Norbornene-type monomers and polymers containing pendent lactone or sultone groups
View Patent ↗The disclosed invention relates to novel norbornene-type monomers containing pendent lactone or sultone groups. The invention also relates to norbornene-type polymers and copolymers comprising one or more repeating units represented by the formula: and containing pendent lactone or sultone groups. These polymers and copolymers are useful in making photoimagable materials. The photoimagable materials are particularly suitable for use in photoresist compositions useful in 193 and 157 nm photolithography.
1. A polymer comprising a repeating unit represented by the formula:
wherein in Formula (I-a):
X is O, S, —CH 2 — or —CH 2 CH 2 —;
n is an integer from 0 to 5 inclusive;
each R1 to R4 independently represents hydrogen, a linear or branched (C 1 to C 20 ) alkyl, or a linear or branched (C 1 to C 20 ) haloalkyl, subject to the proviso that at least one of R1 to R4 is a group represented by the formula:
wherein: G is —SO 2 — or —C(O)—; T is —Si(R 20 ) 3 ; t is 0 or 1;
j is 1 or 2; q is 0 or 1; and A is a spacer moiety represented by —(CH 2 ) m —,
—(CH 2 ) m O—, —(CH 2 ) m O(CH 2 ) m —, O(CH 2 ) m —,
—(CH 2 ) m NR 9 (CH 2 ) m —, —(C(R 10 ) 2 ) m (C(R 10 ) 2 ) m O(C(R 11 ) 2 ) a —,
wherein: each R 9 independently is (C 1 to C 5 ) alkyl; each R 10 independently is hydrogen, halogen, (C 1 to C 5 ) alkyl, or (C 1 to C 5 ) haloalkyl; R 11 independently is hydrogen or halogen; each R 12 independently is hydrogen, (C 1 to C 10 ) alkyl or (C 1 to C 5 ) haloalkyl; each R 20 independently is a (C 1 to C 4 ) alkyl; each a independently is 2 to 6; and each m independently is 0 to 4.
2. The polymer of claim 1 wherein G is —C(O)—, T is —Si(CH 3 ) 3 , t is 1, n is 0, q is 0 and j is 1.
3. The polymer of claim 2 wherein X is —CH 2 —, and R1, R2 and R3 are each hydrogen.
4. The polymer of claim 1 wherein G is —SO 2 —, T is —Si(CH 3 ) 3 , n is 0, q is 0 and j is 2.
5. The polymer of claim 4 wherein X is —CH 2 —, and R1, R2 and R3 are each hydrogen.
6. The polymer of claim 1 further comprising a repeating unit represented by the following formula (II-a):
wherein in Formula (II-a):
X′ is O, S, —CH 2 — or —CH 2 CH 2 —;
n′ is an integer from 0 to 5 inclusive; and
each R5 to R8 independently is selected from: hydrogen; linear or branched (C 1 to C 20 ) alkyl; linear or branched (C 1 to C 20 ) haloalkyl; substituted or unsubstituted (C 4 –C 12 ) cycloalkyl; substituted or unsubstituted (C 1 to C 10 ) hydroxyalkyl;
—(CH 2 ) b C(CF 3 ) 2 OR 13 ; —(CH 2 ) b C(O)R 14 ; —(CH 2 ) b OR 14 ; —(CH 2 ) b OC(O)R 14 ; —(CH 2 ) b C(O)R 14 ;
—(CH 2 ) b OC(O)OR 14 ; —(CH 2 ) b C(O)OR 15 ; —(CH 2 ) b Si(R 16 ) 3 ;
—(CH 2 ) b Si(OR 16 ) 3 ; —(CH 2 ) b NR 17 SO 2 R 18 ; or —(CH 2 ) b SO 2 NR 17 R 18 ;
wherein: b is 0 to 4; each R 13 independently is selected from hydrogen, linear or branched (C 1 –C 10 ) alkyl, or linear or branched (C 1 –C 10 ) haloalkyl; each R 14 is selected from hydrogen, linear or branched (C 1 to C 10 ) alkyl, or substituted or unsubstituted (C 4 –C 8 ) cycloalkyl; R 15 is an acid labile group; each R 16 independently is selected from hydrogen and (C 1 to C 5 ) alkyl; each R 17 independently is selected from hydrogen, linear or branched (C 1 –C 5 ) haloalkyl, linear or branched tri(C 1 —C 10 ) alkylsilyl, —C(O)CF 3 , —C(O)OR 19 , or —OC(O)OR 19 ; each R 18 independently is selected from hydrogen, linear or branched (C 1 –C 10 ) alkyl, linear or branched (C 1 –C 5 ) haloalkyl, —OR 3 , —C(O)R 3 , substituted or unsubstituted (C 3 –C 8 ) cycloalkyl, substituted or unsubstituted cyclic esters containing 2 to 8 carbon atoms, substituted or unsubstituted cyclic ketones containing 4 to 8 carbon atoms, substituted or unsubstituted cyclic ethers or cyclic diethers containing 4 to 8 carbon atoms; each R 19 independently is selected from linear or branched (C 1 –C 10 ) alkyl, or linear or branched (C 1 –C 10 ) haloalkyl; R5 and R6 and/or R7 and R8 independently taken together can form a (C 1 –C 5 ) alkylidenyl group or a spiral anhydride group; R6 and R7 taken together with the two ring carbon atoms to which they are attached can form a cyclic (C 3 to C 6 ) anhydride group, a cyclic (C 3 to C 6 ) sulfonamide group, or a cyclic (C 3 to C 6 ) sultone group.
