Photoresist compositions and methods of forming photolithographic patterns
View Patent ↗Provided are photoresist compositions useful in forming photolithographic patterns by a negative tone development process. Also provided are methods of forming photolithographic patterns by a negative tone development process and substrates coated with the photoresist compositions. The photoresist compositions include one or more polymer additive that contains a basic moiety and which is substantially non-miscible with a resin component of the resist. The compositions, methods and coated substrates find particular applicability in the manufacture of semiconductor devices.
1. A photoresist composition, comprising:
a first polymer comprising an acid labile group;
a second polymer comprising:
a first unit formed from a first monomer having the following general formula (I):
wherein: P is a polymerizable functional group; R 1 is chosen from substituted and unsubstituted C1 to C20 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from substituted and unsubstituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S— and —COO—; and n is an integer from 0 to 5; and
a second unit formed from a second monomer having a basic moiety, wherein the first monomer and the second monomer are different, and wherein the second monomer comprises a polymerizable group chosen from (alkyl)acrylate, vinyl, allyl and maleimide, and the basic moiety is chosen from amides;
wherein the second polymer is free of fluorine and acid-labile groups and wherein the second polymer has a surface energy lower than a surface energy of the first polymer;
a photoacid generator; and
a solvent.
2. The photoresist composition of claim 1 , wherein the first unit is formed from a monomer having the following general formula (I-1):
wherein: R 2 is chosen from hydrogen and C1 to C3 alkyl; R 4 is chosen from C1 to C15 alkyl; and X is oxygen or sulfur.
3. The photoresist composition of claim 2 , wherein R 4 is chosen from C3 to C8 alkyl.
4. The photoresist composition of claim 1 , wherein the second monomer is chosen from one or more of the following monomers:
5. A coated substrate, comprising a substrate and a layer of a photoresist composition of claim 1 over a surface of the substrate.
6. A method of forming a photolithographic pattern by negative tone development, comprising:
(a) providing a substrate comprising one or more layer to be patterned over a surface of the substrate;
(b) applying a layer of a photoresist composition of claim 1 over the one or more layer to be patterned;
(c) patternwise exposing the photoresist composition layer to actinic radiation;
(d) heating the exposed photoresist composition layer in a post-exposure bake process; and
(e) applying a developer comprising an organic solvent to the photoresist composition layer, wherein unexposed portions of the photoresist layer are removed by the developer, leaving a photoresist pattern over the one or more layer to be patterned.
7. The method of claim 6 , wherein the patternwise exposing is conducted by immersion lithography.
8. A photoresist composition, comprising:
a first polymer comprising an acid labile group;
a second polymer comprising:
a first unit formed from a first monomer having the following general formula (I):
wherein: P is a polymerizable functional group; R 1 is chosen from substituted and unsubstituted C1 to C20 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from substituted and unsubstituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S— and —COO—; and n is an integer from 0 to 5; and
a second unit formed from a monomer chosen from one or more of the following monomers:
wherein the first monomer and the second monomer are different;
wherein the second polymer is free of fluorine and acid-labile groups and wherein the second polymer has a surface energy lower than a surface energy of the first polymer;
a photoacid generator; and
a solvent.
9. A method of forming a photolithographic pattern by negative tone development, comprising:
(a) providing a substrate comprising one or more layer to be patterned over a surface of the substrate;
(b) applying a layer of a photoresist composition of claim 8 over the one or more layer to be patterned;
(c) patternwise exposing the photoresist composition layer to actinic radiation;
(d) heating the exposed photoresist composition layer in a post-exposure bake process; and
(e) applying a developer comprising an organic solvent to the photoresist composition layer, wherein unexposed portions of the photoresist layer are removed by the developer, leaving a photoresist pattern over the one or more layer to be patterned.
10. The method of claim 9 , wherein the patternwise exposing is conducted by immersion lithography.
11. A photoresist composition, comprising:
a first polymer comprising an acid labile group;
a second polymer comprising:
a first unit formed from a first monomer having the following general formula (I):
wherein: P is a polymerizable functional group; R 1 is chosen from substituted and unsubstituted C1 to C20 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from substituted and unsubstituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S— and —COO—; and n is an integer from 0 to 5; and
a second unit formed from a second monomer having a basic moiety, wherein the first monomer and the second monomer are different, and wherein the second monomer comprises a polymerizable group chosen from (alkyl)acrylate, vinyl, allyl and maleimide, and the basic moiety is chosen from amides;
wherein the second polymer is insoluble in alkaline developer, is free of acid-labile groups, and has a surface energy lower than a surface energy of the first polymer;
a photoacid generator; and
a solvent.
12. The photoresist composition of claim 11 , wherein the first unit is formed from a monomer having the following general formula (I-1):
wherein: R 2 is chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; R 4 is chosen from fluorinated and non-fluorinated C1 to C15 alkyl; and X is oxygen or sulfur.
13. The photoresist composition of claim 12 , wherein R 4 is chosen from fluorinated and non-fluorinated C3 to C8 alkyl.
14. The photoresist composition of claim 11 , wherein the second monomer is chosen from one or more of the following monomers:
15. The photoresist composition of claim 14 , wherein the basic moiety-containing unit is formed from a monomer chosen from one or more of the following monomers:
16. The photoresist composition of claim 11 , wherein the first monomer of general formula (I) is chosen from one or more of the following monomers:
wherein R 2 is chosen from hydrogen, fluorine and fluorinated and non-fluorinated C1 to C3 alkyl; and X is oxygen or sulfur.
17. A method of forming a photolithographic pattern by negative tone development, comprising:
(a) providing a substrate comprising one or more layer to be patterned over a surface of the substrate;
(b) applying a layer of a photoresist composition of claim 11 over the one or more layer to be patterned;
(c) patternwise exposing the photoresist composition layer to actinic radiation;
(d) heating the exposed photoresist composition layer in a post-exposure bake process; and
(e) applying a developer comprising an organic solvent to the photoresist composition layer, wherein unexposed portions of the photoresist layer are removed by the developer, leaving a photoresist pattern over the one or more layer to be patterned.
18. The method of claim 17 , wherein the patternwise exposing is conducted by immersion lithography.