Photoresist topcoat compositions and methods of processing photoresist compositions
Photoresist topcoat compositions comprise: a matrix polymer and a surface active polymer, wherein the surface active polymer comprises polymerized units of the following general formula (I): wherein: R 1 represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 haloalkyl group; R 2 independently represents a hydrogen atom or an optionally substituted alkyl group, wherein at least one R 2 is not a hydrogen atom, wherein the R 2 groups taken together optionally form a cyclic structure, and wherein the total number of carbon atoms for the R 2 groups taken together is from 2 to 20; R 3 represents an optionally substituted C1-C4 alkylene group, wherein an R 2 group optionally forms a cyclic structure with R 3 ; and R 4 independently represents C1-C4 fluoroalkyl groups; wherein the total polymerized units of general formula (I) are present in the surface active polymer in an amount of 95 wt % or more based on total polymerized units of the surface active polymer; and wherein the surface active polymer is present in the composition in an amount of from 0.1 to 30 wt % based on total solids of the composition; and an organic-based solvent system comprising a plurality of organic solvents. The invention finds particular applicability in the manufacture of semiconductor devices.
1. A photoresist topcoat composition, comprising:
a matrix polymer;
a surface active polymer, wherein the surface active polymer comprises polymerized units of the following general formula (I):
wherein: R 1 represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 haloalkyl group; R 2 independently represents a hydrogen atom or an optionally substituted alkyl group, wherein at least one R 2 is not a hydrogen atom, wherein the R 2 groups taken together optionally form a cyclic structure, and wherein the total number of carbon atoms for the R 2 groups taken together is from 2 to 20; R 3 represents an optionally substituted C1-C4 alkylene group, and an R 2 group optionally forms a cyclic structure with R 3 ; and R 4 independently represents C1-C4 fluoroalkyl groups;
wherein the total polymerized units of general formula (I) are present in the surface active polymer in an amount of 95 wt % or more based on total polymerized units of the surface active polymer; and wherein the surface active polymer is present in the composition in an amount of from 0.1 to 30 wt % based on total solids of the composition;
an acid generator compound; and
an organic-based solvent system comprising a plurality of organic solvents.
2. The photoresist topcoat composition of claim 1 , wherein total polymerized units of general formula (I) are present in the surface active polymer in an amount of 100 wt % based on total polymerized units of the surface active polymer.
3. The photoresist topcoat composition of claim 1 , wherein the surface active polymer is a homopolymer.
4. The photoresist topcoat composition of claim 1 , wherein at least one R 2 is an optionally substituted branched C3-C12 alkyl group.
5. The photoresist topcoat composition of claim 1 , wherein the R 2 groups taken together form a cyclic structure.
6. The photoresist topcoat composition of claim 1 , wherein R 4 is a trifluoromethyl group.
7. The photoresist topcoat composition of claim 1 , further comprising an additive polymer that is different from the matrix polymer and the surface active polymer.
8. A coated substrate, comprising:
a photoresist layer on a substrate; and
a topcoat layer formed from a photoresist topcoat composition of claim 1 on the photoresist layer.
9. A method of processing a photoresist composition, comprising:
(a) applying a photoresist composition over a substrate to form a photoresist layer;
(b) applying over the photoresist layer a photoresist topcoat composition to form a topcoat layer, wherein the photoresist topcoat composition, comprises:
a matrix polymer;
a surface active polymer, wherein the surface active polymer comprises:
polymerized units of the following general formula (I):
wherein: R 1 represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 haloalkyl group; R 2 independently represents a hydrogen atom or an optionally substituted alkyl group, wherein at least one R 2 is not a hydrogen atom, wherein the R 2 groups taken together optionally form a cyclic structure, and wherein the total number of carbon atoms for the R 2 groups taken together is from 2 to 20; R 3 represents an optionally substituted C1-C4 alkylene group, and an R 2 group optionally forms a cyclic structure with R 3 ; and R 4 independently represents C1-C4 fluoroalkyl groups;
wherein the total polymerized units of general formula (I) are present in the surface active polymer in an amount of 95 wt % or more based on total polymerized units of the surface active polymer; and wherein the surface active polymer is present in the composition in an amount of from 0.1 to 30 wt % based on total solids of the composition; and
an organic-based solvent system comprising a plurality of organic solvents;
(c) exposing the topcoat layer and the photoresist layer to activating radiation; and
(d) contacting the exposed topcoat layer and photoresist layer with an aqueous base developer to form a resist pattern.
10. The method of claim 9 , wherein the topcoat layer is formed by spin-coating, and the surface active polymer migrates to an upper surface of the topcoat layer during the spin-coating, wherein an upper surface of the topcoat layer consists essentially of the surface active polymer.
11. The method of claim 9 , wherein total polymerized units of general formula (I) are present in the surface active polymer in an amount of 100 wt % based on total polymerized units of the surface active polymer.
12. The method of claim 9 , wherein the surface active polymer is a homopolymer.
13. The method of claim 9 , wherein at least one R 2 is an optionally substituted branched C3-C12 alkyl group.
14. The method of claim 9 , wherein the R 2 groups taken together form a cyclic structure.
15. The method of claim 9 , wherein R 4 is a trifluoromethyl group.
16. The method of claim 9 , further comprising an additive polymer that is different from the matrix polymer and the surface active polymer.