Polymeric compositions and uses therefor
The present invention relates to polycyclic polymers, methods for producing polycyclic polymers, and methods for their use as photoresists in the manufacture of integrated circuits. In one embodiment, the present invention relates to photoresist compositions formed from the polymerization of at least one halogenated polycyclic monomer or hydrohalogenated polycyclic monomer. In another embodiment, the present invention relates to photoresist compositions formed from the co-polymerization of at least one halogenated polycyclic monomer or hydrohalogenated polycyclic monomer with at least one non-halogenated polycyclic monomer. Additionally, the present invention relates to methods by which to post-treat such photoresist compositions in order to obtain one or more of: (1) a reduction in optical density of the polymer composition; and (2) a reduction in the amount of residual metal and/or monomer in the polymer composition. Also disclosed are catalyst systems for use in producing the photoresist compositions of the present invention which permit molecular weight control of the photoresist products.
1. A method for reducing the optical density of a polymer comprising polycyclic repeating units, at least one of such polycyclic repeating units containing an unsaturated terminal group, the method comprising:
providing a solution of such polymer;
incorporating a post-fuctionalization agent selected from hydrogen, a peracid, a hydrosilation agent, and a hydroformylation agent into such solution; and
causing such post-fuctionlization agent to react with the unsaturated terminal group of the dissolved polymer.
2. The method according to claim 1 wherein said peracid is a mixture of glacial acetic acid and hydrogen peroxide.
3. A method for reducing the optical density, residual metal content and residual monomer content of an addition polymer comprising polycyclic repeating units containing pendant acid labile groups and terminal unsaturated end groups comprising:
a) reacting a mixture comprising said polymer and a solvent with peracid at elevated temperature for a period of time sufficient to epoxidize said unsaturated end groups; and
b) separating said epoxidized polymer from said solvent.
4. The method of claim 3 wherein said peracid is a 1:1 mixture of glacial acetic acid and hydrogen peroxide.
5. The method of claim 3 wherein said mixture further comprises a fibrous ion exchange resin.
6. The method of claim 5 wherein said polymer comprises repeating units selected from one or more of the repeating units represented by the formula;
wherein R 1 to R 4 independently represent hydrogen linear or branched (C 1 to C 30 ) alkyl, linear and branched (C 1 to C 24 ) halohydrocarbyl, linear or branched (C 2 to C 30 ) olefin; —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —C(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(R) 2 —CH(R)(C(O)OR**), —(CH 2 ) n —(CR 2 ) n —CH(R)(C(O)OR**), —(CH 2 ) n —C(OR***)—(CF 3 ) 2 , —(CR′ 2 ) n —O—R— and —(CH 2 ) n —C(R) 2 —CH(C(O)OR**) 2 ; where R represents hydrogen, linear and branched (C 1 to C 10 ) alkyl; R′ represents hydrogen or a halogen; R* represents an acid labile moiety; R** independently represents R or R*; R*** represents —CH 2 OR, —C(O)OR or —C(O)R; n is an integer from 0 to 10; m is an integer from 0 to 5; and Z represents —(CH 2 ) p —, oxygen, sulfur, or —NH— and p is equal to 1 or 2; and
wherein R 5 to R 8 independently represent hydrogen, linear or branched (C 1 to C 30 ) alkyl, linear or branched (C 2 to C 30 ) olefin; —(CH 2 ) n —C(O)OR* , —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —C(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(R) 2 —CH(R)(C(O)OR**), —(CH 2 ) n —(CR 2 ) n —CH(R)(C(O)OR**), —(CR′ 2 ) n —O—R— and —(CH 2 ) n —C(R) 2 —CH(C(O)OR**) 2 ; where R represents hydrogen, linear and branched (C 1 to C 10 ) alkyl, —(CH 2 ) s — where s is an integer from 1 to 10; Z including p, R′, R″, R**, n and m are as defined above, with the proviso, that one of R 1 to R 8 must represent arm acid labile moiety.
7. The polymer of claim 6 wherein Z is methylene.
8. The polymer of claim 7 wherein at least one of R 1 to R 8 is selected from the group represented by the formula —(CH 2 ) n —C(O)OR*.