7. The polymer of claim 6 wherein X′ is —CH 2 —, n′ is 0, each of R5, R6 and R7 is H, and R8 is —(CH 2 ) b C(O)OR 14 , wherein b is 0 and R 14 is t-butyl.
8. The polymer of claim 7 wherein X is —CH 2 —, n is 0, each of R1, R2 and R3 is H, q is 0, j is 2, T is H, t is 1, and G is —SO 2 —.
9. The polymer of claim 6 wherein X′ is —CH 2 —, n is 0, each of R5, R6 and R7 is H, and R8 is —(CH 2 ) b C(O)OR 14 , wherein b is 0 and R 14 is 1-methyl cyclopentyl.
10. The polymer of claim 9 wherein X is —CH 2 —, n is 0, each of R1, R2 and R3 is H, q is 0, j is 1, T is —Si(R 20 ) 3 wherein each R 20 is methyl, t is 1, and G is —C(O)—.
11. The polymer of claim 10 wherein the polymer further comprises another repeating unit, the another repeating unit being represented by Formula (II) wherein X′ is —CH 2 —, n′ is 0, each of R5, R6 and R7 is H, and R8 is —(CH 2 ) b C(CF 3 ) 2 OR 13 wherein b is 1 and R 13 is hydrogen.
12. A photoresist composition comprising the polymer of claim 1 .
13. A photoresist composition comprising the polymer of claim 6 .
14. A process for generating an image on a substrate, comprising:
(a) coating the substrate with a photoresist composition comprising the polymer of claim 1 ;
(b) image wise exposing the film to radiation; and
(c) developing the image.
15. The process of claim 14 wherein the radiation has a wavelength of about 157 nm.
16. The process of claim 14 wherein the radiation has a wavelength of about 193 nm.
17. A process for generating an image on a substrate, comprising:
(a) coating the substrate with a photoresist composition comprising the polymer of claim 6 ;
(b) image wise exposing the film to radiation; and
(c) developing the image.
18. The process of claim 17 wherein the radiation has a wavelength of about 157 nm.
19. The process of claim 17 wherein the radiation has a wavelength of about 193 nm.
20. A compound represented by the formula:
wherein in Formula (I):
X is O, S, —CH 2 — or —CH 2 CH 2 —;
n is an integer from 0 to 5 inclusive;
each R1 to R4 independently represents hydrogen, a linear or branched (C 1 to C 20 ) alkyl, or a linear or branched (C 1 to C 20 ) haloalkyl, subject to the proviso that at least one of R1 to R4 is a group represented by the formula:
wherein: G is —C(O)— or —SO 2 —; T is H or —Si(R 20 ) 3 wherein R 20 is H or (C 1 to C 4 ) alkyl; t is 0 or 1; j is 1 or 2; q is 0 or 1; and A is a spacer moiety represented by —(CH 2 ) m —, —(CH 2 ) m O—, —(CH 2 ) m O(CH 2 ) m —, O(CH 2 ) m —, —(CH 2 ) m NR 9 (CH 2 ) m —, —(C(R 10 ) 2 ) m (C(R 10 ) 2 ) m O(C(R 11 ) 2 ) a —,
wherein: each R 9 independently is (C 1 to C 5 ) alkyl; each R 10 independently is hydrogen, halogen, (C 1 to C 5 ) alkyl, or (C 1 to C 5 ) haloalkyl; each R 11 independently is hydrogen or halogen; each R 12 independently is hydrogen, (C 1 to C 10 ) alkyl or (C 1 to C 5 ) haloalkyl; each a independently is 2 to 6; and each m independently is 0 to 4.
21. The compound of claim 20 wherein G is —C(O)—, T is —Si (CH 3 ) 3 , t is 1, n is 0, q is 0 and j is 1.
22. The compound of claim 21 wherein X is —CH 2 —, and R1, R2 and R3 are each hydrogen.
23. The compound of claim 20 wherein G is —SO 2 —, T is —Si(CH 3 ) 3 , t is 1, n is 0, q is 0, and j is 2.
24. The compound of claim 23 wherein X is —CH 2 —, and R1, R2 and R3 are each hydrogen.
25. A compound represented by the formula:
wherein G is —C(O)— or SO 2 —, T is H or —Si(CH 3 ) 3 t is 1, and j is 1 or 2.
26. A polymer comprising a repeating unit represented by the formula
wherein: G is —SO 2 —or —C(O)—; T is —Si(R 20 ) 3 , each R 20 independently is (C 1 to C 4 ) alkyl; t is 1; and j is 1 or 2.