Photoresist composition and method of forming photoresist pattern
A method of forming a photoresist pattern includes forming a protective layer over a photoresist layer formed on a substrate, and selectively exposing the protective layer and the photoresist layer to actinic radiation. The protective layer and the photoresist layer are developed to form a pattern in the photoresist layer, and the protective layer is removed. The protective layer includes a polymer having pendant fluorocarbon groups and pendant acid leaving groups.
1. A photoresist composition, comprising:
a photoresist material; and
a polymer having pendant fluorocarbon groups and pendant acid leaving groups,
wherein the polymer having the pendant fluorocarbon groups and the pendant acid leaving groups comprises from 0.1 wt. % to 10 wt. % of one or more polar functional groups selected from the group consisting of —NH 3 and —NH 2 based on a total weight of the polymer having the pendant fluorocarbon and the pendant acid leaving groups, and
the pendant fluorocarbon groups are attached to a polymer main chain via a linking unit including at least one selected from the group consisting of —P—; —P(O 2 )—; —C(═O)S—; —SO 2 S—; and —SO—.
2. The photoresist composition of claim 1 , wherein the photoresist material comprises metal oxide nanoparticles.
3. The photoresist composition of claim 1 , wherein the polymer having the pendant fluorocarbon and the pendant acid leaving groups comprises from 30 wt. % to 70 wt. % of the pendant fluorocarbon groups and from 30 wt. % to 70 wt. % of the pendant acid leaving groups based on the total weight of the polymer having the pendant fluorocarbon and the pendant acid leaving groups.
4. The photoresist composition of claim 1 , wherein the pendant fluorocarbon groups are selected from the group consisting of C x F y , where 1≤x≤9 and 3≤y≤12.
5. The photoresist composition of claim 1 , wherein the pendant acid leaving groups are selected from the group consisting of
6. The photoresist composition of claim 1 , further comprising a photoacid generator.
7. A photoresist composition, comprising:
a protective polymer having pendant fluorocarbon groups and pendant acid leaving groups;
a polymer resin having pendant acid leaving groups;
a photoactive compound; and
a photo decomposable base,
wherein the protective polymer having the pendant fluorocarbon groups and the pendant acid leaving groups comprises from 0.1 wt. % to 10 wt. % of one or more polar functional groups selected from the group consisting of —NH 3 , —NH 2 , and —SO 3 based on a total weight of the polymer having the pendant fluorocarbon and the pendant acid leaving groups, and
the pendant fluorocarbon groups are attached to a polymer main chain via a linking unit including at least one selected from the group consisting of —P—; —P(O 2 )—; —C(═O)S—; —SO 2 S—; and —SO—.
8. The photoresist composition of claim 7 , wherein the protective polymer having the pendant fluorocarbon and the pendant acid leaving groups comprises from 30 wt. % to 70 wt. % of the pendant fluorocarbon groups and from 30 wt. % to 70 wt. % of the pendant acid leaving groups based on the total weight of the polymer having the pendant fluorocarbon and the pendant acid leaving groups.
9. The photoresist composition of claim 7 , wherein the pendant fluorocarbon groups are selected from the group consisting of C x F y , where 1≤x≤9 and 3≤y≤12.
10. The photoresist composition of claim 7 , wherein the pendant acid leaving groups are selected from the group consisting of
11. A photoresist composition, comprising:
a first polymer having pendant fluorocarbon groups and first pendant acid labile groups, wherein the pendant fluorocarbon groups are attached to a polymer main chain via a linking unit including at least one selected from the group consisting of —P—; —P(O 2 )—; —C(═O)S—; —SO 2 S—; and —SO—;
a second polymer having second pendant acid labile groups;
metal oxide nanoparticles complexed with a sulfonic acid ligand;
a photoacid generator; and
a solvent.
12. The photoresist composition of claim 11 , wherein the pendant fluorocarbon groups are selected from the group consisting of C x F y , where 1≤x≤9 and 3≤y≤12; and —(C(CF 3 ) 2 OH)—.
13. The photoresist composition of claim 11 , wherein the first pendant acid labile groups are selected from the group consisting of
14. The photoresist composition of claim 11 , wherein the second polymer includes a repeating unit that forms a skeletal backbone of the second polymer, and the repeating unit is one or more of an acrylic ester, a methacrylic ester, a crotonic ester, a vinyl ester, a maleic diester, a fumaric diester, an itaconic diester, a (meth)acrylonitrile, a (meth)acrylamide, a styrene, and a vinyl ether.
15. The photoresist composition of claim 11 , wherein the polymer having the pendant fluorocarbon groups and the first pendant acid labile groups comprises from 30 wt. % to 70 wt. % of the pendant fluorocarbon groups and from 30 wt. % to 70 wt. % of the first pendant acid labile groups based on a total weight of the polymer having the pendant fluorocarbon groups and the first pendant acid labile groups.
16. The photoresist composition of claim 1 , further comprising a photo decomposable base.
17. The photoresist composition of claim 11 , wherein an amount of the metal oxide nanoparticles in the photoresist composition ranges from 0.1 wt. % to 20 wt. % based on a total weight of the photoresist composition.
18. The photoresist composition of claim 7 , wherein the photo decomposable base has a structure according to the following formula:
wherein R is an alicyclic group of 5 or more carbon atoms which may have a substituent, X is a divalent linking group, Y is a linear, branched, or cyclic alkylene group or an arylene group; Rf is a hydrocarbon group containing a fluorine atom, and M ⊕ is an organic cation or a metal cation.
19. The photoresist composition of claim 11 , further comprising a photo decomposable base.
20. The photoresist composition of claim 19 , wherein the photo decomposable base has a structure according to the following formula:
wherein R is an alicyclic group of 5 or more carbon atoms which may have a substituent, X is a divalent linking group, Y is a linear, branched, or cyclic alkylene group or an arylene group; Rf is a hydrocarbon group containing a fluorine atom, and M ⊕ is an organic cation or a metal cation.