9. The polymer of claim 8 wherein at least one of R 1 to R 4 is a halohydrocarbyl group represented by the formula C r X″ 2r+1 wherein X″ is independently selected from fluorine, chlorine, bromine and iodine, and r is an integer from 1 to 20.
10. The polymer of claim 8 wherein said repeating unit is represented by the formula:
wherein n is an integer from 0 to 10 and R*** is as previously defined.
11. The method according to claim 1 where said incorporating comprises incorporating hydrogen and a hydrogenation catalyst.
12. The method according to claim 11 where said hydrogenation catalyst is selected from H 2 PtCl 4 , RuHCl(Ph 3 ) 3 , RhCl(Ph 3 ) 3 or [Ir(1,5-cyclooctadiene)(P(cyclohexyl) 3 )(pyridine)]PF 6 .
13. The method according to claim 1 where said incorporating comprises incorporating a silane post-functionalization agent and a hydrosilation catalyst.
14. The method according to claim 13 where said hydrosilation catalyst is selected from H 2 PtCl 4 , RuHCl(Ph 3 ) 3, RhCl(Ph 3 ) 3 or [Ir(1,5-cyclooctadiene)(P(cyclohexyl) 3 )(pyridine)]PF 6 and said silane post-functionalization agent comprises a (C 1 -C 10 ) trialkyl silane or pentamethyldisiloxane.
15. The method of claim 1 where said polymer comprises a vinyl addition polymer.
16. The method of claim 1 where said polycyclic repeating units are represented by at least one of the following formulae:
whore R 1 to R 4 independently represent hydrogen, linear or branched (C 1 to C 3 ) alkyl, linear and branched (C 1 to C 24 ) halohydrocarbyl, linear or branched (C 2 to Ca 30 ) olefin; —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —C(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(R) 2 —CH(R)(C(O)OR**), —(CH 2 ) n —(CR 2 ) n —CH(R)(C(O)OR**), —(CH 2 ) n —C(OR***)—(CF 3 ) 2 , —(CR′ 2 ) n —O—R— and —(CH 2 ) n C(R) 2 —CH(C(O)OR**) 2 ; where R represents hydrogen, linear and branched (C 1 to C 10 ) alkyl; R′ represents hydrogen or a halogen; R* represents an acid labile moiety; R** independently represents R or R*; R*** represents —CH 2 OR, —C(O)OR or —C(O)R; n is an integer from 0 to 10; m is an integer from 0 to 5; and Z represents —(CH 2 ) p —, oxygen, sulfur, or —NH— and p is equal to 1 or 2; and
where R 5 to R 8 independently represent hydrogen, linear or branched (C 1 to C 30 ) alkyl, linear or branched (C 2 to C 30 ) olefin; —(CH 2 ) n —C(O)OR*, —(CH 2 ) n —C(O)OR, —(CH 2 ) n —OR, —(CH 2 ) n —OC(O)R, —(CH 2 ) n —C(O)R, —(CH 2 ) n —OC(O)OR, —(CH 2 ) n —C(R) 2 —CH(R)(C(O)OR**), —(CH 2 ) n —(CR 2 ) n —CH(R)(C(O)OR**), —(CR′ 2 ) n —O—R— and —(CH 2 ) n —C(R) 2 CH(C(O)OR**) 2 ; where R represents hydrogen, linear and branched (C 1 to C 10 ) alkyl, —(CH 2 ) s — where s an integer from 1 to 10; Z including p, R′, R*, R**, n and m are as defined above, with the proviso that one of R 1 to R 8 must represent an acid labile moiety.
17. The polymer of claim 16 where Z is methylene.
18. The polymer of claim 17 where at least one of R 1 to R 8 is selected from the group represented by the formula —CH 2 ) n —C(O)OR*.
19. The polymer of claim 18 where at least one of R 1 to R 4 is a halohydrocarbyl group represented by the formula C r X″ 2r+1 wherein X″ is independently selected from fluorine, chlorine, bromine and iodine, end r is an integer from 1 to 20.
20. The polymer of claim 18 where said repeating unit is represented by the formula: