety; and
said onium cationic component is selected from the group consisting of sulfonium cations and iodonium cations.
8. The photoresist composition of claim 7 wherein at least one of G 1 -G 5 is an electron withdrawing moiety selected from the group consisting of CN, NO, NO 2 , Cl, Br, I, SO 2 Me, and CHO.
9. The photoresist composition of claim 8 wherein at least one of G 1 -G 5 is selected from the group consisting of CN and NO 2 .
10. The photoresist composition of claim 8 wherein at least two of G 1 -G 5 are electron withdrawing moieties.
11. The photoresist composition of claim 7 wherein said onium cationic component comprises an aromatic moiety.
12. The photoresist composition of claim 11 wherein said onium cationic component has a structure selected from the group consisting of
wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of H;
linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl;
unsubstituted and substituted aromatic groups; and unsubstituted and substituted heteroaromatic groups.
13. The photoresist composition of claim 7 wherein said imaging polymer comprises a lactone moiety.
14. The photoresist composition of claim 7 wherein said imaging polymer has a weight concentration ranging from about 5% to about 20% of the total weight of said photoresist composition.
15. The photoresist composition of claim 7 wherein said fluorine-free photoacid generator has a weight concentration ranging from about 0.5% to about 15% based on the total weight of said imaging polymer.
16. A method of forming a patterned material feature on a substrate, said method comprising:
(a) providing a material layer on a substrate;
(b) forming a photoresist layer over said material layer, said photoresist layer comprising:
(i) an acid sensitive imaging polymer; and
(ii) a fluorine-free photoacid generator comprising an onium cationic component and an anionic component of formula (II):
wherein:
X is O;
Y is C;
each of G 1 -G 5 is selected from the group consisting of H; linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl; unsubstituted and substituted aromatic groups; unsubstituted and substituted heteroaromatic groups; and an electron withdrawing moiety, provided that at least one of G 1 -G 5 is an electron withdrawing moiety;
(c) patternwise exposing said photoresist layer to radiation, thereby creating a pattern of radiation-exposed regions in said photoresist layer;
(d) selectively removing portions of said photoresist layer to expose portions of said material layer; and
(e) etching or ion implanting said exposed portions of said material layer, thereby forming said patterned material feature.
17. The method of claim 16 wherein said radiation is provided by an ArF laser.
18. The method of claim 16 wherein at least one of the G 1 -G moieties is an electron withdrawing moiety selected from the group consisting of CN, NO, NO 2 , Cl, Br, I, SO 2 Me, and CHO.
19. The method of claim 18 wherein at least one of G 1 -G 5 is selected from the group consisting of CN and NO 2 .
20. The method of claim 18 wherein at least two of G 1 -G 5 are electron withdrawing moieties.
21. The method of claim 16 wherein said onium cationic component is selected from the group consisting of sulfonium cations and iodonium cations.
22. The method of claim 21 wherein said onium cationic component comprises an aromatic moiety.
23. The method of claim 22 wherein said onium cationic component has a structure selected from the group consisting of
wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from the group consisting of H;
linear, branched, tertiary, or cyclic alkyl; linear, branched, tertiary or cyclic alkoxyl;
unsubstituted and substituted aromatic groups; and unsubstituted and substituted heteroaromatic groups.
24. The method of claim 16 wherein said imaging polymer comprises a lactone moiety.
25. The method of claim 16 wherein said imaging polymer has a weight concentration ranging from about 5% to about 20% of the total weight of said photoresist composition.
26. The method of claim 16 wherein said fluorine-free photoacid generator has a weight concentration ranging from about 0.5% to about 10% based on the total weight of said imaging polymer.