Photoresist overcoat compositions
View Patent ↗Photoresist overcoat compositions are provided. The compositions comprise: a matrix polymer, an additive polymer a basic quencher and an organic solvent. The additive polymer has a lower surface energy than a surface energy of the matrix polymer, and the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition. The compositions have particular applicability in the semiconductor manufacturing industry for use in negative tone development processes.
1. A photoresist overcoat composition, comprising:
a matrix polymer comprising a unit formed from a monomer of the following general formula (I):
wherein: R 1 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 2 is chosen from optionally substituted C1 to C15 alkyl; X 1 is oxygen, sulfur or is represented by the formula NR 3 , wherein R 3 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 1 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 4 — wherein R 4 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and
an additive polymer comprising a unit formed from a monomer of the following general formula (II):
wherein: R 10 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 11 is chosen from optionally substituted C1 to C15 alkyl; X 2 is oxygen, sulfur or is represented by the formula NR 12 , wherein R 12 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 3 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —NHSO 2 —, —COO— and —CONR 13 — wherein R 13 is chosen from hydrogen and optionally substituted C1 to C10 alkyl;
a basic quencher; and
an organic solvent;
wherein the additive polymer has a lower surface energy than a surface energy of the matrix polymer, and wherein the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition; and
wherein the composition is free of photoacid generator compounds.
2. The photoresist overcoat composition of claim 1 , wherein the additive polymer comprises a unit containing a fluorine atom.
3. The photoresist overcoat composition of claim 2 , wherein the additive polymer comprises a unit containing a fluoroalcohol.
4. The photoresist overcoat composition of claim 1 , wherein the matrix polymer is free of fluorine and silicon.
5. The photoresist overcoat composition of claim 1 , wherein the basic quencher comprises a basic moiety on the matrix polymer.
6. The photoresist overcoat composition of claim 1 , wherein the basic quencher is an additive separate from the additive polymer and the matrix polymer.
7. The photoresist overcoat composition of claim 1 , wherein the additive polymer is present in the overcoat composition in an amount of from 3 to 15 wt % based on total solids of the overcoat composition.
8. The photoresist overcoat composition of claim 1 , wherein the matrix polymer is present in the overcoat composition in an amount of from 70 to 99 wt % based on total solids of the overcoat composition.
9. A photoresist overcoat composition, comprising:
a matrix polymer comprising a unit formed from a monomer of the following general formula (I):
wherein: R 1 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 2 is chosen from optionally substituted C1 to C15 alkyl; X 1 is oxygen, sulfur or is represented by the formula NR 3 wherein R 3 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 1 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 4 — wherein R 4 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and
an additive polymer comprising a unit formed from a monomer of the following general formula (III):
wherein: R 14 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 15 is independently chosen from optionally substituted C1 to C15 alkyl; X 3 is oxygen, sulfur or is represented by the formula NR 16 , wherein R 16 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; Z 4 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 17 —, wherein R 17 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and n is an integer from 0 to 2;
a basic quencher; and
an organic solvent;
wherein the additive polymer has a lower surface energy than a surface energy of the matrix polymer, and wherein the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition.
10. The photoresist overcoat composition of claim 9 , wherein the additive polymer comprises a unit containing a fluorine atom.
11. The photoresist overcoat composition of claim 9 , wherein the additive polymer comprises a unit containing a fluoroalcohol.
12. The photoresist overcoat composition of claim 9 , wherein the matrix polymer is free of fluorine and silicon.
13. The photoresist overcoat composition of claim 9 , wherein the basic quencher comprises a basic moiety on the matrix polymer.
14. The photoresist overcoat composition of claim 9 , wherein the basic quencher is an additive separate from the additive polymer and the matrix polymer.
15. The photoresist overcoat composition of claim 9 , wherein the additive polymer is present in the overcoat composition in an amount of from 3 to 15 wt % based on total solids of the overcoat composition.
16. The photoresist overcoat composition of claim 9 , wherein the matrix polymer is present in the overcoat composition in an amount of from 70 to 99 wt % based on total solids of the overcoat composition.
17. The photoresist overcoat composition of claim 9 , wherein the composition is free of photoacid generator compounds.
18. A photoresist overcoat composition, comprising:
a matrix polymer comprising a unit formed from a monomer of the following general formula (I):
wherein: R 1 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 2 is chosen from optionally substituted C1 to C15 alkyl; X 1 is oxygen, sulfur or is represented by the formula NR 3 , wherein R 3 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 1 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 4 — wherein R 4 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and
an additive polymer comprising a unit formed from a monomer of the following general formula (II): or (III):
wherein: R 10 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 11 is chosen from optionally substituted C1 to C15 alkyl; X 2 is oxygen, sulfur or is represented by the formula NR 12 , wherein R 12 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 3 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —NHSO 2 —, —COO— and —CONR 13 — wherein R 13 is chosen from hydrogen and optionally substituted C1 to C10 alkyl;
wherein: R 14 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 15 is independently chosen from optionally substituted C1 to C15 alkyl; X 3 is oxygen, sulfur or is represented by the formula NR 16 , wherein R 16 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; Z 4 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 17 —, wherein R 17 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and n is an integer from 0 to 2;
a basic quencher; and
an organic solvent;
wherein the additive polymer has a lower surface energy than a surface energy of the matrix polymer, and wherein the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition; and
wherein the additive polymer comprises a unit containing a fluorine atom.
19. The photoresist overcoat composition of claim 18 , wherein the additive polymer comprises a unit containing a fluoroalcohol.