Photoresist composition for deep UV and process thereof
View Patent ↗The present invention relates to a novel photoresist composition sensitive to radiation in the deep ultraviolet and a process for imaging the composition. The photoresist composition comprises a) a novel polymer that is insoluble in an aqueous alkaline solution and comprises at least one acid labile group, and b) a compound capable of producing an acid upon irradiation. The novel polymer of the present invention comprises at least one unit with a bisester group, (—C(O)OWC(O)O—), attached on one side to a polymer backbone unit (A) comprising an aliphatic group, and attached on the other side to an adamantyl group. The invention also relates to the novel polymer and a novel monomer for obtaining the novel polymer.
1. A photoresist composition comprising a photoacid generator and a polymer comprising at least one unit derived from a cyclo olefin monomer and, at least one unit as described by structure 1,
where, A has the structure
where R 1 ′, R 1 ″ and R 1 ′″ are independently hydrogen, (C 1 –C 6 ) alkyl or cyano, and Y is X, C(O)OX, OX, where X is an aliphatic (C 1 –C 6 ) alkylene group, and m is 0 or 1,
W is a (C 1 –C 8 ) linear or branched alkylene group,
R is independently selected from substituted hydrocarbyl group, unsubstituted hydrocarbyl group, hydrogen, hydroxyl, and (C 1 –C 10 )alkyl,
R′ is hydrogen or (C 1 –C 6 ) alkyl, and n=1–9.
2. The composition according to claim 1 , where the polymer further comprises at least one comonomeric unit.
3. The composition according to claim 2 , where the comonomeric unit is derived from monomers selected from cyclic anhydrides, (meth)acrylate esters, and vinyl acetals.
4. The process of imaging a positive photoresist composition comprising the steps of:
a) coating a substrate with a film of photoresist composition of claim 1 ;
b) baking the substrate to substantially remove the solvent;
c) imagewise irradiating the photoresist film;
d) baking the photoresist film; and,
e) developing the irradiated photoresist film using an alkali developer.
5. The process according to claim 4 , further comprising coating an antireflective film on the substrate prior to coating the photoresist.
6. The process according to claim 5 , further where the antireflective coating is sensitive at 193nm.
7. The process of claim 4 , wherein the photoresist film is imagewise irradiated with light of wavelength in the range of 100nm to 300nm.
8. The process of claim 4 , wherein the heating in step d) ranges from a temperature of from about 90° C. to about 50° C. for from about 30 seconds to about 180 seconds on a hot plate.
9. The process of claim 4 , wherein the alkali developer comprises an aqueous solution of tetramethyl ammonium hydroxide.
10. A polymer comprising at least one unit derived from a cyclo olefin monomer and, at least one unit as described by structure 1,
where, A has the structure
where R 1 ′, R 1 ″and R 1 ′″ are independently hydrogen, (C 1 –C 6 ) alkyl or cyano, and Y is X, C(O)OX, OX, where X is an aliphatic (C 1 –C 10 ) alkylene group, and m is 0 or 1,
W is a (C 1 –C 8 ) linear or branched alkylene group,
R is independently selected from substituted hydrocarbyl group, unsubstituted hydrocarbyl group, hydrogen, hydroxyl, and (C 1 –C 10 )alkyl,
R′ is hydrogen or (C 1 –C 6 ) alkyl, and n=1–9.
11. The composition of claim 1 where W is selected from methylene, methyl methylene, dimethyl methylene, isopropylene and propylene.
12. The composition of claim 1 where W is CH 2 .
13. The composition of claim 10 , where W is selected from methylene, methyl methylene, dimethyl methylene, isopropylene and propylene.
14. The composition of claim 10 where W is CH 2 .
15. The composition of claim 1 , where the unit of structure 1 is derived from a monomer of the structure:
16. The composition of claim 1 , where the unit of structure 1 is derived from a monomer of the structure:
17. The composition of claim 1 , where the cyclo olefin is a norbornene derivative.
18. The composition of claim 1 , where the cyclo olefin monomer is selected from t-butyl norbornene carboxylate (BNC), hydroxyethyl norbornene carboxylate (HNC), norbornene carboxylic acid(NC), t-butyl tetracyclo[4.4.0.1. 2,6 1. 7,10 ]dodec-8-ene-3-carboxylate, and t-butoxycarbonylmethyl tetracyclo[4.4.0.1. 2,6 1. 7,10 ]dodec-8-ene-3-carboxylate.
19. The composition of claim 10 , where the cyclo olefin is a norbornene derivative.
20. The composition of claim 10 , where the cyclo olefin monomer is selected from t-butyl norbornene carboxylate (BNC), hydroxyethyl norbornene carboxylate (HNC), norbornene carboxylic acid(NC), t-butyl tetracyclo[4.4.0.1. 2,6 1. 7,10 ]dodec-8-ene-3-carboxylate, and t-butoxycarbonylmethyl tetracyclo[4.4.0.1. 2,6 1. 7,10 ] dodec-8-ene-3-carboxylate.